JP2001205736A - Resin coated metal panel and resin coated metal container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin coated metal panel excellent in impact resistance, chemical resistance, moldability, heat resistance, gas barrier properties and the adhesion with a metal and having good flavor properties and excellent corrosion resistance and a resin coated metal container comprising the resin coated metal panel. SOLUTION: The resin coated metal panel for a container is constituted by forming a two-layered film comprising metal chromium and chromium oxide hydrate on at least the surface of a base metal panel becoming inner surface side of the container so that metal chromium is on the side of the metal panel and laminating a resin composition layer containing a polyester resin (A), a vinyl polymer (B) containing 1 mass % or more of a unit having a polar group and a radical inhibitor thereon.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a resin composition having good impact resistance, chemical resistance, moldability, heat resistance, gas barrier property and adhesion to metal, high decomposition resistance of resin, and reduction of organic matter from resin. The present invention relates to a resin-coated metal plate excellent in corrosion resistance, which is coated on one or both surfaces of a metal plate using a resin composition having a small amount of eluted material and having particularly excellent flavor properties, and further includes a resin coating formed by molding the resin-coated metal plate. Related to metal containers.

[0002]

2. Description of the Related Art Polyester resins have excellent mechanical properties, electrical properties, heat resistance, gas barrier properties and adhesion to metals, and are used for resin moldings such as structural materials and housings.
Also, it is used as a material for coating a metal plate for the purpose of preventing corrosion. However, properties such as impact resistance, adhesion between resin and metal, and gas barrier properties strongly depend on the crystallinity of polyester resin, so the target properties can be obtained unless the crystal structure of resin is strictly controlled. Absent. Specifically, the crystallization rate is reduced in order to improve the adhesiveness in the area where the resin comes into contact with the metal, and in other areas, the crystallization is increased to ensure impact resistance and gas barrier properties. In order to simultaneously satisfy the adhesiveness, the impact resistance, and the gas barrier property, it is necessary to appropriately tilt the crystallinity of the resin. As a result, manufacturing conditions such as temperature control have been severely restricted.

When a resin is used as a material for coating a metal plate, adhesion, impact resistance and gas barrier properties between the resin and the metal are important. No. 269074 discloses a method of laminating a resin composition comprising a crystalline polyester resin and an amorphous polyester resin. In this method, the crystallization rate at the interface can be easily reduced during the laminating step, so that the adhesion is improved. There is a restriction on the process, such as the use of a method for positively leaving crystallization.

However, JP-A-7-195617 and JP-A-7-195617
As disclosed in Japanese Patent No. 290644, by using a composition with a polyester resin and an ionomer resin, mechanical properties, electrical properties, heat resistance, gas barrier properties and adhesion to metals are improved, and As disclosed in WO99 / 27026, a rubber elastic resin is further added to a resin composition of the polyester resin and a vinyl polymer having a polar group such as an ionomer, and a rubber elastic resin is added to the polyester resin. Was finely dispersed, and a technique of encapsulating the elastic resin with a vinyl polymer having a polar group was developed, further improving the various properties was achieved, and the above-mentioned various problems could be almost solved. .

[0005]

However, from the resin compositions of these polyester resins and vinyl polymers having a polar group such as ionomers, organic low molecular substances are generated, and the impact resistance and the like are reduced. There was. In particular, when a container using the resin is used for beverages and foods, the odor may be generated in the content and the flavor of the content may be reduced.

[0006] In general, the causes of the generation of organic low molecular weight substances from resin include raw materials remaining in the resin, low molecular components having a low degree of polymerization, and the contents of containers of decomposition products generated during resin production or can manufacturing. Elution to the substance is considered. Various methods have been disclosed to resolve these elutions. For example, a method using a raw material having a low content of a low molecular component (Japanese Unexamined Patent Application Publication No.
-6436) and a method of removing low molecular components using water or an organic solvent after resin production (JP-A-9-316216). The former is effective when the eluate is a low-molecular component contained in the raw material, but is ineffective when the eluate is a low-molecular component resulting from decomposition of a resin generated during raw material production or molding. . The latter is not economical because it requires extraction and drying steps.

As a method for suppressing the elution of the organic low-molecular components due to the decomposition of the resin, it is generally effective to carry out each step such as resin production and molding at a temperature lower than the decomposition temperature of the resin. Even if the temperature of each step such as kneading and molding of the resin composition is set to be equal to or lower than the decomposition temperature of each resin of the polyester resin, the vinyl polymer having a polar group such as an ionomer, and the rubber elastic resin, the organic low The generation of molecular substances did not go away. Therefore, it is considered that the generation of the organic low molecular substance in each step such as kneading and molding of the resin composition is not caused by simple thermal decomposition of the component resin.

When oxygen promotes the decomposition of the resin, it may be effective to manufacture and mold the resin in an inert gas atmosphere, but an apparatus for introducing an inert gas is required. It is difficult to say that this is a simple method, and when the decomposition of the resin is caused by something other than oxygen, the method using an inert gas atmosphere has no effect. The object of the present invention is to provide good impact resistance, chemical resistance, moldability, heat resistance, gas barrier properties and good adhesion to metals, little decomposition of the resin and less leaching of organic substances from the resin, and particularly excellent flavor properties. An object of the present invention is to provide a resin-coated metal plate for a container, which is coated with a resin film using an excellent resin composition and has improved corrosion resistance, and further provides a resin-coated metal container formed by molding the resin-coated metal plate.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and have found the following phenomena. (1) An organic low molecular weight substance may be generated from a resin composition comprising a polyester resin (A) and a vinyl polymer (B). (2) Polyester resin (A) or vinyl polymer (B)
Even if each of them is melt-kneaded alone, no organic low-molecular substances are generated and no odor is generated. (3) When the resin composition is used for a container or a resin-coated metal container, an organic low-molecular-weight substance is eluted from the container into the contents, which may cause odor. (4) According to (1) and (2), the generation of organic low molecular weight substances is due to the interaction between the polyester resin (A) and the vinyl polymer (B). (5) As a result of closely examining the eluate, the main component was vinyl polymer.
(B) is an organic substance decomposed by a radical reaction. (6) In the polyester resin (A), metal compounds such as germanium, antimony, and titanium, which are residues of the polyester production catalyst, remain in the range of 1 ppm to 500 ppm, which cause the decomposition of the vinyl polymer (B). .

That is, a vinyl polymer having a polar group (B)
Is usually thermally stable and decomposition is not a problem.However, by mixing and heating with a PET resin containing a metal compound involved in electron transfer as described above, the polar group of the vinyl polymer is Radicals are generated in the vicinity of, and the resin is decomposed by cutting the main chain of the vinyl polymer, and organic substances that cause odor are generated. Further, in order to prevent the radical decomposition of such a vinyl polymer (B), a certain amount of a radical inhibitor, that is, a compound having a radical scavenging ability and a compound having an ability to decompose a radical precursor are added in appropriate amounts. The metal compound remaining in the polyester resin (A) without impairing the excellent physical properties such as impact resistance and adhesion to metal of the resin composition comprising the polyester resin (A) and vinyl polymer (B) The present inventors have found that it is possible to suppress radical decomposition of the vinyl polymer (B), and have reached the present invention.

That is, the present invention relates to a polyester resin (A)
In a resin-coated metal plate for a container using a resin composition containing a vinyl polymer (B) containing at least 1% by weight of a unit having a polar group and a radical inhibitor, the base metal and the resin composition layer A gist of the present invention is a resin-coated metal container formed by forming a specific plating layer therebetween, and formed by molding a resin-coated metal plate for the container.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The resin-coated metal plate for a container and the resin-coated metal container of the present invention will be described below. First, the resin composition used in the present invention is a polyester resin (A),
It contains a vinyl polymer (B) containing 1% by mass or more of a unit having a polar group, and a radical inhibitor. Although the composition of these resins is not particularly limited, a vinyl polymer (B) is preferably used with respect to 100 parts by mass of the polyester resin (A).
The resin composition comprises 1 to 50 parts by mass, and preferably contains 0.001 to 7, more preferably 0.005 to 1 part by mass of a radical inhibitor per 100 parts by mass of the resin composition.
If the amount of the vinyl polymer (B) is less than 1 part by mass, the impact resistance may decrease, and if it exceeds 50 parts by mass, the heat resistance may decrease.

The polyester resin (A) used in the present invention has an intrinsic viscosity of 0.3 to 2.0 dl / g, preferably 0.40 to 1.7 dl / g.
, More preferably 0.50 to 1.5 dl / g. Intrinsic viscosity
If less than 0.3dl / g, polar monomer-containing vinyl polymer
Since it does not mix uniformly with (B), the mechanical strength and the impact resistance are liable to be lowered, while when the intrinsic viscosity exceeds 2.0 dl / g, the moldability is liable to be poor, and neither is preferable.

The intrinsic viscosity is measured at a concentration of 0.5% in o-chlorophenol at 25 ° C., and is determined by the following equation (i). In the formula, C represents the concentration represented by the number of grams of resin per 100 ml of the solution, t ₀ represents the flow time of the solvent, and t represents the flow time of the solution. Intrinsic viscosity = {ln (t / t ₀ )} / C (i) The polyester resin (A) used in the present invention refers to only a hydroxycarboxylic acid compound residue, a dicarboxylic acid residue and a diol compound residue. Or a thermoplastic polyester having a hydroxycarboxylic acid compound residue, a dicarboxylic acid residue and a diol compound residue as constituent units. Further, a mixture thereof may be used.

Examples of the hydroxycarboxylic acid compound as a raw material of the hydroxycarboxylic acid compound residue include p-hydroxybenzoic acid, p-hydroxyethylbenzoic acid, 2- (4-
Hydroxyphenyl) -2- (4′-carboxyphenyl) propane, and the like.
Two or more types may be mixed and used. Further, when a dicarboxylic acid compound forming a dicarboxylic acid residue is exemplified,
Terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid and adipic acid, pimelic acid, sebacic acid, azelaic acid, decanedicarboxylic acid , Malonic acid, succinic acid, malic acid, aliphatic dicarboxylic acids such as citric acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc., and these may be used alone or as a mixture of two or more. You may use it.

Next, an example of a diol compound forming 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, bis (4-hydroxyphenyl) 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-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-methyl- 4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 1,1,1,3,3 , 3-Hexafluoro-2,2-bis (4-hydroxyphenyl) propane,
Aromatic diols such as 4'-biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone and ethylene glycol, trimethylene glycol, propylene glycol, tetra Aliphatic diols such as methylene glycol, 1,4-butanediol, pentamethylene glycol, neopentyl glycol, hexamethylene glycol, dodecamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, hydrogenated bisphenol A, and cyclohexane Examples thereof include alicyclic diols such as dimethanol and the like, and these can be used alone or as a mixture of two or more. Further, the polyester resins obtained therefrom may be used alone or in combination of two or more.

The polyester resin (A) used in the present invention
May be composed of these compounds or a combination thereof. Preferred from a viewpoint. Further, the polyester resin (A) used in the present invention, trimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, a small amount of structural units derived from a polyfunctional compound such as pentaerythritol, for example, It may contain up to 2 mol%.

From the viewpoint of heat resistance and processability, the most preferred 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. Preferred polyester resins (A) used in the present invention include, for example, polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene-2,6-naphthalate and the like. Among them, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene-2,6-naphthalate having moderate mechanical properties, gas barrier properties, and metal adhesion are most preferable.

The polyester resin (A) used in the present invention
Is the glass transition temperature (Tg, sample amount about 10 mg, heating rate
10 ° C / min with a differential thermal analyzer (DSC))
To 120 ° C, preferably 60 to 100 ° C. The polyester resin (A) may be amorphous or crystalline, and when crystalline, the crystal melting temperature (Tm) is usually from 210 to 265 ° C, preferably from 210 to 245 ° C.
° C, and the low temperature crystallization temperature (Tc) is usually 110-220 ° C,
Preferably it is 120-215 ° C. Tm 21
If the temperature is lower than 0 ° C. or the temperature Tc is lower than 110 ° C., the heat resistance may be insufficient and the film shape may not be maintained during drawing. In addition, Tm is over 265 ° C or Tc is 220 ° C
In the case of exceeding, the resin may not sufficiently enter the unevenness of the surface of the metal plate, resulting in poor adhesion.

Next, the vinyl polymer (B) containing 1% by mass or more of the unit having a polar group used in the present invention is
A vinyl polymer containing 1% by mass or more of a unit having a group to which an element having a Pauling electronegativity difference of 0.39 (eV) 0.5 or more is bonded. If the amount of the unit having a polar group is less than 1% by mass, the impact resistance may be reduced. Specific examples of the group in which the element having a difference in the electronegativity of Pauling of 0.39 (eV) 0.5 or more is -CO-, -C = O, -COO-
, Epoxy group, C ₂ O ₃ , C ₂ O ₂ N-, -CN, -NH ₂ , -NH-, -X
(X; F, Cl, Br), —SO ₃ −, and the like. Further, it may have an acid radical ion neutralized with a metal ion as a polar group. In this case, examples of metal ions are Na ⁺ , K
⁺ , Li ⁺ , Zn2 ⁺ , Mg2 ⁺ , Ca2 ⁺ , Co2 ⁺ , Ni2 ⁺ , Pb2 ⁺ , Cu
^Monovalent , divalent or trivalent such as ²⁺ , Mn ²⁺ , Ti ³⁺ , Zr ³⁺ , Sc ³⁺
Valent metal cations.

