JP2001205771A - Method for manufacturing resin-coated metal plate and resin-coated metal container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a resin-coated metal plate obtained by being coated with a resin film having impact resistance, chemical resistance, moldability, heat resistance, gas barrier properties and adhesive properties with a metal and particularly having good flavorfulness and a method for manufacturing a resin-coated metal container made of the resin-coated plate. SOLUTION: The resin-coated metal plate is obtained by the steps of throwing a resin composition containing a polyester resin (A), a vinyl polymer (B) containing a unit having a polar group of 1 wt.%; or more and a radical inhibitor or a polyester resin (A), a vinyl polymer (B) having a unit including a polar group of 1 wt.%; or more, a rubber-like elastic resin (C) and a radical inhibitor in a non-molten state in a hopper of an extruder with a T-die, then extruding a film from the T-die, and heat press bonding the film to at least one surface of the metal plate.

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. Less eluted, resin-coated metal plate coated on one or both sides of the metal plate with a film-like molten resin or resin film using a resin composition particularly excellent in flavor, furthermore,
The present invention relates to a resin-coated metal container formed by molding the resin-coated metal plate.

[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, it was necessary to pay particular attention to the manufacturing conditions such as temperature control.

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. Generally, organic low-molecular-weight substances are generated from resins as raw materials remaining in the resin, low-molecular components having a low degree of polymerization, and decomposition products generated during resin production or can-making to the contents of the container. Elution is possible. 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 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 evolution of molecular material 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. However, 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 resin and less leaching of organic substances from resin, and particularly to flavor. Provided is a resin-coated metal plate coated with a resin coating obtained by laminating a film-like molten resin or a resin film using an excellent resin composition, and further provides a resin-coated metal container formed by molding the resin-coated metal plate. That is.

[0008]

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, in the present invention, the polyester resin (A) and the unit having a polar group
% Or more of a vinyl polymer (B) and a resin composition containing a radical inhibitor in a non-molten state into a hopper of an extruder with a T die, and melt-kneaded in the extruder,
Then, the molten resin is extruded from the T-die, the molten resin is supplied in a film form to at least one surface of the metal plate, and then the film-like molten resin is cooled and adhered to the metal plate to obtain a resin-coated metal plate. A method for producing a resin-coated metal sheet, or a non-molten state, is put into a hopper of an extruder equipped with a T die, which is melted and kneaded in the extruder.
Forming a film after extruding the kneaded molten resin from the die, by thermocompression bonding the film to at least one side of the metal plate, a method for producing a resin-coated metal plate, characterized in that a resin-coated metal plate is obtained. I do. The present invention further provides a method for producing a resin-coated metal container obtained by molding the resin-coated metal plate.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A method for producing a resin-coated metal plate and a method for producing a resin-coated metal container according to the present invention will be described below. First, the resin composition used in the present invention contains a polyester resin (A), a vinyl polymer (B) containing at least 1% by mass of a unit having a polar group, and a radical inhibitor. Although the composition of these resins is not particularly limited,
100 parts by mass of polyester resin (A), vinyl polymer
(B) is preferably 1 to 50 parts by mass, and a radical inhibitor is preferably added to 100 parts by mass of the resin composition.
The resin composition contains 1 to 7, more preferably 0.005 to 1 part by mass. 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 intrinsic viscosity of the polyester resin (A) used in the present invention is 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 which is 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 preferable combination of these dicarboxylic acid compounds and diol compounds is 50 to 95 mol% of terephthalic acid, 50 to 5 mol% of isophthalic acid and / or orthophthalic acid. And a diol compound of a glycol having 2 to 5 carbon atoms. 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 metal cations such as ²⁺ , Mn ²⁺ , Ti ³⁺ , Zr ³⁺ , Sc ^{3+ and the} like.

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 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 and the like can be mentioned. -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 And aromatic vinyl monomers such as addition polymer units of styrene monomers such as α-methylstyrene.

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 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. Thus, part or all of the carboxyl groups in the copolymer are sodium, potassium,
Examples include resins neutralized with metal ions such as 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.

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 (measured by differential thermal analysis insertion (DSC) with a Tg, a sample amount of about 10 mg, and a heating rate of 10 ° C./min.) Of 50 ° C. or less is high in terms of high performance in improving impact resistance. A vinyl polymer (B) having a Young's modulus of 1000 MPa or less at room temperature and a breaking elongation of 50% or more is preferred. Examples of the preferred vinyl polymer (B) used in the present invention include methacrylic acid, acrylic acid, and polar olefins in which some or all of these acidic functional groups are neutralized with metal ions, methyl acrylate, acrylic acid Examples include ethyl, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, maleic anhydride, and a copolymer of vinyl acetate and an α-olefin.

