JP2001342329A - Resin composition, and resin film, resin coated metal plate, and resin coated metal container therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in impact strength, chemicals resistance, moldability, heat resistance, gas barrier properties, adhesiveness with metals, and odorlessness and coating film uniformity, and to provide resin film made of the resin, a coated metal plate with the resin film, and a resin coated metal container made of the resin coated metal plate. SOLUTION: This resin composition contains 0.001-7 parts mass radical inhibitor per 100 parts mass resin composition comprising a polyester resin (A), and a vinyl polymer (B) containing not less than 1 mass % unit having a polar group. It is preferable that a rubber-like elastomer resin (C) is minutely dispersed in the polyester resin (A), and at least a part of the rubber-like elastomer resin (C) has a capsule structure in the vinyl polymer (B). This resin film uses the resin composition, this resin coated metal plate is coated with the resin film, and this resin coated metal container is prepared by molding the resin coated metal plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition, particularly to a resin composition, which has good impact resistance, chemical resistance, moldability, heat resistance, gas barrier property and adhesion to metal, and has a high decomposition resistance. The present invention relates to a resin composition which has a small amount of a gelled product due to burning of a resin component and a small amount of an organic substance eluted from a resin, and is particularly excellent in flavor. Furthermore, the present invention is a resin film using such a resin composition, a resin-coated metal plate coated and coated on one or both sides of a metal plate in a single layer or in a multilayered form by laminating or applying the resin film, and 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, manufacturing conditions such as temperature control have been severely restricted.

When a resin is used as a material for coating a metal plate, adhesion, impact resistance, and gas barrier properties between the resin and the metal are important. No. 269074 discloses a method of laminating a crystalline polyester resin and a resin composition comprising an amorphous polyester resin. In this method, the crystallization rate at the interface can be easily reduced in the laminating step, so that the adhesion is improved, but the gas barrier property and the impact resistance are reduced. 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 JP 290644, by using a composition of a polyester resin and an ionomer resin,
The mechanical properties, the electrical properties, the heat resistance, the gas barrier properties and the adhesion to metals have been improved. A technology has been developed in which a rubber elastic resin is further added to the resin composition with the union, the rubber elastic resin is finely dispersed in a polyester resin, and the elastic resin is encapsulated by a vinyl polymer having a polar group. Thus, various characteristics were further improved, and the above-mentioned various problems could be almost solved.

[0005]

However, the present inventors have further studied the resin compositions of the above polyester resin and a vinyl polymer having a polar group such as an ionomer. There is a problem that low-molecular organic substances are generated and the impact resistance and the like are reduced. In particular, when a container using the resin is used for beverages and foods, odor is generated in the contents and the flavor of the contents is generated. Was sometimes reduced. In addition, gelled material resulting from burning of the resin component remains in the resin composition, causing fisheye when forming a film, causing breakage at the time of film or defective can making and metal corrosion when used for containers. Was sometimes

[0006] In general, the causes of the generation of organic low molecular weight substances from resin include raw materials remaining in the resin, low molecular components having a low degree of polymerization, and the contents of containers of decomposition products generated during resin production or can manufacturing. Elution to the substance is considered. Further, it is considered that the gel-like foreign matter remaining in the resin is caused by a thermally degraded substance generated during kneading or processing.

[0007] As a method for suppressing the elution of organic low-molecular components and gel-like foreign matter due to the decomposition of the resin, it is generally effective to carry out each step of resin production and molding at a temperature lower than the decomposition temperature of the resin. However, kneading of the above resin composition, the temperature of each step such as molding, polyester resin, vinyl polymer having a polar group such as ionomer, and even if set to a decomposition temperature of each resin of rubber elastic resin or less. However, the generation of low molecular organic substances did not go away. Therefore, it is considered that the generation of the organic low-molecular substance or the gel-like foreign matter in each step such as kneading and molding of the resin composition is not caused by simple thermal decomposition of the component resin.

When oxygen promotes the decomposition of the resin, it may be effective to manufacture and mold the resin in an inert gas atmosphere, but an apparatus for introducing an inert gas is required. It is difficult to say that this is a simple method, and when the decomposition of the resin is caused by something other than oxygen, the method using an inert gas atmosphere has no effect. In view of the above-mentioned problems of the prior art, the present invention has good impact resistance, chemical resistance, moldability, heat resistance, gas barrier properties and adhesion to metal, It is an object of the present invention to provide a resin composition in which the amount of gel-like foreign substances mixed therein and the amount of organic substances eluted from the resin are small, and the resin composition is particularly excellent in resin uniformity and flavor.

Further, the present invention provides a resin film using such a resin composition, a resin-coated metal sheet covered with a resin film obtained by laminating the resin film, and further provides the resin-coated metal sheet. It is another object of the present invention to provide a resin-coated metal container obtained by molding the above.

[0010]

Means for Solving the Problems The present inventors diligently studied to solve the above problems, obtained the following findings, and completed the present invention. That is, polyester resin (A), vinyl polymer
An organic low molecular weight substance or a gel-like foreign substance may be generated from the resin composition comprising (B) and the rubber-like elastic resin (C).
In particular, when a resin composition containing (A), (B) and (C) is used for a container or a resin-coated metal container, an organic low-molecular-weight substance is eluted into the contents from these containers, causing odor and flavor. In some cases, the corrosion resistance deteriorates, or a defect originating from the gel-like foreign matter occurs in the coated resin film, and the corrosion resistance deteriorates. However, even if the polyester resin (A), vinyl polymer (B), or rubber-like elastic resin (C) is melt-kneaded under the same conditions (temperature, time, continuity) alone, organic low-molecular substances or gel No foreign matter is generated, and no odor is generated.