As an example of a unit having a polar group, -C
Vinyl alcohol as an example having a -O- group, vinyl chloromethyl ketone as an example having a -C = O group, acrylic acid, methacrylic acid, vinyl acetate as an example having a -COO- group,
Examples of vinyl acids such as vinyl propionate and metal salts or ester derivatives thereof, and examples having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaacrylate.
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 Acrylamine as an example having a group,
Acrylamide Examples having an -NH- group, a vinyl chloride as an example having an -X group, -SO ₃ - styrene sulfonic acid, and the like are mentioned as examples having the group, also all or a portion of these acidic functional groups Examples include the compounds neutralized with the above-mentioned metal ions, and these may be contained alone or in plural in the vinyl polymer (B). The unit having a polar group contained in the vinyl polymer (B) may be a unit having a group to which an element having a Pauling electronegativity difference of 0.39 (eV) 0.5 or more is bonded. It is not limited.

The vinyl polymer (B) used in the present invention is exemplified by the above-mentioned polar group-containing unit alone or in combination of two or more polymers, and the above-mentioned polar group-containing unit and the following general formula (ii). Copolymers with a non-polar vinyl monomer are exemplified. -CHR ¹ = CR ² R ^3- (ii) (wherein, R ¹ and R ³ each independently represent an alkyl group having 1 to 12 carbon atoms or hydrogen, R ² represents an alkyl group having 1 to 12 carbon atoms, phenyl A non-polar vinyl monomer of the general formula (ii).
Ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,
Α-olefins such as 1-dodecene, aliphatic vinyl monomers such as isobutene and isobutylene, styrene monomers, o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene and t-butylstyrene Alkylated styrene, α-
An aromatic vinyl monomer such as an addition polymer unit of a styrene-based monomer such as methylstyrene is exemplified.

Examples of the homopolymer of the polar group-containing unit include polyvinyl alcohol, polymethyl methacrylate, and polyvinyl acetate. Examples of a copolymer of a polar group-containing unit and a nonpolar vinyl monomer include ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, and copolymers thereof. Ionomer resin in which some or all of the acidic functional groups are neutralized with metal ions, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid Ethyl copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-maleic anhydride copolymer, butene-ethylene-glycidyl methacrylate copolymer, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Maleic anhydride copolymers and the like, and ionomer resins in which all or a part of their acidic functional groups are neutralized with metal ions are exemplified.

As the ionomer resin, known ionomer resins can be widely used. In particular,
It is a copolymer of a vinyl monomer and an α, β-unsaturated carboxylic acid, wherein some or all of the carboxylic acid in the copolymer is neutralized with a metal cation. Examples of the vinyl monomer include the above-mentioned α-olefins and styrene-based monomers.Examples of the α, β-unsaturated carboxylic acid include α, β-unsaturated carboxylic acids having 3 to 8 carbon atoms. Acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic acid monomethyl ester, maleic anhydride,
Monoethyl maleate and the like can be mentioned.

As an example of the metal cation to be neutralized, N
a ⁺ , K ⁺ , Li ⁺ , Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Co ²⁺ , Ni ²⁺ , Pb
^Monovalent , divalent or trivalent metal cations such as ²⁺ , Cu ²⁺ , Mn ²⁺ , Ti ³⁺ , Zr ³⁺ , Sc ^{3+ and the} like. In addition, some of the remaining acidic functional groups that have not been neutralized with the metal cation may be esterified with a lower alcohol. Specific examples of ionomer resins include ethylene and acrylic acid,
A copolymer with an unsaturated monocarboxylic acid such as methacrylic acid,
Alternatively, a copolymer of ethylene and an unsaturated dicarboxylic acid such as maleic acid or itaconic acid, wherein part or all of the carboxyl groups in the copolymer is a metal such as sodium, potassium, lithium, zinc, magnesium, or calcium. Resins neutralized with ions are exemplified. Among them, the most preferable for the purpose of improving the compatibility between the polyester resin (A) and the rubber-like elastic resin body (C) is a copolymer of ethylene and acrylic acid or methacrylic acid (a structure having a carboxyl group). The resin has a unit of 2 to 15 mol%) and 30 to 70% of the carboxyl groups in the polymer are neutralized with a metal cation such as Na or Zn.

From the viewpoint of ensuring the barrier properties, a copolymer of an α-olefin and a unit having a polar group is a preferred combination. The vinyl polymer used in the present invention
(B) may be a vinyl polymer containing 1% by mass or more of a unit having a polar group, and is not limited to the above specific examples. Although the molecular weight of the vinyl polymer (B) is not particularly limited, the number average molecular weight is 2,000 to 50.
It is preferably 0000 or less. If it is less than 2000 or more than 500,000, the impact resistance may decrease.

The glass transition temperature (Tg, sample amount: about 10 mg, measured by a differential thermal analyzer (DSC) at a heating rate of 10 ° C./min.) Is 50 ° C. or less because of its high impact resistance. A vinyl polymer (B) having a Young's modulus at room temperature of 1000 MPa or less and an elongation at break of 50% or more is preferred. Illustrative of the preferred vinyl polymer (B) used in the present invention, methacrylic acid,
Acrylic acid and polar olefins in which some or all of these acidic functional groups have been neutralized with metal ions, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, maleic anhydride , Vinyl acetate and α-
Olefin copolymers are exemplified.

In particular, ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-vinyl acetate copolymers, and acidic functional groups in these copolymers are more preferred because of their high impact resistance improving ability. Ionomer resin, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer in which some or all of , Ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl acrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-vinyl acetate-
Glycidyl acrylate copolymer, ethylene-carbon monoxide-glycidyl methacrylate copolymer, ethylene-carbon monoxide-glycidyl acrylate copolymer, ethylene-maleic anhydride copolymer, butene-ethylene-glycidyl methacrylate copolymer, butene -Ethylene-glycidyl acrylate copolymer.

In the present invention, a polyester resin (A) and a polar vinyl polymer (B) are used as the resin composition.
In addition, in order to improve the impact resistance, a resin of the third component which does not hinder the function of the radical inhibitor may be added. As the resin of the third component, for example, a rubber-like elastic resin
(C). Rubber-like elastic resin used in the present invention
For (C), known rubber-like elastic resins can be widely used. Among them, the glass transition temperature (Tg, sample amount about 10 mg, temperature rise rate of 10 ° C / min.
Rubbery resin having a Young's modulus at room temperature of not more than 1000 ° C. and a breaking elongation of not less than 50% is preferred. If the Tg of the rubber elasticity developing portion exceeds 50 ° C., the Young's modulus at room temperature exceeds 1000 MPa, and the breaking elongation is less than 50%, sufficient impact resistance cannot be exhibited. In order to ensure impact resistance at low temperatures, Tg is preferably 10 ° C. or less, more preferably -30 ° C. or less. Also, in order to ensure more reliable impact resistance, the Young's modulus at room temperature should be 100 MPa or less, more preferably 10 MPa or less, and the elongation at break should be 100% or more, more preferably 300% or more. Is preferred.

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

Among them, polyolefin resins are preferable because of their low water vapor permeability. Polyolefin resins represented by the following formula ^{(iii) -R 4 CH-CR} 5 R 6 - in (iii) (wherein, R ⁴ and R ⁶ each independently represents an alkyl group or hydrogen having 1 to 12 carbon atoms, R ⁵ 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 types, or a copolymer of resin units formed of these units. Examples of the repeating unit include when propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene In addition to aliphatic olefins and styrene monomers such as repeating units that appear and repeating units when isobutene is added, o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene, and t-butylstyrene Alkylated styrenes, halogenated styrenes such as monochlorostyrene, α-
Aromatic olefins such as an addition polymer unit of a styrene monomer such as methylstyrene are exemplified.

Examples of polyolefin resins include α-olefin homopolymers such as polyethylene, polypropylene, polybutene, polypentene, polyhexene, and polyoctenylene. Further, as the copolymer of the above unit, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer Examples thereof include aliphatic polyolefins such as a coalesced unit and aromatic polyolefins such as a styrene-based polymer, but are not limited thereto, and may be any units that satisfy the above-mentioned repeating units. These resins may be used alone or in combination of two or more.

The polyolefin resin only needs to contain the above-mentioned olefin unit as a main component, and a vinyl monomer, a polar vinyl monomer,
A diene monomer may be copolymerized in a monomer unit or a resin unit. The copolymer composition is at most 50 mol%, preferably at most 30 mol%, based on the above units. If it exceeds 50 mol%, the properties as a polyolefin resin, such as dimensional stability, deteriorate.

Examples of polar vinyl monomers include acrylic acid derivatives such as acrylic acid, methyl acrylate and ethyl acrylate, methacrylic acid derivatives such as methacrylic acid, methyl methacrylate and ethyl methacrylate, acrylonitrile, maleic anhydride, and anhydride. Examples include maleic acid imide derivatives and vinyl chloride. Examples of the diene monomer include butadiene, isoprene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, cyclopentadiene, and 1,4-hexadiene.

The most preferred resins for imparting impact strength as polyolefin resins are ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1
-A copolymer of ethylene and an α-olefin having 3 or more carbon atoms, such as a pentene copolymer, an ethylene-3-ethylpentene copolymer, and an ethylene-1-octene copolymer, or the binary copolymer Composed of ethylene copolymerized with butadiene, isoprene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, cyclopentadiene, 1,4-hexadiene, etc., α-olefins having 3 or more carbon atoms and non-conjugated dienes3 It is an original copolymer. Among them, ethylene-propylene copolymer and ethylene-1-butene copolymer binary copolymer, or ethylene-propylene copolymer and ethylene-1-butene copolymer, for ease of handling, 5-methylidene-2- as a non-conjugated diene
Using norbornene, 5-ethylidene-2-norbornene, cyclopentadiene, and 1,4-hexadiene, the amount of α-olefin is 20 to 60 mol%, and the amount of non-conjugated diene is 0.5 to 10 mol%.
Copolymerized resins are most preferred.

The polyester resin (A) and the polar vinyl polymer (B) used in such a ternary system include a rubber-like elastic resin (C) as a third component in which the above-mentioned resins can be used. The resin composition containing is a polyester resin
(A) a vinyl polymer (B) containing at least 1% by weight of a unit having a polar group, a rubber-like elastic resin (C), and a radical inhibitor; Resin (C) is finely dispersed, and a resin composition having a structure in which at least a part of the rubber-like elastic resin (C) is encapsulated with a vinyl polymer (B), impact resistance, This is preferable because the adhesion to the metal plate is higher.

Here, the fine dispersion means a rubber-like elastic resin.
In this case, 70% by volume or more of all the particles in (C) are dispersed in the polyester resin (A) with an equivalent spherical equivalent diameter of 100 μm or less. The equivalent spherical equivalent diameter of the rubber-like elastic resin (C) is
If it exceeds 100 μm, the impact resistance decreases, and the film forming property of the resin composition of the present invention decreases. It is desirable that 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 (C) encapsulated with the vinyl polymer (B) means that at least 80%, preferably at least 95%, of the interface of the rubber-like elastic resin (C) is a vinyl polymer. (B)
Covered with polyester resin (A) and rubber-like elastic resin
The structure is such that the direct contact area with (C) is less than 20%. With such a structure, the fine dispersion of the rubber-like elastic resin body (C) encapsulated with the vinyl polymer (B) is facilitated, the impact resistance and the film-forming properties are improved, and the fine dispersion is achieved. Even when the particles come into contact with the metal plate, the vinyl polymer (B) has adhesion to the metal plate, so that the adhesion between the resin composition and the metal plate can be ensured.

It is not necessary that all particles of the rubber-like elastic resin (C) are encapsulated in the vinyl polymer (B), and at least 70% by volume or more of the rubber-like elastic resin (C) is a vinyl polymer. What is necessary is just to be encapsulated by union (B). If the unencapsulated rubber-like elastic resin body (C) is present in a volume ratio of more than 30%, fine dispersion becomes difficult, impact resistance decreases,
Further, when the resin composition is coated on a metal plate, the ratio of the rubber-like elastic resin body (C) directly in contact with the metal plate increases, and further, the adhesion between the resin composition and the metal plate cannot be secured. . Unencapsulated rubber-like elastic resin (C)
The equivalent spherical equivalent diameter is not particularly specified, but is preferably 1.0 μm or less from the viewpoint of impact resistance and workability.

Further, an excessive amount of the vinyl polymer (B) may be dispersed alone in the polyester resin (A) without encapsulating the rubber-like elastic resin body (C). The amount and diameter of the unencapsulated vinyl polymer (B) are not particularly limited, but may be 20% or less by volume of all vinyl polymers (B) and 1.0 μm or less in terms of equivalent sphere. desirable. If the volume ratio exceeds 20%, the basic properties such as heat resistance of the resin composition may change. On the other hand, if the equivalent spherical equivalent diameter exceeds 1.0 μm, workability may decrease.

Vinyl polymer in polyester resin (A)
To finely disperse the rubber-like elastic resin body (C) encapsulated in (B), the vinyl polymer (B) and the polyester resin (A)
It is important to properly balance the interfacial tension with the rubber-like elastic resin body (C). Preferably vinyl polymer
Spread Parameter for (B) Rubbery Elastic Resin (C)
It is desirable to control the content of the unit having a polar group so that (λ (Resin C) / (Resin B)) becomes positive. λ (R
By making esin C) / (Resin B) positive, thermodynamic stability can be ensured even if the rubber-like elastic resin body (C) is encapsulated with the vinyl polymer (B). Spread Param between different polymers
eter, SY Hobbs; Polym., Vol. 29, p1598 (1989)
Λ (Resin C) / (Resin B) = γ (Resin B) / (Resin A) -γ (Resin C) / (Resin B) -γ (Res in C) / (Resin A) (iv) [wherein, Resin A represents the polyester resin (A)
sin B indicates the rubbery elastic resin body (C), Resin C indicates the vinyl polymer (B), and Υi / j indicates the resin i
Is the interfacial tension between the resin i and the resin j.
It is proportional to the 0.5 power of a parameter Χi / j indicating the compatibility between j (the smaller the value, the better the compatibility). ].