[0026] In particular, ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-vinyl acetate copolymers, and acidic functional groups in these copolymers are more preferable 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 part 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-
Examples include a maleic anhydride copolymer, a butene-ethylene-glycidyl methacrylate copolymer, and a 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 may not be exhibited. In order to ensure impact resistance at low temperatures, Tg should be 10 ° C or less, more preferably
It is preferably -30 ° C or lower. In order to ensure more reliable impact resistance, the Young's modulus at room temperature should be 100MPa.
Below, more preferably 10 MPa or less, elongation at break is 100% or more, more preferably 300% or more,
preferable.

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), and polyisoprene ( IPR), diene elastomers such as polybutadiene (BR), styrene-butadiene-styrene copolymer (SBS) and hydrogenated products thereof (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 preferred 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 polyethylene, polypropylene, polybutene, polypentene, polyhexene and polyoctenylene, which are homopolymers of α-olefins. 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 the polar vinyl monomer 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 polyolefin resins for imparting impact strength 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 may decrease, and the resin composition of the present invention may decrease the film forming property. 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. Further, the rubber-like elastic resin (C) encapsulated with the vinyl polymer (B) is at least 80% of the interface of the rubber-like elastic resin (C), preferably
95% or more is covered with vinyl polymer (B), and the direct contact area between polyester resin (A) and rubbery elastic resin (C) is 20%
The structure is less than. 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 the molten resin extruded from the T-die onto the metal plate surface is bonded while cooling, or the molten resin extruded from the T-die Even when a solidified film is formed by thermocompression bonding, the adhesion between the resin composition and the metal plate can be sufficiently ensured.

It is not necessary that all particles of the rubber-like elastic resin (C) are encapsulated with the vinyl polymer (B), and at least 70% or more of the rubber-like elastic resin (C) by volume ratio is a vinyl polymer. What is necessary is just to encapsulate in the 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 are not more than 20% by volume of the entire vinyl polymer (B).
It is desirable that the equivalent spherical equivalent diameter be 1.0 μm or less. 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 (Resin 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 γ (Resin B) / (Resin A)> 0, so the non-polar vinyl monomer (Mon
(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 is shown 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.

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 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 method described later. Specifically, polyester resin (A), vinyl polymer (B), and rubber-like elastic resin body having appropriate difference in interfacial tension
By melt-kneading (C) at a predetermined temperature, for example, 200 to 350 ° C. by using an extruder with a die, 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), a method of dispersing the rubber-like elastic resin body with the vinyl polymer (B) is used. 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 because it has 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, the acrylate polymer constituting the core is preferably 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.

Since the core-shell type rubber-like elastic body has a soft rubber-like material at the core, the resin constituting the shell needs to be hard from the viewpoint of 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 within 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 bonding 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 rubber-like elastic body desirably contains a rubber-like polymer core 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.

In the first stage polymerization, the above-mentioned unit monomers constituting the core are radically polymerized. 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).

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 7 parts by mass, the effect of reducing the amount of elution saturates substantially, resulting in excessive addition, which is uneconomical. In addition, the resin properties such as the elastic modulus and adhesion of the resin are reduced. Not preferred. To achieve higher effects,
A radical inhibitor was added to 100 parts by mass of the resin composition.
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 vinyl polymer and the polyester resin, the content before kneading decreases.

The 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 diffusibility of the radical inhibitor in the resin, the molecular weight is 50.
It is preferably at most 00. 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-based radical inhibitor include bis (2-dodecylphenyl) amine, bis (3-octylphenyl) amine, bis (4-octylphenyl) amine and the like. 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 materials, the amount of the radical inhibitor contained in the resin composition may satisfy the 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 of 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. Also, once the raw material resin containing no radical inhibitor is mixed to prepare the above resin composition, it may be added by adding the radical inhibitor into a hopper of an extruder when preparing the resin composition.

It is necessary to suppress the formation of pinholes and fish eyes in order to improve the formability, appearance, and rust resistance. 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. Further, a method of removing impurities by passing through a screen in at least one place of a melt extrusion step such as kneading and / or film formation is also useful.

The resin composition of the present invention may contain a fiber reinforcing agent such as glass fiber, metal fiber, potassium whisker, carbon fiber, etc. 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, inorganic white pigments such as titanium dioxide, calcium carbonate and barium sulfate are used for the purpose of imparting white light-shielding properties for printing (for example, JP-A-6-49234). . As the plasticizer, 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 JP-A-5-222357 for the purpose of preventing winding of a film around a roll during film formation and prevention of electrostatic damage such as adhesion of dirt on the film surface. A method of applying an antistatic agent as described above can be applied as needed. In addition, antibacterial agents, JP-A-11-48431,
A conventionally known antibacterial agent disclosed in JP-A-11-138702 may be added as necessary.

In the method of the present invention, the above resin composition
(A dry blended mixture) is charged in a non-molten state into a hopper of an extruder with a T-die. The polymer components in the resin composition, that is, the components (A) and (B), or the components (A), (B) and (C) can be added without being previously blended. And (B) component, (A) and (C) component, (B)
The components (C) and (A), (B) and (C) are mixed in advance by dry blending using a tumbler blender, Henschel mixer, V-type blender, etc., and then put into the hopper. It is more suitable for uniform dispersion of each component. In that case, at least a part of the components to be dry-blended may be pellets. The radical inhibitor may be added to other components as described above, or may be added to the hopper. The same applies to other additives. That is, these resin compositions contain at least the desired components when melt-kneaded in the extruder, but the melt-kneading can be performed by a conventional method. The extruder is not particularly limited as long as it has a T die, and a single-screw or twin-screw extruder is preferably used.
From the viewpoint of the kneading function and the extrusion performance, a two-shaft in which two screws rotate in the same cylinder is more preferable. The biaxial rotation directions may be different directions or the same direction. The melt-kneaded resin composition is, as described above, a polyester resin (A), a vinyl polymer (B), or a rubber-like elastic resin (C) encapsulated with a vinyl polymer (B).
Are finely dispersed.

Next, the melt-kneaded product is extruded as a molten resin from a T-die into a film on at least one surface of a metal plate, cooled, and can be bonded to the metal plate. It is preferable from the viewpoint of the process. This melt-kneaded product is extruded from a T die,
A film is formed and the film is thermocompression bonded to at least one side of a metal plate. The formed film is preferably subjected to thermocompression bonding directly (as it is) without storage once from the viewpoint of saving steps. The T die is not particularly limited as long as it extrudes the above-mentioned melt-kneaded product from a narrow slit-shaped gap, and a lip is usually used for flow rate adjustment.
The film may be unstretched or may be stretched in one or two directions. It is preferable to heat the metal plate for supplying the molten resin in advance or to heat the metal plate for thermocompression bonding of the film in advance because the adhesion of the resin composition (C) is further stabilized. Although the metal plate to be coated is not particularly limited, tinplate, thin tin plated steel sheet, electrolytic chromic acid-treated steel sheet (tin-free steel),
Nickel-plated steel sheet for cans, hot-dip galvanized steel sheet, hot-dip zinc-iron alloy coated steel sheet, hot-dip zinc-aluminum-magnesium alloy coated steel sheet, hot-dip aluminum
-Hot-dip steel sheet such as silicon alloy-coated steel sheet, hot-dip lead-tin alloy-coated steel sheet, electro-galvanized steel sheet, electric zinc
-Nickel plated steel sheet, electric zinc-Iron alloy plated steel sheet,
Examples include surface-treated steel sheets such as electroplated steel sheets such as electroplated zinc-chromium alloy-plated steel sheets, cold-rolled steel sheets, and metal sheets such as aluminum, copper, nickel, zinc, and magnesium. Further, the coating on the metal plate may be either one side or both sides. Further, the thickness of the coating film when the resin composition of the present invention is coated on a metal plate is not particularly limited, but is 1 to 300.
μm is preferred. If the thickness is less than 1 μm, the impact resistance of the coating may not be sufficient, and if it exceeds 300 μm, the economy is poor. The surface roughness of the film is arbitrarily set to 1 mm
It is preferable that the result of the length measurement be 500 nm or less in Rmax. If it exceeds 500 nm, bubbles may be involved when coating by thermocompression bonding.

Further, in order to improve the fixability to a film and the corrosion resistance, the metal plate is made of metal chromium,
A plating layer of chromium oxide, tin or the like can be formed on the surface. When a resin-coated metal plate is used for a container of a can body, it is preferable to provide a primer layer on the plating layer.

By combining this primer layer, even in a can body which has been subjected to severe molding such as drawing and ironing, the impact resistance at low temperatures is excellent, so that the film hardly cracks at the time of impact and the base metal is melted. I rarely give it out. Further, since the flavor hardly changes even after retort sterilization, it is suitable as a resin-coated metal plate for can making. Examples of such a primer layer include phenol-epoxy paints 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.
% Of a curing agent resin and 0.05 to 10% by weight of a curing catalyst (JP-A-5-269917). In the present invention, the method of the thermocompression bonding is not particularly limited, and according to the method of the present invention, sufficient impact resistance can be exhibited without inclining the crystallinity inside the coated film. Due to the high impact properties of the resin composition used, high impact properties are exhibited even when used without stretching. Thermocompression bonding to metal is possible without stretching, and the number of steps can be reduced. In the case of thermocompression bonding to metal 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 further enlarged and high-speed production can be performed. Further, since temperature control for controlling the degree of crystallinity during film formation and thermocompression bonding is easy, it is possible to manufacture a product with stable performance.