Polyester resin (A) and rubber-like elastic resin body
(C) is low in compatibility, and Υ (Resin B) / (Resin A)> 0.
(omerV) and the polar group-containing unit (Monomer U) by adjusting the mixing ratio, and the following formulas (iii) and (iv) ΧA / C = φΧ (Resin A) / (Monomer V) + (1-φ) Χ (Resin A) / (Monomer U)-φ (1-φ) Χ (Monomer V) / (Monomer U) (v) ΧB / C = φΧ (Resin B) / (Monomer V) + (1-φ) Χ (Resin B) / (Monomer U)-φ (1-φ) Χ (Monomer V) / (Monomer U) (vi) [where, φ is the mixing ratio of nonpolar vinyl monomer (volume ratio)
Is shown. ] Shows the compatibility between the rubber-like elastic resin body (C) and the vinyl polymer (B) given by ΧB / C and shows the compatibility between the polyester resin (A) and the vinyl polymer (B) ΧA / C To 0
, It is possible to make λ (Resin C) / (Resin B) positive.

Accordingly, the preferred vinyl polymer (B)
Is determined according to the types of the polyester resin (A) and the rubber-like elastic resin body (C) in consideration of the compatibility with these resins. When a preferred combination is specifically exemplified, when the polyester resin (A) is an aromatic polyester resin composed of an aromatic dicarboxylic acid residue and a diol residue, and the rubbery elastic resin body (C) is a polyolefin resin, As the vinyl polymer (B), a copolymer of ethylene and a unit having a polar group, or SEBS in which maleic anhydride or glycidyl methacrylate is introduced at 1% by weight or more is preferable. By appropriately controlling the mixing ratio between ethylene and the unit having a polar group, λ (Resin C) / (Resin B)
Is easy to control positively. More preferably, a polyester resin (A) to a copolymer of ethylene and a unit having a polar group
When a functional group having a chemical action such as a covalent bond, a coordination bond, a hydrogen bond, an ionic bond, etc. is introduced, the interface between the polyester resin (A) and the vinyl polymer (B) is heated when encapsulated. This is desirable because it can be more mechanically stabilized.

More specifically, a copolymer of ethylene and a unit having a polar group can be described as an ethylene-vinyl acid copolymer, an ethylene-vinyl acid ester copolymer or an ionomer resin thereof, and ethylene and α, β. -Copolymers of glycidyl esters of unsaturated acids, terpolymers of ethylene and vinyl acids or vinyl esters and glycidyl esters of α, β-unsaturated acids, and the like. Among them, ionomer resins, copolymers of ethylene and glycidyl esters of α, β-unsaturated acids, and terpolymers of ethylene and vinyl acids or vinyl acid esters and glycidyl esters of α, β-unsaturated acids are mentioned. preferable. These resins show relatively strong chemical interactions with the polyester resin (A),
Forms a stable capsule structure with the rubber-like elastic resin body (C). Among them, the ionomer resin is the most preferable from the viewpoint of moldability because the intensity of the chemical action with the polyester resin (A) changes depending on the temperature.

As the ionomer resin, known ionomer resins can be widely used. In particular,
It is a copolymer of a vinyl monomer and an α, β-unsaturated carboxylic acid, wherein some or all of the carboxylic acid in the copolymer is neutralized with a metal cation. Examples of the vinyl monomer include the above-mentioned α-olefins and styrene-based monomers.Examples of the α, β-unsaturated carboxylic acid include α, β-unsaturated carboxylic acids having 3 to 8 carbon atoms. Acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic acid monomethyl ester, maleic anhydride,
Monoethyl maleate 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
^Monovalent , divalent or trivalent metal cations such as ²⁺ , Cu ²⁺ , Mn ²⁺ , Ti ³⁺ , Zr ³⁺ , Sc ^{3+ and the} like. In addition, some of the remaining carboxyl groups not neutralized by the metal cation may be esterified with a lower alcohol. Specific examples of the ionomer resin include a copolymer of ethylene and an unsaturated monocarboxylic acid such as acrylic acid and methacrylic acid, and a copolymer of ethylene and an unsaturated dicarboxylic acid such as maleic acid and itaconic acid. And a resin in which part or all of the carboxyl groups in the copolymer is neutralized with metal ions such as sodium, potassium, lithium, zinc, magnesium, and calcium. Among them, the most preferable for the purpose of improving the compatibility between the polyester resin (A) and the rubber-like elastic resin body (C) is a copolymer of ethylene and acrylic acid or methacrylic acid (a structure having a carboxyl group). The resin has a unit of 2 to 15 mol%) and 30 to 70% of the carboxyl groups in the polymer are neutralized with a metal cation such as Na or Zn.

The polyester resin (A) used in the present invention,
The resin composition containing the vinyl polymer (B) and the rubber-like elastic resin body (C) can be produced by a known mixing method. Specifically, polyester resin (A), vinyl polymer (B), and rubber-like elastic resin body having appropriate difference in interfacial tension
By melting and kneading (C) at a predetermined temperature, for example, 200 to 350 ° C. using a known various mixer, a capsule structure can be formed by utilizing a difference in interfacial tension.

As a method for finely dispersing the rubber-like elastic resin body (C) encapsulated with the vinyl polymer (B) in the polyester resin (A), the rubber-like elastic resin body is used for the vinyl polymer (B). There is also a method of adding a core-shell type rubber-like elastic material in which (C) is encapsulated to the polyester resin (A). This core-shell type rubbery elasticity is
It has a two-layer structure consisting of a core part and a shell part. The core part is in a soft rubber state, and the vinyl polymer (B) as the shell part on the surface has a polar unit as described above. Resin that is harder than the core. For example, the core portion is made of an acrylic rubber-like elastic material, a diene rubber-like elastic material, or a silicon-based rubber-like elastic material, and an acrylic polymer mainly composed of acrylate or methacrylate grafted on the core material constitutes a shell portion. Resin. The term “graft” means graft copolymerization of the resin of the core and the resin of the shell. This core-shell type rubber-like elastic body is preferable in terms of high impact resistance, dispersibility in polyester resin, and high adhesion to metal.

Specific examples of the rubber-like elastic body constituting the core portion include an acrylate-based polymer, a diene-based polymer, or dimethylsiloxane composed of a unit having the structure of general formula (vii). It is a rubber-like elastic body mainly used. CH ₂ = CR ¹ -CO-OR ² (vii) 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 carbon number. 1 to 12 alkyl groups, and R ² has 1 to 12 carbon atoms
Those having 12 acrylic groups are preferred. More specifically, examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and n-octyl methacrylate. 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 polymer forming the core may be a homopolymer thereof or a copolymer of two or more thereof.

The acrylate polymer constituting the core portion may be copolymerized with another vinyl monomer as long as the above acrylate is the main component. The main component is 50
% By weight or more. Specific examples of vinyl monomers include α-olefin monomers, styrene monomers, and polar vinyl monomers. More specifically,
α-olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-
Hexene, 1-octene, 1-decene, 1-dodecene, and the like.Examples of the styrene-based monomer include o-, m-, p-ethylstyrene, and alkylated styrenes such as t-butylstyrene, in addition to the styrene monomer. Halogenated styrene such as monochlorostyrene, α-methylstyrene and the like;
Examples of the polar vinyl monomer include acrylic acid, acrylonitrile, maleic anhydride and its imide derivative, vinyl acetate, vinyl chloride, and vinyl propionate.

Further, it is preferable that the acrylate polymer constituting the core part is partially cross-linked by a cross-linking agent in order to exhibit rubber elasticity. Illustrative examples of the crosslinking agent are vinyl monomers having ethylenic unsaturation, divinylbenzene, butylene diacrylate, ethylene dimethacrylate, butylene dimethacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate,
Triallyl isocyanate and the like can be mentioned. The amount of the crosslinking agent added is 30% by weight or less, preferably 20% by weight or less, more preferably 5% by weight or less. If it exceeds 30% by weight, it often hardens and cannot exhibit rubber elasticity.

The diene polymer constituting the core is a polymer of a diene monomer or a hydrogenated polymer thereof, and specifically, polybutadiene and a hydrogenated polymer thereof.
Copolymers of butadiene and styrene and hydrogenated polymers thereof are exemplified. The molecular weight of the polymer constituting the core portion is
Although not particularly limited, 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 portion is a crosslinked acrylate polymer, the molecular weight between crosslink points is preferably 2000 or more from the viewpoint of imparting sufficient rubber elasticity.

Glass transition temperature of polymer constituting core part
(Measured with a differential thermal analyzer (DSC) at a heating rate of 10 ° C / min)
Is preferably 30 ° C. or lower, more preferably 10 ° C.
° C or lower, more preferably -10 ° C or lower. If the glass transition temperature is higher than 30 ° C., rubber elasticity at room temperature or lower is difficult to exert. Next, the shell portion of the core-shell type rubber-like elastic body will be described. The shell portion is preferably composed of an acrylate polymer composed of a unit having a polar group. Fine dispersion is possible by utilizing the polarity of the acrylate polymer, and the core-shell type rubber-like elastic material is used. Can secure the adhesion when it comes into contact with the metal plate.

The acrylate polymer constituting the shell portion is a polymer comprising a unit represented by the general formula (vii). Specifically, it is a polymer of the monomers mentioned above, 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 weight
That is all. When copolymerized with another vinyl monomer, the composition ratio of the acrylate component is preferably 70% by weight or more. If it is less than 70% by weight, the polarity of the acrylate unit cannot be sufficiently utilized, and the fine dispersion and the adhesion to the metal plate may be insufficient.

In the core-shell type rubber-like elastic body, the core portion is made of a soft rubber-like substance, so that the resin constituting the shell portion is required to be hard for handling properties. For this purpose, the glass transition temperature of the acrylate polymer constituting the shell portion (heating rate 10 ° C./min, measured by a differential thermal analyzer (DSC)) is preferably 30 ° C. or more, more preferably Is 50 ° C. or higher.

The most preferred acrylate polymer unit constituting the shell portion is methyl methacrylate because the glass transition temperature is in the above range and the polymerization rate can be easily controlled. Further, the acrylate polymer constituting the shell portion includes a polyester resin.
To improve the compatibility with (A), polyester resin (A)
It is preferable that a functional group or a bonding group capable of reacting with a residual terminal functional group or an ester bond 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 grafting the shell part, a known vinyl monomer having these functional groups is added. By doing so, a functional group can be introduced. Examples of the bonding group include an ester bond, a carbonate bond, and an amide bond.When grafting the shell portion, TO Ahn et al .; J. Polym.Sci.
Linking groups can be introduced by using initiators having these linkages as disclosed in Part A Vol. 31, 435 (1993). Among these functional groups and bonding groups, the most preferable from the viewpoint of reactivity are an epoxy group and an aromatic group.
Glycidyl methacrylate, TO Ahn
The above-mentioned epoxy group and ester bond can be introduced by adding a polyarylate azo initiator disclosed in J. Polym. Sci. Part A Vol. 31, 435 (1993).

Specific examples of the core-shell type rubber-like elastic material include an MBA resin having a core portion of polybutyl acrylate, a shell portion of polymethyl methacrylate, a core portion of a butadiene-styrene copolymer, and a shell portion of a polystyrene. MBS resin composed of methyl methacrylate, a polymer composed of polydimethyl siloxane in the core part and polymethyl methacrylate in the shell part, and the like.
Acrylate-based core disclosed in 4096202
Polymerized acrylate shell polymers can be used in the present invention.

The amounts of the units containing these functional groups and binding groups are determined depending on the reactivity.
There is no particular limitation on the range in which 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 weight or less, more preferably 5% by weight or less. 15 weight
If it exceeds%, comb polymers are generated 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 weight or less. 15 weight
Above%, the unit having a binding group forms a domain,
In some cases, the compatibility with the polyester resin (A) cannot be improved.

The core-shell type rubbery elastic body desirably contains a rubbery polymer core portion in an amount of 20% by weight or more, preferably 50% by weight or more, more preferably 80% by weight or more. If it is less than 20% by weight, sufficient impact resistance may not be exhibited. The core-shell type rubber-like elastic body is obtained by grafting a vinyl polymer (B) and a rubber-like elastic resin body (C) to form a core-shell type rubber-like elastic body, and then forming a polyester resin (A). It can be manufactured by mixing. For example, polymerization can be carried out by a known radical polymerization method. Among them, an emulsion polymerization method as described in US Pat. No. 4,096,202 is preferable from the viewpoint of controlling the particle size of a polymer produced microscopically. Specific examples of the polymerization method include the following methods, but the core-shell type graft rubber-like elastic body may be any acrylate-based polymer in the shell portion, and the production method is not limited to the production method.

As the first stage polymerization, radical polymerization of the above-mentioned unit monomer constituting the core portion is carried out. At this time, about 0.1 to 5% by weight of a monomer having polyethylene unsaturation and having a plurality of double bonds is added as a grafting agent. The plurality of double bonds of the grafting agent preferably have different reaction rates, and specific examples include allyl methacrylate and diallyl maleate. After the polymerization of the core polymer, as a second stage polymerization, a core-shell type rubber-like elastic material can be obtained by adding a monomer and an initiator constituting the shell portion and graft-polymerizing the shell portion. .