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 using at least the above resin film to form a single layer or a multilayer. 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, there is a method in which a multilayer film of the resin film of the present invention and another resin film or a resin composition film is manufactured using a multilayer T die, and this is thermocompression-bonded.

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 plate of the present invention only needs to be coated with the resin film of the present invention.If necessary, a known resin film may be laminated on the lower layer and / or upper layer of the resin film of the present invention to cover the metal plate. You may. Further, a known adhesive can be laminated between the metal plate and the resin film of the present invention. Examples of the adhesive include a polyester resin aqueous dispersant disclosed in JP-B-60-12233, an epoxy adhesive disclosed in JP-B-63-13829, and JP-A-61-149341. Examples include polymers having various functional groups disclosed herein.

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. Specifically, draw ironing molding, draw redraw molding, stretch draw molding,
Stretch draw ironing molding and the like are mentioned,
Any resin-coated metal container using the resin-coated metal plate of the present invention may be used, and the forming method is not limited to the above-described forming method.

The resin composition used 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.

In addition to the polyester resin (A), the vinyl polymer (B) containing at least 1% by weight of a unit having a polar group, and the radical inhibitor, the resin composition used in the present invention may be a rubber-like elastic resin body. It is a resin composition containing (C), and particularly has a structure in which a rubber-like elastic resin body (C) encapsulated with a vinyl polymer (B) in a polyester resin (A) is finely dispersed, The impact resistance of the polyester resin (A) can be improved by the rubber-like elastic resin body (C), and the rubber-like elastic resin body (C) is encapsulated by the vinyl polymer (B). And rubber-like elastic resin body (C)
In addition to improving the compatibility with the resin and improving the impact resistance, the direct contact between the metal plate and the rubber-like elastic resin body (C) can be prevented to ensure the adhesion between the metal plate and the resin composition. Are better. Further, the addition of the radical inhibitor suppresses the decomposition of the resin composition, 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 widely used for metal containers such as metal cans, members for housing of home electric appliances and metal furniture, automobile members such as automobile outer panels, and interior / exterior members for building materials such as interior walls and doors. . 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.

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.

[0088]

Next, the present invention will be described more specifically based on examples and comparative examples. In the following Examples and Comparative Examples, as the polyester resin (A), polyethylene terephthalate (PET) [RN163 manufactured by Toyobo Co., Ltd.], polybutylene terephthalate (PBT) [1401-X04 manufactured by Toray Industries, Inc.], having a polar group Vinyl polymer (B) having units of 1% by weight or more
As an ethylene ionomer [Himilan 1706, 1707 manufactured by DuPont-Mitsui Co., Ltd.]; an ethylene-methacrylic acid copolymer [Nucrel N103 manufactured by DuPont-Mitsui Co., Ltd.]
5], and polybutyl acrylate-polymethyl methacrylate copolymer (M
BA) [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].

Examples 1 to 15 Each of the resins shown in Table 1 and the radical inhibitor tetrakis [methylene (3,5-di-t-butyl-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. A part of this mixture was melt-kneaded at 260 ° C. with a twin-screw extruder to obtain resin composition pellets containing a radical inhibitor. 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. Rubbery elastic resin
When (C) was added, the dispersion state of the vinyl polymer (B) and the rubbery elastic resin (C) in the polyester resin (A) was analyzed by a transmission electron microscope. As a result, when the rubber-like elastic resin (C) was not added, the equivalent sphere equivalent diameter of the vinyl polymer (B) was 1 μm or less as shown in Table 1 and was finely dispersed in the polyester resin (A). Was. Rubbery elastic resin
When (C) was added, 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 As shown in Table 1
It was finely dispersed in the polyester resin (A) at 1 μm or less.

[0090]

[Table 1]

The remainder of the mixture obtained by the above dry blending was melt-kneaded at 280 ° C. using a twin screw extruder equipped with a T die, and a 30 μm thick film was obtained with an extruded T die (extrusion temperature: 280 ° C.). ). This film was heated to 250 ° C
It was bonded to both sides of 0.25 mm thick tin-free steel, and rapidly cooled to 100 ° C. or less within 10 seconds by water cooling.

The room-temperature resin-coated metal plate thus obtained was evaluated for each of the following items by the following evaluation methods: fragrance retention, taste retention, adhesion, room temperature impact resistance, and low temperature impact resistance. Was done. 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 placed 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

[0094]

[Table 2]

<Adhesion, Impact Resistance at Room Temperature and Impact Resistance at Low Temperature>
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 2 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.

[0097]

[Table 3]

(Examples 16 to 28) Composition ratio of each resin shown in 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.
Each of the various radical inhibitors shown in (1) was added in an amount of 0.1 part by mass with respect to 100 parts by mass of the resin composition, and a resin composition pellet was prepared from a part of the dry blend mixture. After cutting out an ultra-thin section from the resin composition with a microtome, staining with ruthenic acid, the vinyl polymer in the polyester resin (A)
The dispersion state of (B) was analyzed with a transmission electron microscope. As a result, the equivalent spherical equivalent diameter of the vinyl polymer (B) was the same as that of Example 2, and it was finely dispersed in the polyester resin (A) at 1 μm or less.

Using the remaining dry blend mixture,
Melt kneading at 0 ° C, and directly from the T die at the same extrusion temperature,
The molten resin is supplied in the form of a film to the surface of the metal plate, and the molten resin is cooled to prepare a resin-coated metal plate, which has good fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance. Each item was evaluated. Table 4 shows the results.

[0100]

[Table 4]

(Example 29) A mixture of the composition ratio of each resin shown in the above Example 5 (polyester resin (A): vinyl polymer (B): rubber-like elastic material (C) = 87: 3: 10) And the radical inhibitor tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane (resin pellets 100
(0.01% based on parts by mass), and dry-blended using a V-type blender. Put this mixture in a T-die with 2
The mixture was melt-kneaded at 260 ° C with a screw extruder to form a film 30 mm wide and 25 microns thick. 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. Rubbery elastic resin
When (C) was added, the dispersion state of the vinyl polymer (B) and the rubbery elastic resin (C) in the polyester resin (A) was analyzed by a transmission electron microscope. As a result, 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 0.6 μm.
And the resin was finely dispersed in the polyester resin (A). Using this film, a resin-coated metal plate was prepared in the same manner as in Example 5, and evaluated by the same evaluation method as in Example 5. Table 5 shows the results.

[0102]

[Table 5]

(Examples 30 to 42) Composition ratio of each resin shown in Example 5 (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, various radical inhibitors shown in Table 6 were added in an amount of 0.1 part by mass with respect to 100 parts by mass of the resin composition 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, 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 in Example 1. Yes,
It was finely dispersed in the polyester resin (A) at 1 μm or less.

Using the remaining dry blend mixture, a resin-coated metal plate was prepared in the same manner as described above, and each of the items of fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance was evaluated. An evaluation was performed. Table 6 shows the results.

[0105]

[Table 6]

(Examples 43 to 47) Composition ratio of each resin shown in the above Example 2 (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 from a part of the mixture. 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) is 0.5 μm or more and 1 μm or less, and the polyester resin (A)
It was finely dispersed inside.

Using the remaining mixture, a resin-coated metal plate is prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion,
Each item of the normal temperature impact resistance and the low temperature impact resistance was evaluated. Table 7 shows the results.

[0108]

[Table 7]

(Examples 48 to 52) Composition ratio of each resin shown in Example 6 (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).

The remaining mixture was melt-kneaded at 280 ° C., and the molten resin was supplied directly from a T-die at the same extrusion temperature to one side of the metal plate in the form of a film (about 30 μm in thickness). Using a twin-screw extruder with a T-die, the mixture was melt-kneaded at 280 ° C, extruded from a T-die into a cooling roll to form a solidified film (thickness: 20μm), then hot-pressed, and heated to 260 ° C at 0.18mm Each side of the thick tin-free steel was coated with a resin, cooled with water and rapidly cooled to 100 ° C. or less. Each item of fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance was evaluated. Table 8 shows the results.

[0111]

[Table 8]

(Example 53) Composition ratio of each resin shown in Example 2 (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 a part of the mixture was melt-kneaded at 260 ° C. using a twin-screw extruder 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. As a result, the equivalent spherical equivalent diameter of the vinyl polymer (B) was 0.7 μm and the polyester resin
(A) Finely dispersed therein.

The remaining dry blend mixture is used for 20
Melt kneading at 0 ° C, and directly from the T die at the same extrusion temperature,
Molten resin film directly on one side of metal plate (about 30μm thick)
On the other side, using a twin-screw extruder with T dies on the other side.
The mixture was melt-kneaded at 0 ° C and extruded from a T-die into a cooling roll to form a solidified film (thickness: 20μm).
Each surface of a 0.18 mm thick tin-free steel heated to 180 ° C. was coated with a resin, cooled with water and rapidly cooled to 100 ° C. or less.
Each item of fragrance retention, flavor retention, adhesion, room temperature impact resistance and low temperature impact resistance was evaluated. Table 9 shows the results.