The resin composition comprising the polyester resin (A) and the core-shell type rubber-like elastic material used in the present invention improves the compatibility between the polyester resin (A) and the core-shell type rubber-like elastic material. A known compatibilizer may be added for the purpose. The amount of the compatibilizer added is preferably 15% by weight or less, more preferably 5% by weight or less. 15% by weight
If the amount is too large, the compatibilizing agent may form a phase structure independently, and it is difficult to exert a sufficient compatibility improving effect. Specific examples of the compatibilizer include a reactive compatibilizer and a non-reactive compatibilizer. Examples of the reactive compatibilizer include polyester resins (A )) And a polymer having a functional group or a bond capable of reacting with a terminal residual functional group or a bond. More specifically, glycidyl methacrylate, a polymer obtained by random copolymerization of maleic anhydride and a polymer constituting the shell portion of the core portion of the rubber-type elastic body, or a polymer constituting the shell portion are formed by blocking an aromatic polyester, A graft copolymerized polymer is exemplified. In addition, as a non-reactive compatibilizer,
Examples of the core-shell type rubber-like elastic body include a block copolymer and a graft copolymer of a polymer constituting the shell portion of the rubber-like elastic material and the polyester resin (A).

For mixing the resin composition used in the present invention, known resin mixing methods such as a resin kneading method and a solvent mixing method can be widely used. As an example of the resin kneading method, after mixing by dry blending using a tumbler blender, Henschel mixer, V-type blender, etc., a single or twin screw extruder,
A method of melt-kneading with a kneader, a Banbury mixer or the like can be used. Examples of the melt mixing method include a method of dissolving each resin in a common solvent of the raw material resins contained in the resin composition, and then evaporating the solvents or adding a common poor solvent to recover a precipitated mixture. There is.

The resin composition used in the present invention contains a radical inhibitor. Preferably, 0.001 to 7 parts by mass of the radical inhibitor is added to 100 parts by mass of the resin. Addition of less than 0.001 part by mass is not preferable because a remarkable effect cannot be obtained. On the other hand, radical inhibitors
Even if it is added in excess of parts by mass, the effect of reducing the elution amount is substantially saturated, so that excessive addition is uneconomical. Absent. In order to achieve a higher effect, a radical inhibitor is added to 100 parts by mass of the resin composition (I).
It is preferable to add 0.005 to 1 part by mass.

The organic low molecular weight substance generated from the resin composition used in the present invention is generated by radical decomposition of a vinyl polymer having a polar group by the action of a metal compound in a polyester resin. Therefore, as the radical inhibitor used in the present invention, a phenolic radical inhibitor or a nitrogenous radical inhibitor having an effect of stopping a radical reaction by trapping a radical, and reacting with peroxides which are radical precursors However, a phosphorus-based and sulfide-based radical inhibitor having a function of suppressing the initiation of a radical reaction and inactivating a reaction intermediate is preferred.

Since the radical inhibitor acts in the coexistence of the above-mentioned vinyl polymer and polyester resin, the above-mentioned content before kneading decreases. A phenolic radical inhibitor refers to a compound having one or more phenolic hydroxyl groups in the molecule. In order to improve the efficiency of terminating the chain of the radical reaction, a compound having a sterically bulky t-butyl group or the like in the vicinity of the phenolic hydroxyl group is preferable, and radical kneading in resin kneading, film forming, and can manufacturing processes is prohibited. It is preferable that the molecular weight is 350 or more in that the volatilization of the agent is small. Further, from the viewpoint of the diffusibility of the radical inhibitor in the resin, the molecular weight is preferably 5,000 or less. From the viewpoint of improving the reactivity and the molecular weight, it is also preferable to use a compound having a plurality of phenolic hydroxyl groups in one molecule.

Examples of phenolic radical inhibitors include tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane and triethylene glycol-bis [3- (3-t- Butyl-5-methyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, and the like.

The phosphorus radical inhibitor refers to a compound having one or more phosphite groups and / or phosphonate groups in the molecule. In addition, the molecular weight is less than 350 due to less volatilization of the radical inhibitor in the resin kneading, film forming, and canning processes.
It is preferable that it is above. From the viewpoint of the diffusibility of the radical inhibitor in the resin, the molecular weight is preferably 5,000 or less. From the viewpoint of improving the reactivity and the molecular weight, it is also preferable to use a compound having a plurality of phosphite groups and / or phosphonate groups in one molecule.

Examples of the phosphorus radical inhibitor include 2,2-
Methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like. A sulfide radical inhibitor refers to a compound having one or more sulfide groups in a molecule. The molecular weight is preferably 350 or more from the viewpoint of little kneading of the resin and volatilization of the radical inhibitor in the molding step. Further, from the viewpoint of the diffusibility of the radical inhibitor in the resin, the molecular weight is preferably 5,000 or less. From the viewpoint of improving the reactivity and the molecular weight, it is also preferable to use a compound having a plurality of sulfide groups in one molecule.

Examples of the sulfide radical inhibitor include tetrakis [methylene-3- (dodecylthio) propionate] methane, bis (tridecyloxycarbonylethyl) sulfide and the like. The nitrogen-based radical inhibitor refers to a compound in which an amino group is bonded to an aliphatic hydrocarbon or an aromatic hydrocarbon group and the generated radical is donated with hydrogen to eliminate the radical.

Examples of the nitrogen radical inhibitor include bis (2-dodecylphenyl) amine, bis (3-octylphenyl) amine and bis (4-octylphenyl) amine. The radical inhibitors used in the present invention may be used alone or as a mixture. In the radical decomposition of the vinyl polymer (B) observed in the resin composition of the present invention, one of the main factors of ordinary thermal radical decomposition is a radical reaction caused by thermal decomposition of accumulated peroxide groups. Unlike the above, the main factor is the generation of radicals due to an electron transfer reaction from a metal compound such as a residual catalyst. This is preferable in that the effect of cutting the resin is high, and as a result, the effect of suppressing decomposition of the resin is high. Phosphorus-based and sulfide-based radical inhibitors have the effect of decomposing peroxides, which are radical sources and intermediates of radical reactions. Demonstrate. Further, the same synergistic effect is observed in a complex type radical inhibitor having two or more phenolic hydroxyl groups, phosphite groups and / or phosphonate groups, amino groups and sulfide bonds in one molecule, This use is also preferred.

Examples of the complex type radical inhibitor include 2,2
2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl] -o-cresol, 2,6-di- t-butyl
-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like. The resin composition of the radical inhibitor used in the present invention (I)
As a method of addition to the resin, at least one of the polyester resin (A) and the vinyl polymer (B) as the raw material resin, and the resin composition (I) contains the rubber-like elastic resin (C) In the case of, a polyester resin (A), a vinyl polymer (B) or a rubber-like elastic resin (C) by adding a radical inhibitor in advance to one or more of the resin composition to form a resin composition, What is necessary is just to make the said resin composition contain a radical inhibitor. At this time, adding a radical inhibitor to the raw material resin (B) in advance effectively suppresses decomposition of the raw material resin (B), and the addition of a smaller amount of the radical inhibitor has a high effect of reducing eluted substances. Is preferred in that the following is obtained.

When a radical inhibitor is added to a plurality of raw resin materials, the amount of the radical inhibitor contained in the resin composition as a result may satisfy the above-mentioned required amount of the radical inhibitor. As another method of adding a radical inhibitor to the raw resin (A), (B) and / or (C), a method of directly adding a radical inhibitor to a reaction tank during polymerization of the resin,
After polymerization, heating roll, Banbury mixer, kneader,
A method using an extruder or the like is used.

As a method for adding another radical inhibitor, (A) and (B) containing no radical inhibitor or
It may be added when the above resin composition or film is prepared by mixing the raw resin composed of (A), (B) and (C). At this time, the radical inhibitor may be directly added to the radical inhibitor itself, or may be added by a master batch method. Further, once the raw material resin containing no radical inhibitor is mixed to prepare the above resin composition, it may be added by charging the radical inhibitor into a hopper of a film forming machine when preparing the film. .

It is necessary to suppress the formation of pinholes and fish eyes in order to improve moldability, appearance, and rust prevention. A method such as drying is effective. In order to prevent the formation of secondary aggregates of the fine particles and to prevent deterioration due to the attachment and mixing of foreign substances, there are mentioned a method of using a raw material having a low content of fine particles, a method of manufacturing in a clean room, and the like. It is also useful to remove impurities by passing through a screen at least at one of the steps of melt extrusion such as kneading and / or film formation.

The resin composition of the present invention may further contain a fiber reinforcing agent such as glass fiber, metal fiber, potassium whisker, or carbon fiber for the purpose of improving rigidity and linear expansion characteristics.
Fillers such as talc, calcium carbonate, mica, glass flake, milled fiber, metal flake, and metal powder may be mixed. Among these fillers, glass fibers and carbon fibers desirably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. Also,
The amount of these additives is 0.
It is desirable that the amount be 5 to 50 parts by mass.

Further, the present resin composition may contain,
It is also possible to add appropriate amounts of heat stabilizers, light stabilizers, release agents, lubricants, pigments, flame retardants, plasticizers, antistatic agents, antibacterial antifungal agents and the like. In addition, the resin composition may be used in combination with another resin composition and / or an adhesive together with the present resin composition for the purpose of improving flavor and impact resistance.

That is, for the purpose of improving the lubricating property in the step of coating the metal plate or processing the metal plate, a known lubricant as disclosed in JP-A-5-186613 may be added. The particle size of the lubricant is preferably 2.5 μm or less. 2.5 μ
If it exceeds m, the mechanical properties of the resin film deteriorate. The amount of the lubricant to be added is determined according to the winding property and deep drawing workability of the metal sheet, but is preferably 0.05 to 20%.

As the pigment, for example, an inorganic white pigment such as titanium dioxide, calcium carbonate, barium sulfate or the like is used for the purpose of imparting a white light-shielding property for printing (for example, JP-A-6-49234). . As the plasticizer, for example, a conventionally known plasticizer such as a polyester plasticizer disclosed in JP-A-10-244645 may be added.

Further, an antistatic agent is disclosed in Japanese Patent Application Laid-Open No. HEI 5-59, for the purpose of preventing the film from being wound around a roll and preventing electrostatic damage such as adhesion of dirt on the film surface.
A method of kneading an antistatic agent or the like disclosed in 222357 JP into a resin composition, a method of applying an antistatic agent as shown in JP-A-5-1164 to the film surface, etc., as necessary Can be applied.

Further, antibacterial agents are disclosed in JP-A-11-4843.
Conventionally known antibacterial agents disclosed in JP-A-11-138702 and JP-A-11-138702 may be added as necessary. The resin-coated metal sheet according to the present invention is obtained by forming a specific plating film on the surface of a base metal sheet, and laminating the resin composition thereon. Preferred embodiments are as follows.

(I) In the resin-coated metal plate for a container, a two-layer film of chromium metal and chromium hydrated oxide is formed on at least the surface of the base metal plate on the inner surface side of the container from the side of the metal plate. A resin-coated metal sheet comprising a polyester resin (A), a vinyl polymer (B) containing at least 1% by mass of a unit having a polar group, and a resin composition layer containing a radical inhibitor.

In this case, the plating amount of metallic chromium is 10 to 30.
Coating weight of 0 mg / m ² and hydrated chromium oxide is in the range of 1 to 50 mg / m ² in terms of chromium are preferred. (II) In a resin-coated metal plate for a container, a three-layer coating of tin, chromium chromium, and chromium hydrated oxide is formed from the metal plate side on at least the surface of the base metal plate on the inner side of the container, and polyester is formed thereon. Resin (A), a unit having a polar group
A resin-coated metal plate comprising a resin composition layer containing a vinyl polymer (B) containing at least 1% by mass and a radical inhibitor.

In this case, the tin plating amount is 0.1 to 10 g / m
^2. The plating amount of chromium metal is 1 to 200 mg / m ² and the plating amount of hydrated chromium oxide is 1 to 50 mg / m ^{2 in} terms of chromium.
It is preferred that (III) In a resin-coated metal plate for a container, a four-layer coating of metal chromium, tin, metal chromium, and chromium hydrated oxide is formed from the metal plate side on at least the surface of the base metal plate on the inner side of the container. Polyester resin (A) on top, vinyl polymer (B) containing at least 1% by mass of a unit having a polar group
And a resin composition layer containing a radical inhibitor.

In this case, the plating amount of metallic chromium is 10-30.
0 mg / m ² , tin plating amount is 50-5000 mg / m ² , metallic chromium plating amount is 1-300 mg / m ^2, and chromium hydrated oxide plating amount is preferably 1-50 mg / m ² It is.
The base metal sheet is not particularly limited, but cans such as tinplate, thin tin-plated steel sheet, electrolytic chromic acid-treated steel sheet (tin-free steel), nickel-plated steel sheet, hot-dip galvanized steel sheet, hot-dip zinc-iron Alloy plated steel sheet, hot-dip zinc
-Aluminum-magnesium alloy-coated steel sheet, hot-dip aluminum-silicon alloy-coated steel sheet, hot-dip-tin alloy-coated steel sheet, hot-dip coated steel sheet, electro-galvanized steel sheet, electro-zinc-nickel-plated steel sheet, electro-zinc-iron alloy-plated steel sheet, Examples include surface-treated steel sheets such as electroplated steel sheets such as electro-zinc-chromium alloy-plated steel sheets, cold-rolled steel sheets, and metal sheets such as aluminum, copper, nickel, zinc, and magnesium.