[0114]

[Table 9]

(Example 54) Composition ratio of each resin shown in Example 5 (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 pellet and polyester resin (A) and rubber-like elastic resin (C) pellets are dry-blended using a V-type blender, and a part of this mixture is extruded using a twin-screw extruder.
The mixture was melt-kneaded at 260 ° C to prepare resin composition pellets.
After cutting out an ultra-thin section from the resin composition with a microtome, staining with ruthenic acid, 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 microscopy. Analyzed with a microscope. As a result, 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 0.5 μm.
m, it was finely dispersed in the polyester resin (A).

Using the remaining mixture, a resin-coated metal plate was prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion,
Each item of the normal temperature impact resistance and the low temperature impact resistance was evaluated. Table 10 shows the results.

[0117]

[Table 10]

Examples 55 to 58 Each of the resins shown in Table 11 and tetrakis [methylene (3,5-di-t-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. A part of 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 Examples 1 to 15, the equivalent spherical equivalent diameter of the dispersed particles was 0.3 μm or more and 1 μm or less as shown in Table 10, and the particles 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).

[0119]

[Table 11]

Further, a film was prepared from the remaining mixture in the same manner as in Examples 1 to 15 and bonded to both sides of a tin-free steel sheet having a thickness of 0.25 mm to evaluate the fragrance retention, taste retention, adhesion and impact resistance. did. Table 12 shows the results.

[0121]

[Table 12]

Examples 59 to 61 Tetrakis methylene (3,5-di-t-t-
Butyl-4-hydroxyhydrocinnamate)] methane
Dry blending was performed using a V-type blender. The mixing ratio of each resin is 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. A part of this mixture was melt-kneaded at 240 ° C. with a twin-screw extruder to obtain resin composition pellets. Examples 1 to 15
As a result of analyzing the dispersion state in the same manner as described above, the core-shell type rubber-like elastic body had an equivalent spherical equivalent diameter of 1 μm as shown in Table 13.
m or less, it was finely dispersed in the polyester resin (A).

[0123]

[Table 13]

Further, a film was prepared from the remaining mixture in the same manner as in Examples 1 to 15 (however, the extrusion temperature was 240 ° C.).
It was bonded to both sides of a 0.2 mm thick tin-free steel and evaluated for its fragrance retention, taste retention, adhesion and impact resistance.
Table 14 shows the results.

[0125]

[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. A portion of this mixture was extruded 230
The resulting mixture was melt-kneaded at a temperature of ° C. to obtain resin composition pellets. Example 1
As a result of analyzing the dispersion state in the same manner as in Examples 11 to 11, as shown in Table 15, the particles were finely dispersed in the polyester resin (A) at an equivalent sphere diameter of 1 μm or less. Rubbery elastic resin
(C) was 100% encapsulated with vinyl polymer (B).

[0127]

[Table 15]

Further, a film was prepared from the remaining mixture in the same manner as in Examples 1 to 15 and bonded to both sides of tin-free steel having a thickness of 0.25 mm to evaluate the fragrance retention, taste retention, adhesion and impact resistance. did. Table 16 shows the results.

[0129]

[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 the 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. A part of 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 Examples 1 to 15, the core-shell type rubber-like elastic body was finely dispersed in the polyester resin with an equivalent sphere equivalent diameter of 0.25 μm. Further, using the remaining dry blend mixture, a film was prepared in the same manner as in Examples 1 to 15 and bonded to both sides of a 2.5 mm-thick tin-free steel, and the fragrance retention, taste retention, adhesion and impact resistance were measured. evaluated. The results are shown in FIG.

[0131]

[Table 17]

Adhesion, room temperature impact resistance, and low temperature impact resistance are not changed, but are inferior in flavor retention and taste retention as compared with the case where a resin composition to which a radical inhibitor is added is used. 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 part by mass of 1,2,4-triazole was added to 100 parts by mass of the resin composition, and a resin composition pellet was prepared from a part of the dry blend. As a result of analyzing the dispersion state in the same manner as in Examples 1 to 15, the vinyl polymer (B) was finely dispersed in the polyester resin with an equivalent sphere equivalent diameter of 0.5 μm.

Using the remaining mixture, a resin-coated metal plate was prepared, and each of the items was evaluated for fragrance retention, taste retention, adhesion, room temperature impact resistance, and low temperature impact resistance. The results are shown in Table 18.