The above embodiment of the present invention will be described with reference to the drawings. In FIGS. 1 to 3, 1 is a metal plate, 2, 2 ',
2 '', 2 '''is a chromium plating layer, 3, 3', 3 '' is a chromium hydrated oxide layer, 4 is a resin composition layer, 5, 5 'is a diffusion layer, 6,
Reference numeral 6 ′ denotes a tin plating layer, and the resin composition layer 4 side is the inner surface side of a container such as a can. FIGS. 1 to 3 show the above (I) to (I), respectively.
Corresponds to II). The plating amount of each plating layer is not limited, but chromium is about 1 to 300 mg / m ² and tin is 0.05 to 10 mg / m ^2.
g / m ² , hydrated chromium oxide (calculated as chromium) 1 to 200 mg
/ M ² is generally selected appropriately in consideration of adhesion, corrosion resistance, and economy.

For example, in FIG. 1, the chromium plating layer has a plating amount of 10 to 300 mg / m ² . Desirably, it is 70 to 130 mg / m ² . The reason for setting the lower limit to 10 mg / m ² is to improve the corrosion resistance by coating the steel sheet.
The reason for setting the upper limit to 300 mg / m ² is that even if it is further increased, the effect of improving the corrosion resistance saturates and becomes economical.

In FIGS. 2 and 3, the tin plating layer suppresses the exposure of ground iron after processing, so that the elution of iron from the resin composition layer (film) defect can be further reduced.
Also, in order to ensure the adhesion between the tin plating layer and the film,
The tin layer can be covered with a metal chromium layer to suppress the formation of tin oxide. Although a diffusion layer is provided in FIGS. 2 and 3, in the present invention, any one of nickel, tin, and chromium or an alloy thereof is diffused into the metal plate on the surface layer of the metal plate. It is desirable that a layer be formed. Further, it is preferable that the content of any component of nickel, tin or chromium or an alloy thereof contained in the diffusion layer is 50 to 600 mg / m ² .

Each of these plating layers and diffusion layers can be formed by a method generally used per se after the surface of a metal plate is degreased and pickled. In the metal plate according to the present invention, a primer layer may be provided on the plating layer. By combining this primer layer, even in a can body that has been subjected to severe molding such as drawing and ironing, since the impact resistance at low temperatures is excellent, the base metal can be melted out because cracks are not easily generated in the film at impact. rare. Further, since the flavor hardly changes even after retort sterilization, it is suitable as a resin-coated metal plate for can making.

As such a primer layer, for example, a phenol-epoxy paint composed of a resol type phenol formaldehyde resin derived from phenols and formaldehyde and a bisphenol type epoxy resin (Japanese Patent Publication No. 7-10696), 50 ~ 98 wt% polyamide dicarboxylic acid modified epoxy resin and 2 ~ 50 wt%
And a composition containing 0.05 to 10% by weight of a curing catalyst (JP-A-5-269917).

The thickness of the coating when the resin composition of the present invention is coated on the above-mentioned metal plate is not particularly limited, but is preferably 1 to 300 μm. If the thickness is less than 1 μm, the impact resistance of the coating may not be sufficient.
If it is super, the economy is bad. A known method can be used for coating the metal plate. Specifically, (1) a method in which the resin composition prepared by melt-kneading the raw material resin in advance with a kneading machine is formed into a film with an extruder equipped with a T-die, and this is thermocompression-bonded to a metal plate (in this case, Even if the film is not stretched, 1
(Or may be stretched in two directions) or (2) a method of directly thermocompression-bonding a film coming out of a T-die. Another method for directly thermocompression bonding a film is as follows: (3) Instead of the present resin composition, put the resin as a raw material of the present resin composition and a radical inhibitor into a hopper of an extruder equipped with a T die, Knead the resin composition in an extruder,
There is a method of directly thermocompression-bonding it.

Further, the resin composition of the present invention can exhibit sufficient impact resistance even if the degree of crystallinity is not inclined inside the film after coating. Therefore, (4) a method of melting the resin composition and coating it with a bar coater or a roll, (5) a method of dipping a metal plate in the molten resin composition, and (6) a method of dissolving the resin composition in a solvent and spin coating. It is also possible to coat the metal plate by such a method as mentioned above, and the coating method is not particularly limited.

The methods (1), (2) and (3) described above are the most preferable as the method of coating a metal plate from the viewpoint of work efficiency. When coating is performed using the method (2), the film thickness is preferably 1 to 300 μm for the same reason as described above. Further, as for the surface roughness of the film, it is preferable that the result of arbitrarily measuring the length of the film surface by 1 mm is 500 nm or less in Rmax. If it exceeds 500 nm, bubbles may be involved when coating by thermocompression bonding.

Further, due to the high impact properties of the present resin composition, high impact properties are exhibited even when used without stretching. Therefore, it can be used as a metal coating material without stretching, and the number of steps can be reduced. In addition, when used as a metal coating material without stretching, it is not necessary to control the crystallinity in the thin film by controlling the temperature, the passing speed, and the like, so that the process window can be enlarged and high-speed production can be performed. Further, temperature control for controlling the degree of crystallinity at the time of film formation and coating is easy, so that a product with stable performance can be manufactured.

The resin film of the present invention is a resin film comprising the resin composition of the present invention. The resin film before coating may be a resin film formed after coating by the above-mentioned method (4) to (6). There may be. Further, in order to improve the lubricating property at the time of coating the metal plate and processing the metal plate, Japanese Patent Application Laid-Open No.
A known lubricant as disclosed in JP-A-186613 may be added. The particle size of the lubricant is preferably 2.5 μm or less. If it exceeds 2.5 μm, the mechanical properties of the resin film deteriorate. The amount of the lubricant to be added is determined according to the winding property and deep drawing workability of the metal sheet, but is preferably 0.05 to 20%.

When the resin film of the present invention is coated on a metal plate, it is coated on at least one surface and / or both surfaces of the metal plate by laminating a single layer or a multilayer using at least the above resin film. be able to. At this time, one or two or more types of resin films may be used to form a single-layer or multilayer structure on one side and / or both sides of the metal plate.If necessary, a PET film, a polycarbonate film, etc. Polyester film, polyolefin film such as polyethylene film, polyamide film such as 6-nylon film, other known resin films such as ionomer film, or crystalline / non-crystalline polyester composition film, polyester / ionomer composition A known resin composition film such as a film or a polyester / polycarbonate composition film may be laminated and coated on the lower layer and / or the upper layer. As a specific laminating method, when the above-mentioned methods (1), (2) and (3) are used, the resin film of the present invention and other resin films or resin compositions can be formed using a multilayer T-die. There is a method of manufacturing a multilayer film with a film and thermocompression bonding the film. Further, when using the above methods (4) to (6), after coating the resin composition of the present invention after coating another resin composition, or after coating the resin composition of the present invention conversely By coating with another resin composition, it is possible to laminate in multiple layers.

The resin-coated metal plate of the present invention is a metal plate coated with the resin film of the present invention, and the coating may be on one side or both sides. The thickness of the metal plate is not particularly limited, but is preferably 0.01 to 5 mm. 0.01
If it is less than 5 mm, it is difficult to develop strength, and if it is more than 5 mm, it is difficult to process. The resin-coated metal container of the present invention is a resin-coated metal container made of the resin-coated metal plate of the present invention, and can be formed by a known processing method. Specific examples include draw ironing molding, draw redraw molding, stretch draw molding, and stretch draw ironing molding. A resin-coated metal container using the resin-coated metal plate of the present invention may be used. It is not limited to the above-mentioned molding method.

The resin composition layer in the present invention contains a ternary component of a polyester resin (A), a vinyl polymer (B) containing at least 1% by weight of a unit having a polar group, and a radical inhibitor. The impact resistance of the polyester resin (A) can be improved by the vinyl polymer (B), and the adhesion between the metal plate and the resin composition is also good. Furthermore, the addition of the radical inhibitor suppresses the decomposition of the resin composition, and the decomposition products are less eluted.

The resin composition layer of the present invention comprises a rubber-like elastic resin body (A), a polyester resin (A), a vinyl polymer (B) containing at least 1% by weight of a unit having a polar group, and a radical inhibitor. C), especially a resin composition having a structure in which a rubber-like elastic resin body (C) encapsulated with a vinyl polymer (B) is finely dispersed in a polyester resin (A). The impact resistance of the polyester resin (A) can be improved by the resin body (C), and the vinyl polymer (B)
Since the rubber-like elastic resin body (C) is encapsulated in the resin, the compatibility between the polyester resin (A) and the rubber-like elastic resin body (C) is improved, and the impact resistance is improved. It is excellent in that direct contact with the elastic resin body (C) can be prevented and adhesion between the metal plate and the resin composition can be ensured. further,
The decomposition of the resin composition is suppressed by the addition of the radical inhibitor, and the decomposition products are hardly eluted.

As a result, the resin composition used in the present invention is:
Since it has excellent moldability, heat resistance, impact resistance, chemical resistance, mechanical strength, gas barrier properties, adhesion to metals, etc., and excellent flavor properties, the resin-coated metal plate obtained by the method of the present invention is In addition to excellent adhesion between resin and metal plate, corrosion resistance, impact resistance and workability, it also has excellent coating and printing characteristics and is easy to impart design, and the addition of a radical inhibitor suppresses the decomposition of resin. Therefore, it can be suitably used for a metal container such as a metal can. In particular, the metal container is excellent in followability of the resin at the time of drawing or drawing and ironing, and can form a metal container having an excellent appearance.

Further, the resin-coated metal container of the present invention is a metal container formed by molding the resin-coated metal plate of the present invention. It has heat resistance enough to withstand drying, printing, baking, etc., and has particularly long-term storage properties with excellent flavor properties (perfume retention properties).
Therefore, it can be suitably used as a container for soft drinks and foods.

[0102]

Next, the present invention will be described more specifically with reference to Examples, Production Examples and Comparative Examples. In the following, polyethylene terephthalate is used as the polyester resin (A).
(PET) [Toyobo Co., Ltd. RN163], polybutylene terephthalate (PBT) [Toray Co., Ltd. 1401-X04], an ethylene ionomer as a vinyl polymer (B) having at least 1% by weight of a unit having a polar group [Himilan 1706, 1707, manufactured by DuPont-Mitsui Co., Ltd.], ethylene-methacrylic acid copolymer
[Nucrel N1035 manufactured by DuPont-Mitsui Co., Ltd.], and polybutyl acrylate-polymethyl methacrylate copolymer (MBA) as a core-shell type rubber-like elastic material [“PARALOID” EXL2314 manufactured by Kureha Chemical Co., Ltd.] Ethylene-propylene rubber (EPR) as rubber-like elastic resin (C) [JSR
EP07P], ethylene-butene rubber (EBM) [JSR
EBM2041P].

(Production Examples 1 to 15) Each of the resins shown in Table 1 and the radical inhibitor tetrakis [methylene (3,5-di-t-butyl-4) -4
-Hydroxyhydrocinnamate)] methane was dry-blended at each composition ratio shown in Table 1 using a V-type blender. The composition of each resin is as shown in Table 1. In each case, 0.1 part by mass of the radical inhibitor was added to 100 parts by mass of the resin composition (I). This mixture is extruded in a twin-screw extruder
The mixture was melt-kneaded at 260 ° C. to obtain a resin composition pellet containing a radical inhibitor. Ultrathin sections were cut out from the resin composition with a microtome, stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) in the polyester resin (A) was analyzed with a transmission electron microscope. Rubbery elastic resin (C)
In the case where was added, the dispersion state of the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A) was analyzed by a transmission electron microscope. As a result, the rubber-like elastic resin
When (C) is not added, the equivalent spherical equivalent diameter of the vinyl polymer (B) is 1 μm or less as shown in Table 1 and the polyester resin
(A) Finely dispersed therein. Rubbery elastic resin (C)
In all cases, the rubber-like elastic resin (C) is almost 100% encapsulated with the vinyl polymer (B), and the equivalent spherical equivalent diameter of the rubber-like elastic resin (C) is shown in Table 1. 1 μm as shown
Below, it was finely dispersed in the polyester resin (A).

[0104]

[Table 1]

The pellets were extruded using a T die at 30
A film having a thickness of μm was obtained (extrusion temperature: 280 ° C.). This film is laminated to both sides of 0.19mm thick tin-free steel heated to 250 ° C, and cooled to 100 ° C within 10 seconds by water cooling.
It was quenched to the following. With respect to the thus-obtained normal-temperature resin-coated metal sheet, each item of the fragrance retention, taste retention, adhesion, ordinary-temperature impact resistance and low-temperature impact resistance was evaluated by the evaluation methods described below. . In addition, the evaluation of the fragrance retention and taste retention was evaluated using the same test piece, and the adhesion, room temperature impact resistance and low temperature impact resistance were the same as those of the test piece evaluated for fragrance retention and taste retention. Was evaluated using different specimens.

<Fragrance retention and flavor retention> The above-mentioned resin-coated metal plate (12.5 cm × 8 cm square) was put in a glass container together with distilled water (300 mL), sealed with a glass stopper, and kept at 85 ° C. for 7 hours. Heated for days. Changes in the scent and taste of the content water were organoleptically evaluated according to the following criteria. Table 2 shows the results. ◎: No change in fragrance or taste ○: Slight change in fragrance or taste △: Change in scent or taste was observed ×: Unpleasant scent or taste was observed

[0107]

[Table 2]

<Adhesion, room-temperature impact resistance and low-temperature impact resistance> The above resin-coated metal plate was treated with 1.5% by weight of citric acid and 1.
After immersion in a 5 wt% aqueous solution (UCC solution) at room temperature for 24 hours,
The evaluation was based on the length (mm) (average of 10 samples) from which the film was peeled off. Evaluation: ◎: 0.0 mm, ○: 0.0 to 0.5 mm, Δ: 0.5 to
2.0 mm and ×: more than 2.0 mm. Table 3 shows the results of the adhesion test.
Shown in

Further, the impact resistance of the resin-coated metal plate was evaluated by a DuPont type drop impact test. After dropping a 0.5 kg iron ball on a metal plate from a height of 30 cm, place the metal plate on the bottom so that the convexly swelling side (r = 8 mm) of the sample is the top surface, and place it around the convex part. An ERV value when a voltage of +6 V is applied by forming a wall with a soft rubber-like resin, putting 1.0% saline solution into the sample, using the sample as an anode, and using platinum placed near the convex portion as a cathode as a cathode. mA) was measured. The ERV value was evaluated by the following indicators. After placing the resin-coated metal plate in a thermostat at 0 ° C. for 24 hours, the same impact resistance was evaluated, and the impact resistance at low temperature was evaluated. Evaluation is ◎: All samples
Less than 0.01 mA, ○: 1 to 3 samples 0.01 mA or more, Δ: 3 to 6
The test was performed on the basis that the sample was 0.01 mA or more and x: 7 samples or more were 0.01 mA or more. Table 3 shows the results.

[0110]

[Table 3]

(Production Examples 16 to 28) Composition ratio of each resin shown in Production Example 2 (polyester resin (A): vinyl polymer (B) =
92: 8) in preparing the resin composition of Table 4 in place of tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane as a radical inhibitor.
The following various radical inhibitors were added in an amount of 0.1 part by mass with respect to 100 parts by mass of the resin composition (I) to prepare resin composition pellets. After cutting out an ultra-thin section from the resin composition with a microtome, stained with ruthenic acid, the polyester resin
The dispersion state of the vinyl polymer (B) in (A) was analyzed with a transmission electron microscope. As a result, the equivalent spherical equivalent diameter of the vinyl polymer (B) was equivalent to that of Production Example 2, and was 1 μm or less and was finely dispersed in the polyester resin (A).

Using the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance were measured. Each item was evaluated. Table 4 shows the results.

[0113]

[Table 4]

(Production Example 29) Resin having the composition ratio of each resin shown in Production Example 5 above (polyester resin (A): vinyl polymer (B): rubber-like elastic material (C) = 87: 3: 10) Pellets and the radical inhibitor tetrakis [methylene (3,5-di-t-butyl-4-
Hydroxyhydrocinnamate)] methane (0.01% based on 100 parts by mass of resin pellets) and dry blended using a V-type blender. This mixture was melt-kneaded at 260 ° C with a twin-screw extruder equipped with a T-die, and was 30 mm wide and 25 mm thick.
It was formed into a micron film. Ultrathin sections were cut from the film with a microtome, stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) in the polyester resin (A) was analyzed with a transmission electron microscope. When the rubber-like elastic resin (C) was added, the dispersion state of the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A) was analyzed by a transmission electron microscope. As a result, almost 100% of the rubber-like elastic resin (C) was encapsulated with the vinyl polymer (B), and the equivalent spherical equivalent diameter of the rubber-like elastic resin (C) was 0.6.
It was finely dispersed in the polyester resin (A) at μm. Using this film, a resin-coated metal plate was prepared in the same manner as in Production Example 5, and evaluated by the same evaluation method as in Production Example 5. Table 5 shows the results.

[0115]

[Table 5]

(Production Examples 30 to 42) Composition ratio of each resin shown in Production Example 5 above (polyester resin (A): rubber-like elastic resin)
(C): When preparing a resin composition of vinyl polymer (B) = 87: 10: 3), tetrakis [methylene (3,5
-Di-t-butyl-4-hydroxyhydrocinnamate)]
Instead of methane, 0.1 parts by mass of each of the various radical inhibitors shown in Table 6 was added to 100 parts by mass of the resin composition (I),
Resin composition pellets were prepared. After cutting out an ultra-thin section from the resin composition with a microtome, the section is stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A) is determined by transmission electron transmission. Analyzed with a microscope. As a result, in each case, the rubber-like elastic resin (C) was almost 100% encapsulated with the vinyl polymer (B), and the equivalent spherical equivalent diameter of the rubber-like elastic resin (C) was the same as that of Production Example 1. And it was finely dispersed in the polyester resin (A) below 1 μm.

Using the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance were measured. Each item was evaluated. Table 6 shows the results.

[0118]

[Table 6]

(Production Examples 43 to 47) Composition ratio of each resin shown in Production Example 2 above (Polyester resin (A): vinyl polymer (B) =
92: 8), tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane was added as a radical inhibitor in the ratio shown in Table 7. Thus, a resin composition pellet was prepared. Ultrathin sections were cut out from the resin composition with a microtome, stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) in the polyester resin (A) was analyzed with a transmission electron microscope. As a result, the equivalent spherical equivalent diameter of the vinyl polymer (B) was 0.5 μm or more.
It was finely dispersed in the polyester resin (A) at 1 μm or less.

Using each of the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance were measured. Each item was evaluated. Table 7 shows the results.

[0121]

[Table 7]

(Production Examples 48 to 52) Composition ratio of each resin shown in Production Example 6 above (Polyester resin (A): rubber-like elastic resin)
(C): When preparing a resin composition of vinyl polymer (B) = 87: 10: 3), tetrakis [methylene (3,5
-Di-t-butyl-4-hydroxyhydrocinnamate)]
Methane was added at the ratios shown in Table 6 to prepare resin composition pellets. After cutting out an ultrathin section from the resin composition with a microtome, dyed with ruthenic acid, the vinyl polymer (B) in the polyester resin (A), the rubber-like elastic resin (C)
Was analyzed with a transmission electron microscope. As a result,
In each case, the rubber-like elastic resin (C) is almost a vinyl polymer (B).
The rubber-like elastic resin (C) had an equivalent sphere equivalent diameter of 0.3 μm or more and 1 μm or less, and was finely dispersed in the polyester resin (A).

Using the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance were measured. Each item was evaluated. Table 8 shows the results.

[0124]

[Table 8]

(Production Example 53) Composition ratio of each resin shown in Production Example 2 above (polyester resin (A): vinyl polymer (B) = 9)
2: 8) When preparing the resin composition of
PET was used as (A), and 1706 to which a radical inhibitor was added in advance as vinyl polymer (B) was used. Ie 17
06 and 100 parts by mass of tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane.
01 parts by mass were dry-blended using a V-type blender, and this mixture was melt-kneaded at 150 ° C with a twin-screw extruder to obtain pellets of a vinyl polymer (B) containing a radical inhibitor. The pellets and the polyester resin (A) pellets were dry-blended using a V-type blender, and the mixture was melt-kneaded at 260 ° C. using a twin-screw extruder to prepare resin composition pellets. Ultrathin sections were cut out from the resin composition with a microtome, stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) in the polyester resin (A) was analyzed with a transmission electron microscope. As a result, the vinyl polymer (B)
Was 0.7 μm in equivalent sphere, and was finely dispersed in the polyester resin (A).

Using the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and each of the fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance was measured. The items were evaluated. Table 9 shows the results.

[0127]

[Table 9]

(Production Example 54) Composition ratio of each resin shown in Production Example 5 above (polyester resin (A): rubber-like elastic resin (B):
In preparing the resin composition of vinyl polymer (C) = 87: 10: 3), PET was used as polyester resin (A), EBM was used as rubbery elastic resin (B), and vinyl polymer (C) was used. 1706 to which a radical inhibitor was added in advance was used. That is, 100 parts by mass of 1706 and tetrakis [methylene (3,5-di-t-
Butyl-4-hydroxyhydrocinnamate)] methane was dry-blended in a V-type blender at 0.01 parts by mass, and this mixture was melt-kneaded at 150 ° C with a twin-screw extruder to obtain a vinyl polymer containing a radical inhibitor. A pellet of the combined (B) was obtained. The pellets and the pellets of polyester resin (A) and rubber-like elastic resin (C) are dry-blended using a V-type blender, and the mixture is subjected to 260 ° C with a twin-screw extruder.
To prepare resin composition pellets. After cutting out an ultra-thin section from the resin composition with a microtome, the section is stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A) is determined by transmission electron transmission. Analyzed with a microscope. As a result, the rubber-like elastic resin
(C) was almost 100% encapsulated with the vinyl polymer (B), and the equivalent spherical equivalent diameter of the rubber-like elastic resin (C) was 0.5 μm and was finely dispersed in the polyester resin (A).

Using the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and each of the fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance was measured. The items were evaluated. Table 10 shows the results.

[0130]

[Table 10]

(Production Examples 55 to 58) Each of the resins shown in Table 11 and tetrakis [methylene (3,5-di-t-
Butyl-4-hydroxyhydrocinnamate)] methane
Dry blending was performed using a V-type blender. The composition of each resin is as shown in Table 11, and in all cases, 0.1 part by mass of the radical inhibitor was added to 100 parts by mass of the resin composition (I). This mixture was melt-kneaded at 230 ° C. with a twin-screw extruder to obtain resin composition pellets. As a result of analyzing the dispersion state in the same manner as in Production Examples 1 to 15, as shown in Table 10, the dispersed particles had a diameter of 0.3 μm or more and 1 μm or less, and were finely dispersed in the polyester resin (A). When the rubber-like elastic resin (C) was added, the rubber-like elastic resin (C) was encapsulated 100% with the vinyl polymer (B).

[0132]

[Table 11]

Further, films were prepared in the same manner as in Production Examples 1 to 15 and bonded to both sides of 0.19 mm-thick tin-free steel to evaluate the fragrance retention, taste retention, adhesion and impact resistance. Table 12 shows the results.

[0134]

[Table 12]

(Production Examples 59 to 61) Each of the resins shown in Table 13 and tetrakis [methylene (3,5-di-t-
Butyl-4-hydroxyhydrocinnamate)] methane
Dry blending was performed using a V-type blender. The mixing ratio of each resin is as shown in Table 13. In each case, 0.1 part by mass of the radical inhibitor was added to 100 parts by mass of each resin composition (I). This mixture was melt-kneaded at 240 ° C. with a twin-screw extruder to obtain resin composition pellets. As a result of analyzing the dispersion state in the same manner as in Production Examples 1 to 15, the core-shell type rubber-like elastic material was finely dispersed in the polyester resin (A) with an equivalent spherical equivalent diameter of 1 μm or less as shown in Table 13. Was.

[0136]

[Table 13]

Further, a film was prepared in the same manner as in Production Examples 1 to 15 (extruding temperature: 240 ° C.), and laminated on both sides of 0.19 mm-thick tin-free steel. And impact resistance. Table 14 shows the results.

[0138]

[Table 14]

(Comparative Examples 1 to 8) Each resin shown in Table 15 was dry-blended using a V-type blender without adding a radical inhibitor. This mixture was melt-kneaded at 230 ° C. with a twin-screw extruder to obtain resin composition pellets. As a result of analyzing the dispersion state in the same manner as in Production Examples 1 to 11, the equivalent spherical equivalent diameter of the particles was 1 μm or less as shown in Table 14, and the polyester resin
(A) Finely dispersed therein. Rubbery elastic resin (C)
Was encapsulated 100% with the vinyl polymer (B).

[0140]

[Table 15]

Further, a film was prepared in the same manner as in Production Examples 1 to 15 and bonded to both sides of 0.19 mm thick tin-free steel, and the fragrance retention, taste retention, adhesion and impact resistance were evaluated. Table 16 shows the results.

[0142]

[Table 16]

In each case, the adhesion, room-temperature impact resistance and low-temperature impact resistance are not changed as compared with the case where the resin composition to which a radical inhibitor is added is used. It turned out to be inferior in point. (Comparative Example 9) PET was blended with PET as a polyester resin and MBA as a core-shell rubber-like elastic material at a weight ratio of 90:10 without adding a radical inhibitor. This mixture is melt-kneaded at 240 ° C. with a twin-screw extruder to obtain a resin composition (I).
A pellet was obtained. As a result of analyzing the dispersion state in the same manner as in Production Examples 1 to 15, the core-shell type rubber-like elastic body was finely dispersed in the polyester resin with an equivalent spherical equivalent diameter of 0.25 μm. Furthermore, a film was created in the same manner as in Production Examples 1 to 15.
It was bonded to both sides of a 0.19 mm thick tin-free steel, and its fragrance retention, taste retention, adhesion and impact resistance were evaluated.
The results are shown in FIG.

[0144]

[Table 17]

As compared with the case of using a resin composition to which a radical inhibitor has been added, the adhesiveness, the normal temperature shock resistance and the low temperature impact resistance are not changed, but are inferior in terms of flavor retention and taste retention. I understand. (Comparative Example 10) When preparing a resin composition of the polyester resin (A): vinyl polymer (B) = 92: 8 of Comparative Example 1, 3- (N-salicyloyl) amino- was used as a metal deactivator. 0.1 parts by mass of 1,2,4-triazole was added to 100 parts by mass of the resin composition (I) to prepare a resin composition pellet. As a result of analyzing the dispersion state in the same manner as in Production Examples 1 to 15, the vinyl polymer (B) was analyzed.
Had a microsphere equivalent diameter of 0.5 μm and was finely dispersed in the polyester resin.

Using the pellets thus prepared, a resin-coated metal plate was prepared, and the fragrance retention, taste retention, adhesion,
Each item of the normal temperature impact resistance and the low temperature impact resistance was evaluated. The results are shown in Table 18.