[0134]

[Table 18]

When a metal deactivator was used as an additive, no improvement in flavor 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. Resin composition pellets were prepared from a part of the mixture obtained by adding 0.1 parts by mass of 3- (N-salicyloyl) amino-1,2,4-triazole as an agent to 100 parts by mass of the resin composition. As a result of analyzing the dispersion state in the same manner as in Examples 1 to 15, rubber-like elastic resin (C)
Was 100% encapsulated in the vinyl polymer (B), and was finely dispersed in the polyester resin with an equivalent sphere diameter of 0.5 μm of the rubber-like elastic resin (C).

Using the remaining mixture, a resin-coated metal plate was prepared, and each of the items was evaluated for fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance. Table 19 shows the results.

[0137]

[Table 19]

When a metal deactivator was used as an additive, no improvement in flavor retention and flavor retention was observed. (Comparative Examples 12 and 13) Composition ratio of each resin shown in 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)] A resin composition pellet was prepared from a part of the mixture obtained by adding methane in the following proportions. 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. The equivalent spherical equivalent diameter of the vinyl polymer (B) is 0.3 μm or more
It was finely dispersed in the polyester resin (A) at 1 μm or less.

Using the remaining mixture, a resin-coated metal plate is prepared in the same manner as described above, and the scent retention, taste retention, adhesion,
Each item of the normal temperature impact resistance and the low temperature impact resistance was evaluated. Table 20 shows the results.

[0140]

[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 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 to each of the following proportions to prepare resin composition pellets from a part of the mixture obtained. 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 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 remaining mixture, a resin-coated metal plate is prepared in the same manner as described above, and the scent-retaining property, the taste-retaining property, the adhesion,
Each item of the normal temperature impact resistance and the low temperature impact resistance was evaluated. Table 21 shows the results.

[0143]

[Table 21]

It was found that when the added amount of the radical inhibitor 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
The PET layer: 20 μm, the refractive index of the PET layer in the film thickness direction: 1.526) was thermocompression-bonded on tin-free steel under the same conditions as in Examples 1 to 15 (so that the PBT layer adheres to the tin-free steel). Coating), adhesion and impact resistance of Examples 1-1
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 Examples 1 to 15, and the adhesion and impact resistance were measured in 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 Examples 1 to 15, and the adhesion and impact resistance were evaluated in the same manner as in Examples 1 to 15 (Table 22).

[0147]

[Table 22]

[0148] The resins obtained by these conventional methods could not obtain sufficient adhesion and impact resistance. (Examples 62 to 67, Comparative Examples 19 to 21) 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 II (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.

Δ; For 1 to 5 cans, whitening of the film was observed at the top of the can. X; Film breakage was observed in a part of the film for 6 or more cans. (2) Deep drawing workability II (Evaluation of film inside the can) ○; 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 (1.0% saline was added, 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: 3 or more cans showed a rust prevention test on the film surface inside the can of more than 0.1 mA. (3) Impact resistance For cans with good deep drawing, the samples were thoroughly filled with water, and 10 samples of each sample were dropped from a height of 10 cm onto a PVC tile floor, and then an ERV test was performed in the can. ;: All 10 cans had a current of 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.

[0153]

[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) At a composition ratio of 92: 8, polyester resin (A) and vinyl polymer (B)
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 Examples 1 to 15.
The results are shown in Table 24.

[0156]

[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: Resin Type and TOC Value) Using the resin raw materials described in 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.

[0158]

[Table 25]

Under the conditions of melt-kneading at 260 ° C., the TOC value was 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)

[0160]

[Table 26]

(Reference Example 4: Metal element content in PET resin and TO
C value) Using the PET resin C shown in Table 26 and the PET resin D obtained by adding 200 ppm of germanium oxide to the PET resin C, the resin pellets were obtained by the method described in 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.

[0162]

According to the resin composition of the present invention,
While maintaining properties such as heat resistance, processability, adhesion to metal plates, gas barrier properties, and flavor properties of the polyester resin (A), the vinyl polymer (B) further extends the polyester resin (A) and impact resistance Improved polyester resin
By adding a radical inhibitor which suppresses the decomposition of the vinyl polymer (B) by (A), it is possible to suppress the deterioration of the resin and the generation of low molecular weight organic components. Further, the impact resistance can be improved by adding a rubber-like elastic resin (C) that does not suppress the function of the radical inhibitor. In this case, the compatibility between the polyester resin (A) and the rubber-like elastic resin (C) is improved by encapsulating the rubber-like elastic resin (C) with the polar vinyl polymer (B). In addition, the direct contact between the metal plate and the rubber-like elastic resin (C) can be prevented to ensure the adhesion between the metal plate and the resin composition. As a result, it excels in various properties such as fragrance retention, taste retention, moldability, heat resistance, impact resistance, chemical resistance, mechanical strength, gas barrier properties, and adhesion to metals. It can be suitably used as a material. Therefore, since the resin-coated metal plate of the present invention and the resin-coated metal container use the resin composition of the present invention, respectively, the coating material of the metal plate, various metal members including the container, and the storability. It can be suitably used as a metal container having excellent flavor properties.