[0147]

[Table 18]

When a metal deactivator was used as an additive, no improvement in fragrance retention and flavor retention was observed. (Comparative Example 11) When preparing a resin composition of Comparative Example 3 of a polyester resin (A): rubber-like elastic resin (C): vinyl polymer (B) = 87: 10: 3, metal inactivation was performed. As an agent, 0.1 part by mass of 3- (N-salicyloyl) amino-1,2,4-triazole was added to 100 parts by mass of the resin composition (I) to prepare a resin composition pellet. As a result of analyzing the dispersion state in the same manner as in Production Examples 1 to 15, the rubber-like elastic resin (C) was a vinyl polymer (B) of 10%.
It was encapsulated at 0% and finely dispersed in the polyester resin with an equivalent sphere equivalent diameter of the rubber-like elastic resin (C) of 0.5 μm.

Using the pellets prepared in this manner, a resin-coated metal plate was prepared, and the fragrance retention, taste retention, adhesion,
Each item of the normal temperature impact resistance and the low temperature impact resistance was evaluated. Table 19 shows the results.

[0150]

[Table 19]

When a metal deactivator was used as an additive, no improvement in fragrance retention and flavor retention was observed. (Comparative Examples 12 and 13) Composition ratio of each resin shown in Production Example 2 above
When preparing a resin composition of (polyester resin (A): vinyl polymer (B) = 82: 8), tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydro) is used as a radical inhibitor. Cinnamate)] methane was added in the following proportions to prepare resin composition pellets. After cutting out ultrathin sections from the resin composition with a microtome, stain with ruthenic acid,
The dispersion state of the vinyl polymer (B) in the polyester resin (A) was analyzed with a transmission electron microscope. The equivalent spherical equivalent diameter of the vinyl polymer (B) was 0.3 μm or more and 1 μm or less, and was finely dispersed in the polyester resin (A).

Using each of the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance were measured. Each item was evaluated. Table 20 shows the results.

[0153]

[Table 20]

It was found that when the amount of the radical inhibitor added was less than 0.001 part by mass, the fragrance retention and flavor retention were not sufficiently improved. Further, it was found that when the amount of the radical inhibitor reached 10 parts by mass, the adhesion and the impact resistance were reduced. (Comparative Examples 14 and 15) Composition ratio of each resin shown in Production Example 5 above
When preparing a resin composition of (polyester resin (A): rubber-like elastic resin (C): vinyl polymer (B) = 87: 10: 3), tetrakis [methylene (3,5 -Di-t-butyl-4-hydroxyhydrocinnamate)] methane was added in the following proportions to prepare resin composition pellets. After cutting out ultrathin sections from the resin composition with a microtome,
The dispersion state of the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A) was analyzed with a transmission electron microscope. As a result, in each case, the rubber-like elastic resin (C) was almost 100% encapsulated with the vinyl polymer (B), and the equivalent spherical equivalent diameter of the rubber-like elastic resin (C) was 0.3.
It was finely dispersed in the polyester resin (A) in the range of μm to 1 μm.

Using the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance were measured. Each item was evaluated. Table 21 shows the results.

[0156]

[Table 21]

It was found that when the amount of the radical inhibitor added was less than 0.001 part by mass, the fragrance retention and flavor retention were not sufficiently improved. Further, it was found that when the amount of the radical inhibitor reached 10 parts by mass, the adhesion and the impact resistance were reduced. (Comparative Example 16) Based on the example of Japanese Patent Publication No. 2-9935, PBT
Biaxially stretched film consisting of two layers of PET and PET (PBT layer: 10 μm
(PET layer: 20 μm, refractive index in the thickness direction of the PET layer: 1.526) on a tin-free steel under the same conditions as in Production Examples 1 to 15 (so that the PBT layer adheres to the tin-free steel). Coating), adhesiveness and impact resistance
Evaluation was made in the same manner as in 5.

Comparative Example 17 A biaxially stretched polyester film (terephthalic acid / isophthalic acid / ethylene glycol residue (78/22/1
, A film having a specific gravity of 1.3387, a thickness of 30 μm, and a plane orientation coefficient of 0.120) was thermocompression-bonded on tin-free steel under the same conditions as in Production Examples 1 to 15, and the adhesion and impact resistance were measured in Production Examples 1 to 15. Was evaluated in the same way as

(Comparative Example 18) A 108 μm unstretched PET film was stretched 2.7 times in the longitudinal direction at 95 ° C. and 2.6 times in the transverse direction at 105 ° C. based on Example 1 of JP-A-64-22530. After heat treatment, a stretched film of about 20 μm was obtained. This film was thermocompression-bonded on tin-free steel under the same conditions as in Production Examples 1 to 15, and the adhesion and impact resistance were evaluated in the same manner as in Production Examples 1 to 15 (Table 22).

[0160]

[Table 22]

[0161] The resins obtained by these conventional methods could not obtain sufficient adhesion and impact resistance. (Production Examples 62 to 67, Comparative Examples 19 to 21) Production Examples 2, 5, 11, 57
~ 59, the resin-coated metal plate obtained in Comparative Examples 16 to 18, 150m
Cut into a disk with a diameter of m and use a drawing die and punch
Deep drawing was performed in four steps, and 10 cans of 55 mm diameter side seamless containers (hereinafter abbreviated as cans) were prepared.

The following observations and tests were performed on these cans, and the results of evaluation based on the following criteria are shown in Table 23. (1) Deep drawing processability I (evaluation of film surface layer);: For all 10 cans, the film was processed without any abnormality, and no whitening or breakage was observed in the film on the inner and outer surfaces of the can.

△: For 1 to 5 cans, whitening of the film was observed at the top of the can. ×: Film breakage is observed in a part of the film for 6 or more cans. (2) Deep drawing workability II (Evaluation of can inner film) ○: All 10 cans were processed without any trouble on the inner and outer surfaces, and rust prevention test on the inner film surface of the can (put 1.0% saline solution, the can was used as the anode,
The current value (ERV value) (mA) flowing when a voltage of +6 V is applied using platinum as a cathode is 0.1 mA or less.

X: Three or more cans showed a rust prevention test on the film surface inside the can of more than 0.1 mA. (3) Impact resistance The cans with good deep drawing were filled with water, and 10 samples of each sample were dropped from a height of 10 cm onto a PVC tile floor, and then the ERV test in the can was performed. ;: All 10 cans were 0.1 mA or less.

Δ: 1 to 5 cans exceeded 0.1 mA. ×: More than 6 cans exceeded 0.1 mA. (4) Heat embrittlement resistance A can having good deep drawing was held at 200 ° C for 5 minutes by heating, and then the impact resistance was measured by the above method to evaluate the heat embrittlement resistance.

[0166]

[Table 23]

From the above results, the resin composition to which the radical inhibitor of the present invention was added was excellent in adhesion to metal and impact resistance, particularly excellent in impact resistance at low temperatures, and was superior to the prior art. It can be seen that the fragrance retention and the flavor retention are superior in comparison. In addition, it can be seen that the resin-coated metal plate of the present invention is excellent in processability of coating, and that the resin-coated metal container of the present invention is also excellent in impact resistance and heat embrittlement resistance.

(Reference Example 1: Correlation between TOC and fragrance retention) Polyester resin (A) and vinyl polymer (B) at a composition ratio of 92: 8
The pellets were dry blended using a V-blender. This mixture was melt-kneaded at 260 ° C. with a twin-screw extruder to obtain resin composition pellets. Using the pellets, resin-coated metal plates were prepared in the same manner as in Examples 1 to 15. This resin-coated metal plate (12.5 cm × 8 cm square) was placed in a glass container together with distilled water (300 mL), and sealed with a glass stopper.
After a predetermined time at ° C., the TOC value (ppm) of the content water and changes in aroma and taste were evaluated according to the same criteria as in Production Examples 1 to 15.
The results are shown in Table 24.

[0169]

[Table 24]

From the above results, it was found that the odor of the content water had a correlation with the amount of organic substances contained in the water. (Reference Example 2: Type of resin and TOC value) Using the resin raw materials described in Production Example 5, pellets of the resin composition (I) containing no radical inhibitor were prepared. Further, pellets of a resin mixture containing no radical inhibitor were prepared using two of the resin raw materials described in Example 5. The TOC values of these pellets and raw resin pellets were measured after 7 days by the method shown in Reference Example 1. The results are shown in Table 25.

[0171]

[Table 25]

Under the condition of melt-kneading at 260 ° C., the TOC value is low for the three kinds of raw material resins, the mixed resin of PET and EBM, and the mixed resin of EBM and 1706, and the mixed resin of PET + EBM + 1706 and PET + 1706 The high TOC value revealed that TOC was not caused by simple thermal decomposition. (Reference Example 3: Metal element analysis in PET resin) Elemental analysis of a commercially available PET resin confirmed that the following metal elements were contained (units in the table are mg / Kg) (Table 26)

[0173]

[Table 26]

(Reference Example 4: Metal element content in PET resin and TO
(C value) Using PET resin C shown in Table 26 and PET resin D obtained by adding 200 ppm of germanium oxide to PET resin C, the resin pellets were obtained by the method described in Production Example 5 without adding a radical inhibitor. Prepared. The TOC value of the pellet was measured after 7 days using the method of Reference Example 1.
5ppm from resin pellets prepared using
16ppm TOC from resin pellets prepared using
Was observed, confirming that germanium oxide accelerates the decomposition of the resin.

Example 1 A cold-rolled steel sheet having a thickness of 0.18 mm was electrolytically degreased and pickled by a usual method, and then CrO ₃ : 100 g / l, Na
F: Using a chrome plating bath of 5 g / l, bath temperature: 45 ° C,
100 mg / m ² of chromium metal was plated at a current density of 50 A / dm ² . That is, a chromium plating layer (2 ″) was formed. Immediately thereafter, stannous sulfate 5 g / l (as tin ion), sulfuric acid 20 g / l, ethoxylated α-naphthol: 5 g / l
1, bath temperature: 45 ° C tin plating bath, chrome plating layer
A current of 0.45 clones / dm ² was applied to the top of
A tin plating layer (6 ′) of 0 mg / m ² was formed. Subsequently, CrO ₃ : 30 g / l, sulfuric acid: 0.20 g / l, bath temperature:
Using a post-treatment bath at 60 ° C., electricity of 4 clones / dm ² was applied to the upper part of the tin plating layer (6 ′), and a 10 mg / m ² chromium plating layer (2 ′ ″) and 8 mg / m 2 were applied. Chromium ² hydrated oxide layer (3 '')
Was produced. Further, the film obtained in Production Example 7 was heat-sealed at 250 ° C. on the chromium hydrated oxide layer (3 ″) of the original plate.

(Example 2) Formation of tin diffusion layer A cold-rolled steel sheet having a thickness of 0.18 mm was plated with 200 mg / m ² of tin on both sides, and was subjected to an annealing furnace at 600 to 750 ° C for 30 seconds to 3 minutes. Inside, the plated tin was diffused to the steel sheet surface. Thereafter, in the same manner as in Example 1, 40 mg / m ² of chromium metal was plated (a chromium plating layer (2 ″) was formed). Then, as in Example 1, a tin plating layer of 100 mg / m ² was used in a tin plating bath.
(6 ′) was formed, and subsequently, a chromium plating layer (2 ′ ″) of 32 mg / m ² and 15 mg / m ² were formed using the same post-treatment bath as in Example 1.
² of hydrated chromium oxide layer 'the tin-plated layer (6 (3'') to produce a master plate having formed on). Further production examples on this original plate
The film of No. 7 was heat-sealed at 250 ° C.

Example 3 Chromium Diffusion Layer Formation A cold-rolled steel sheet having a thickness of 0.18 mm was subjected to 50 mg / m ² chromium plating on both sides, and then subjected to an annealing furnace at 600 to 750 ° C. for 30 seconds to 3 minutes. Chromium metal diffused into the surface of the steel sheet. Subsequently, in the same chrome plating bath as in Example 1, 100 mg / m ² of metal chromium was immediately plated on both sides of the plate (a chromium plating layer (2 ″) was formed). Then, a tin plating layer (6 ′) of 500 mg / m ² was formed on one side in a tin plating bath as in Example 1, and then a 10 mg / m ² chromium was formed using the same post-treatment bath as in Example 1. An original plate having a plating layer (2 ′ ″) and a chromium hydrated oxide layer (3 ″) of 8 mg / m ² formed on a tin plating layer (B) was produced. Further, the film of Production Example 7 was bonded to the chromium hydrated oxide layer (3 ″) of the original plate by heat fusion.

Example 4 Formation of Nickel Diffusion Layer A cold-rolled steel sheet having a thickness of 0.18 mm was subjected to nickel plating of 100 mg / m ^{2 on} both sides, and was subjected to an annealing furnace at 600 to 750 ° C. for 30 seconds to 3 minutes. Ni diffused into the surface of the steel sheet. Subsequently, 300 mg / m ² of metallic chromium was plated in the same chromium plating bath as in Example 1 (a chromium plating layer (2 ″) was formed). Immediately thereafter, as in Example 1, 800 m in a tin plating bath
g / m ² of tin plating layer (6 ′) was formed on one side, and subsequently 200 mg / m ² of chromium plating layer (2 ′ ″) and 40 mg / m ² using the same post-treatment bath as in Example 1. ² Chromium hydrated oxide layer
(3 ″) was produced on a tin plating layer (6 ′) to produce an original plate. Further, the film of Production Example 7 was adhered to the chromium hydrated oxide layer (3 ″) of the original plate by heat fusion.

Example 5 Chromium-tin Diffusion Layer Formation A cold rolled steel sheet having a thickness of 0.18 mm was plated with 100 mg / m ² of chromium, and then 200 mg / m ² of tin was plated thereon.
A chromium-tin diffusion layer was formed on the surface of the steel sheet in an annealing furnace under heat treatment conditions of 600 to 750 ° C and 30 seconds to 3 minutes. Thereafter, in the same manner as in Example 1, 100 mg / m ² of metal chromium was plated (a chromium plating layer (2 ″) was formed). Immediately thereafter, as in Example 1, a tin plating layer of 1000 mg / m ^{2 in} a tin plating bath.
(6 ′) was formed, and subsequently, a chromium plating layer (2 ′ ″) of 8 mg / m ² and 20 mg / m ² were formed using the same post-treatment bath as in Example 1.
² of hydrated chromium oxide layer 'the tin-plated layer (6 (3'') to produce a master plate having formed on). Further production examples on this original plate
The film of No. 7 was bonded by heat fusion.

(Example 6) Formation of nickel-tin diffusion layer A cold rolled steel sheet having a thickness of 0.18 mm was coated with 150 mg / m2.^TwoNickel
And then add 150mg / m^TwoTinned
And heat treatment at 600-750 ° C for 30 seconds to 3 minutes in an annealing furnace.
With this, a nickel-tin diffusion layer was formed on the surface of the steel sheet. That
Later, as in Example 1, 200 mg / m^TwoChrome metal
(A chromium plating layer (2 '') was formed). Moreover
Immediately thereafter, as in Example 1, 1800 mg / m in a tin plating bath^Twoof
A tin plating layer (6 ') was formed on one side, and subsequently, Example 1
30mg / m using the same post-treatment bath as ^TwoChrome plating layer
(2 '' ') and 15mg / m^TwoChromium hydrated oxide layer (3 '')
An original plate formed on the plating layer (6 ′) was manufactured. More
The film of Production Example 7 was bonded to the original plate by heat fusion.

Example 7 Formation of Nickel-Chromium Diffusion Layer A cold-rolled steel sheet having a thickness of 0.18 mm was plated with 100 mg / m ² of nickel, and then 100 mg / m ² of chromium was plated thereon. A nickel-chromium diffusion layer was formed on the surface of the steel sheet in an annealing furnace under heat treatment conditions of 750750 ° C. for 30 seconds to 3 minutes. Thereafter, in the same manner as in Example 1, 150 mg / m ² of chromium metal was plated (a chromium plating layer (2 ″) was formed). Immediately thereafter, as in Example 1, 500 mg /
Then, a tin plating layer (6 ′) of m ² was formed on one side, and then a 100 mg / m ² chromium plating layer (2 ′ ″) and a 8 mg / m ² Chromium hydrated oxide layer
(3 ″) was produced on a tin plating layer (6 ′) to produce an original plate. Further, the film of Production Example 7 was bonded to this original plate by heat fusion.

Example 8 Nickel-Chromium-Tin Diffusion Layer Formation A cold-rolled steel sheet having a thickness of 0.18 mm was nickel-plated on both sides at 150 mg / m ² , and then 150 mg / m ² chromium plating thereon. And further subjected to tin plating of 300 mg / m ² , and a nickel-chromium-tin diffusion layer was formed on the surface of the steel sheet in an annealing furnace under heat treatment conditions of 600 to 750 ° C. and 30 seconds to 3 minutes. . Thereafter, in the same manner as in Example 1, 30 mg / m ² of chromium metal was plated (a chromium plating layer (2 ″) was formed). Immediately thereafter, as in Example 1, 50 mg / m in a tin plating bath.
^Then, a tin plating layer (6 ′) was formed on one side, and then a 15 mg / m ² chromium plating layer (2 ′ ″) and a 5 mg / m ² chromium layer were formed using the same post-treatment bath as in Example 1. Hydrated oxide layer (3 '')
Was produced on a tin plating layer (6 ′). Further, the film of Production Example 7 was bonded to this original plate by heat fusion.

(Example 9) A 100 mg / m ² chromium plating layer (2) and a 12 mg / m ² chromium hydrated oxidation were applied to a cold-rolled steel sheet having a thickness of 0.18 mm using the chromium plating bath of Example 1. Material layer (3)
Was produced. Further, the resin film of Production Example 7 was bonded to the original plate by heat fusion.

Example 10 A tin-plated layer (6) of 1300 mg / m ² was formed on a cold-rolled steel sheet having a thickness of 0.18 mm by using the tin plating bath of Example 1. Using the treatment bath, an original plate having a 13 mg / m ² chromium plating layer (2 ′) and a 9 mg / m ² chromium hydrated oxide layer (3 ′) was produced. Further, the resin film of Production Example 7 was bonded to the original plate by heat fusion.

Table 27 shows a list of examples of the present invention. Table 27 also shows the evaluation results.

[0186]

[Table 27]

The adhesion amount of chromium metal and hydrated chromium oxide was measured by the following method. Metal chromium adhesion amount A 5% NaOH aqueous solution was used as an electrolytic solution, and the amount was measured by an electrolytic test method described in JIS H8501. Chromium hydrated oxide adhesion amount The chromium adhesion amount of the plated plate (total of metal chromium and chromium hydrated oxide) is measured by the fluorescent X-ray test method described in JIS H 8501. Immersion in a 30% aqueous NaOH solution for 10 minutes to remove hydrated chromium oxide,
The amount of deposited metal chromium was measured by a fluorescent X-ray test method described in JIS H 8501. The difference between the chromium deposition amount and the metal chromium deposition amount was defined as the chromium hydrated oxide deposition amount.

Further, the adhesion amounts of tin, chromium metal and chromium hydrate oxide were measured by the following method. Tin adhesion amount It was measured by an electrolytic test method described in JIS H 8501 using a 1N aqueous HCl solution as an electrolytic solution.

Adhesion amount of metal chromium [0189] Using a 0.1 mol / l aqueous solution of sodium hydrogen phosphate as an electrolytic solution, the amount was measured by an electrolytic test method described in JIS H8501. Chromium hydrate oxide adhesion amount The chromium adhesion amount (total of metal chromium and chromium hydrate oxide) of the plating plate is measured by the fluorescent X-ray test method described in JIS H 8501, and then the plating plate is heated to 100 ° C. After immersion in a 20% NaOH aqueous solution for 2 minutes to remove chromium hydrated oxide,
The amount of deposited chromium metal was measured by a fluorescent X-ray test method described in SH8501. The difference between the chromium deposition amount and the metal chromium deposition amount was defined as the chromium hydrated oxide deposition amount.

Further, the characteristics in Table 27 were evaluated by the following methods. (1) Film Adhesion The sample on which the resin film was laminated was processed into a deep drawing can with a drawing ratio of 2.8. The film adhesion was evaluated based on the presence or absence of peeling of the film from the flange after processing. (2) .Corrosion resistance After making the can under the same conditions as described in the section on film adhesion in (1) above, the center of the can body was cut out, and a fine dent was given to the film by drop dent with a hard ball at 5 ° C. After that, 1.
The amount of iron eluted after immersion in a model test solution of 5% citric acid + 1.5% salt at 38 ° C. for one week was measured.

The resin-coated metal plate and the resin-coated metal container of the present invention can be suitably used as a metal container excellent in storability, flavor, adhesion and corrosion resistance.
In addition, since the resin-coated metal plate of the present invention has the surface of the metal plate coated with resin in advance, it is possible to omit the painting process at the customer, which also contributes to the saving of the process and the cost at the customer. It has the effect that can be done.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing one embodiment of a resin-coated metal plate of the present invention.

FIG. 2 is a schematic sectional view showing one embodiment of the resin-coated metal plate of the present invention.

FIG. 3 is a schematic sectional view showing one embodiment of the resin-coated metal plate of the present invention.

[Explanation of symbols]

 1… metal plate 2, 2 ′, 2 ″, 2 ″ ′ chrome plating layer 3, 3 ′, 3 ″ chromium hydrated oxide 4… resin composition layer 5, 5 ′… diffusion layer 6, 6 '… tin plating layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 67/00 C08L 101/00 4K024 101/00 101/12 4K041 101/12 C23C 28/00 C C23C 28 / 0025 C5D 5/26 K C25D 5/26 BD 11/38 301A 11/38 301 B65D 1/00 B (72) Inventor Tadaaki Ochiai 5-3 Tokaicho, Tokai City, Aichi Prefecture Nippon Steel Corporation Nagoya Corporation Inside the ironworks (72) Inventor Hiroshi Ueshiro 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation Technology Development Division (72) Inventor Hiroshi Oishi Technology development 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation F-term in head office (reference) 3E033 AA06 BA07 BA17 BB08 CA01 CA07 CA11 CA16 3E061 AA15 AB06 AB07 AB13 AC09 AD01 AD04 AD06 3E062 AA04 JA01 JA07 JB11 JB21 JB25 JC02 JC04 JD04 JD06 4F1 00 AA22C AB01A AB03 AB13B AB13E AB16E AB21E AB31E AH02D AH02H AH04D AH04H AH08D AH08H AK02D AK41D AK42 AK65 AK70 AL05D AL09D AN00D BA04 BA05 BA07 BA10A BA10D CA30D DA01 DE04D EH71B EH71C EH71E GB16 JA13B JA13C JA13E JB01 JB02 JD02 JJ03 JK06 JK10 JL00 JL01 YY00B YY00C YY00D YY00E YY00H 4J002 AC033 AC063 AC073 AC083 AC113 BB033 BB053 BB062 BB072 BB082 BB123 BB153 BB173 BB192 BB232 BC033 BC043 BC062 BC072 BE022 BF022 BF032 BG012 BG042 BG052 BG072 BH012 BH022 BN123 BN143 BN153 BP013 CD192 CF011 CF031 CF041 CF051 CF061 CF071 CF081 CF091 CF101 CF103 CF161 CF173 CF181 CL003 CP033 EJ016 EJ026 EJ036 EN066 EV066 EV076 EW066 FA040 FD010 FD090 FD100 FD180 GF00 GG01 GH02 4K024 AA02 AA03 AA07 AB01 AB02 BA03 BB21 BC01 DB01 DB02 DB04 DB06 DB10 GA04 GA07 GA12 4K044 AA02 CA02 BC02 BA02 BC02 BA02 CA62

Claims (15)

[Claims] 1. A resin-coated metal plate for a container, wherein a two-layer coating of chromium metal and chromium hydrated oxide is formed on at least the surface of the base metal plate on the inner surface side of the container from the metal plate side, and polyester A resin-coated metal plate comprising a resin (A), a vinyl polymer (B) containing at least 1% by mass of a unit having a polar group, and a resin composition layer containing a radical inhibitor. 2. The plating amount of metallic chromium is 10 to 300 mg / m.
² and chromium hydrated oxide plating amount is 1 ~
^2. The resin-coated metal plate according to claim 1, wherein the amount is 50 mg / m ² . 3. A three-layer coating of tin, chromium chromium, and chromium hydrated oxide is formed on at least the surface of the base metal plate on the inner side of the container in the resin-coated metal plate for a container from the metal plate side. A resin-coated metal plate comprising a polyester resin (A), a vinyl polymer (B) containing at least 1% by mass of a unit having a polar group, and a resin composition layer containing a radical inhibitor. 4. The tin plating amount is 0.1 to 10 g / m.^Two,metal
Chromium plating amount is 1 to 200mg / m^TwoAnd chromic acid
Chromium equivalent of 1 to 50mg / m ^TwoIs special
4. The resin-coated metal plate according to claim 3. 5. A resin-coated metal plate for a container, wherein a four-layer coating of chromium metal, tin, chromium metal and hydrated chromium oxide is formed on at least the surface of the base metal plate on the inner surface side of the container from the metal plate side. And a resin-coated metal layer comprising a polyester resin (A), a vinyl polymer (B) containing at least 1% by mass of a unit having a polar group, and a resin composition layer containing a radical inhibitor. Board. 6. The plating amount of metal chromium is 10 to 300 mg / m.
^2, coating weight of tin 50~5000mg / m ^2, the resin of claim 5, wherein the plating amount of coating weight of metallic chromium is 1 to 300 mg / m ² and hydrated chromium oxide is 1 to 50 mg / m ² Coated metal plate. 7. The metal plate according to claim 1, wherein a diffusion layer in which any one of nickel, tin, and chromium or an alloy thereof is diffused into the metal plate is formed on a surface layer of the metal plate. The resin-coated metal plate as described in the above. 8. The resin-coated metal sheet according to claim 7, wherein the content of any one of nickel, tin, and chromium or an alloy thereof contained in the diffusion layer is 50 to 600 mg / m ² . 9. The resin composition further comprises a rubber-like elastic resin.
The resin-coated metal plate according to any one of claims 1 to 8, comprising (C). 10. The rubber-like elastic resin (C) has a structure in which it is finely dispersed in the polyester resin (A), and at least a part of the rubber-like elastic resin (C) is a vinyl polymer (B). 10. The resin-coated metal plate according to claim 9, which is a resin composition having an encapsulated structure. 11. The radical inhibitor is selected from a phenolic radical inhibitor, a phosphorus radical inhibitor, a sulfide radical inhibitor, and a nitrogen radical inhibitor.
The resin-coated metal plate according to any one of claims 1 to 10, wherein the resin-coated metal plate is at least one species. 12. The resin-coated metal plate according to claim 4, wherein the radical inhibitor is a phenolic radical inhibitor. 13. The components (A) and (B), or (A), (B) and
(C) A radical inhibitor is added in an amount of 0.001 to 100 parts by mass of the component.
12. The resin-coated metal plate according to claim 11, wherein the metal plate is contained in an amount of from 7 to 7 parts by mass. 14. A resin-coated metal container formed by molding the resin-coated metal plate according to any one of claims 1 to 13. 15. The resin-coated metal container according to claim 14, wherein the container is a can.