In the resin-coated metal plate of the present invention, since the surface of the metal plate is coated with the resin in advance, it is possible to omit the coating process at the customer, and to save the process and cost at the customer. It also has the effect of contributing to

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) B32B 27/36 B32B 27/36 B65D 1/09 C08K 5/13 C08K 5/13 5/372 5/372 5 / 521 5/521 C08L 67/00 C08L 67/00 101/02 101/02 B29K 67:00 // B29K 67:00 B29L 9:00 B29L 9:00 B65D 1/00 BC (72) Inventor Hidefumi Kikuchi 5-3 Tokai-cho, Tokai City, Aichi Prefecture Nippon Steel Corporation Nagoya Works (72) Inventor Hiroshi Ueshiro 20-1 Shintomi, Futtsu City, Chiba Prefecture Nippon Steel Corporation Technology Development Division (72) Inventor Hiroshi Oishi 20-1 Shintomi, Futtsu-shi, Chiba F-term in the Technology Development Division of Nippon Steel Corporation (reference) 3E033 BA07 BA08 BA09 BA14 BA18 BB08 CA03 CA05 CA07 CA11 CA14 CA16 CA20 EA10 EA12 FA01 4F100 AB01B AB03 AH02A AH02C AH03 A AH03C AH04A AH04C AK01A AK01C AK21A AK21C AK41A AK41C AK64 AK65 AK70 AL05A AL05C AN00A AN00C BA02 BA03 BA06 BA10A BA10C BA44A BA44C CA05A CA05C CA30A CA30C DE04A DE04C EC032 EH232 EJ172 EJ421 EJ422 GB16 JD02 JK06 JK07A JK07C 4F207 AA20 AA24 AA45 AB06 AB15 AD03 AG01 AG03 AH55 KA01 KA17 KB11 KB13 KB26 4J002 AC04Y BB05Y BB15Y BE02X BF02X BG01X BG04X BG06X BG07X CF00W CF05W CF06W CF07W CF08W EJ016 EV046 EW066 FD036 GF00

Claims (12)

[Claims] 1. A polyester resin (A) comprising a vinyl polymer (B) containing at least 1% by mass of a unit having a polar group and a resin composition containing a radical inhibitor in a non-molten state.
It is put into a hopper of an extruder with a die, melt-kneaded in the extruder, and then extrudes a molten resin from a T die,
After supplying the molten resin in the form of a film to at least one side of the metal plate,
A method for producing a resin-coated metal plate, wherein the film-shaped molten resin is cooled and adhered to the metal plate to obtain a resin-coated metal plate. 2. The method for producing a resin-coated metal plate according to claim 1, wherein the metal plate for supplying the molten resin is heated in advance. 3. A polyester resin (A) comprising a vinyl polymer (B) containing 1% by mass or more of a unit having a polar group and a resin composition containing a radical inhibitor in a non-molten state.
It is put into a hopper of an extruder with a die, melt-kneaded in the extruder, then extruded a kneaded molten resin from a T-die to form a film, and thermocompression-bonded the film to at least one surface of a metal plate. A method for producing a resin-coated metal plate. 4. The method for producing a resin-coated metal plate according to claim 3, wherein the metal plate for thermocompression bonding the film is preheated. 5. The resin composition further comprises a rubber-like elastic resin.
The production method according to any one of claims 1 to 4, further comprising (C). 6. The rubber-like elastic resin (C) has a structure in which the rubber-like elastic resin (C) 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). 3. The production method according to claim 2, wherein a film-like molten resin or a film is formed from the resin composition having an encapsulated structure. 7. The method according to claim 1, wherein the radical inhibitor is at least one member selected from the group consisting of a phenolic radical inhibitor, a phosphorus radical inhibitor, a sulfide radical inhibitor, and a nitrogen radical inhibitor. The production method according to any one of the above. 8. The method according to claim 7, wherein the radical inhibitor is a phenolic radical inhibitor. 9. The components (A) and (B), or (A), (B) and
The method according to claim 8, wherein the phenolic radical inhibitor is contained in an amount of 0.001 to 7 parts by mass based on 100 parts by mass of the component (C). 10. The resin composition to be charged comprises (A) and
The method according to any one of claims 1 to 4, wherein the component (B) is dry-blended in advance. 11. The production method according to claim 5, wherein the resin composition to be charged is obtained by previously dry-blending at least two components of the components (A), (B) and (C). 12. A method for producing a resin-coated metal container, comprising molding a resin-coated metal plate obtained by the method according to claim 1 to obtain a resin-coated metal container.