As described above, the generation of low-molecular organic substances and gel-like foreign substances themselves is originally caused by the thermal decomposition of each of the polyester resin (A), vinyl polymer (B) or rubber-like elastic resin (C) alone. Even at a temperature higher than the above, it can occur depending on conditions.
However, the present inventors differ from the generally known thermal decomposition of each resin, because even when melt-mixed alone under the same conditions, organic low-molecular substances and gel-like foreign substances are not generated. It was confirmed that this was an inherent problem when these resins were combined. As a result of further detailed examination, the generation of organic low molecular weight substances was determined for polyester resin (A) and vinyl polymer.
As a result of close examination of the interaction of (B) and the eluate of the organic low molecular weight substance, the main component was an organic substance in which the vinyl polymer (B) was decomposed by a radical reaction. Metal compounds such as germanium, antimony, and titanium, which are residues of the polyester production catalyst, may remain in (A) in the range of about 1 ppm to 500 ppm, and such metal compounds may remain in the polyester resin (A). It was found that the decomposition of the vinyl polymer (B) was caused when the reaction was carried out. That is, the vinyl polymer (B) having a polar group is usually thermally stable and decomposition does not matter, but it is mixed with the polyester resin containing a metal compound involved in electron transfer as described above. When heated, radicals were generated in the vicinity of the polar groups of the vinyl polymer, and it was clarified that the resin was decomposed due to cleavage of the main chain of the vinyl polymer, and organic substances causing odor were generated. Furthermore, as a result of analyzing the cause of the gel-like foreign matter by disassembling the kneading machine, it was found that the gel-like foreign matter was generated at a position where flow stopped in the barrel (upstream of the inserted thermocouple). Further, as a result of analyzing the composition and structure of the gel-like foreign matter, it was found that the gel-like foreign matter was a thermally degraded product of the vinyl polymer (B) or the rubbery elastic body (C). That is, the gel-like foreign matter is generated by mixing the resin that has been thermally degraded with time due to the adhesion and retention of the vinyl polymer (B) and the rubber-like elastic body (C) at the flow stop portion in the barrel. Was revealed. further,
Since no gel-like foreign matter is generated when kneaded alone, it is considered that when the resin composition (I) is used, these adhesion and stagnation occur.

The present inventors have further studied and, in order to prevent radical decomposition of such a vinyl polymer (B) and suppress elution of organic substances, it has a certain radical inhibitor, that is, a radical scavenging ability. By adding an appropriate amount of a compound having the ability to decompose the compound and the radical precursor, the polyester resin (A) and the vinyl polymer (B)
Impact resistance of the resin composition consisting of, without impairing excellent physical properties such as adhesion to metal, polyester resin (A)
It has been found that radical decomposition of the vinyl polymer (B) by the metal compound remaining therein can be suppressed.
Furthermore, it has been found that the addition of these decomposition inhibitors alone is not sufficient because the residence time of the resin is long for suppressing the gel-like foreign matter, and it is necessary to suppress the resin adhesion and residence itself at the flow stopping portion. . As a general method of preventing resin adhesion / retention, there is known a technique of adding a low molecular weight release agent or adding an acrylic processing aid to prevent adhesion to a barrel or a screw. However, even when these methods are applied to this system, the low-molecular release agent migrates to the surface of the metal coating film to form a processing area, or the processing aid decomposes during heating and mixing, and conversely gels There were defects such as an increase in the number of foreign substances. The present inventors have further studied and found the following phenomena, and have reached the present invention. That is, there is a correlation between the melt tension of the resin composition (I) and the amount of the vinyl polymer (B) or the rubber-like elastic body (C) adhered and retained on the barrel or screw. Resin composition
By increasing the melt tension of (I), resin adhesion to the
Stagnation can be suppressed. In order to increase the melt tension, it is effective to add a necessary amount of polytetrafluoroethylene-containing powder and disperse the fluororesin in the resin composition (I) in a microfibril form. If it is a polytetrafluoroethylene-containing powder, it does not decompose during heating and kneading, and does not cause processing problems.

The present invention relates to at least a polyester resin
A resin composition containing (A) and a vinyl polymer (B) containing 1% by mass or more of a unit having a polar group, and a total of 100 parts by mass of the polyester resin (A) and the vinyl polymer (B). A resin composition comprising 0.001 to 7 parts by mass of a radical inhibitor and 0.001 to 7 parts by mass of a polytetrafluoroethylene-containing powder.

In the resin composition, the polytetrafluoroethylene-containing powder preferably has a particle size of 10 μm or less, more preferably polytetrafluoroethylene (a) having a particle size of 10 μm or less, and an organic polymer (b). And a mixture thereof. The addition amount of the polytetrafluoroethylene-containing powder is 0.005-1 to 100 parts by mass of the resin composition (I).
It is preferably in parts by mass. Further, the organic polymer particles (b) are desirably a polymer or a polyester resin containing 1% by mass or more of a (meth) acrylate monomer having an epoxy group.

The present invention also provides a polyester resin
(A), a radical inhibitor is 0.00
1 to 7 parts by mass of polytetrafluoroethylene-containing powder
Provided is a resin composition characterized by containing 0.001 to 7 parts by mass. This resin composition of the present invention, the polytetrafluoroethylene-containing powder has a particle size of 10 μm or less, more preferably polytetrafluoroethylene (a) having a particle size of 10 μm or less and an organic polymer (b) And a mixture thereof. The addition amount of the polytetrafluoroethylene-containing powder is preferably 0.005 to 1 part by mass based on 100 parts by mass of the resin composition (I). Further, the organic polymer particles (b) are desirably a monomer or polyester resin containing 1% by weight or more of a (meth) acrylate monomer having an epoxy group.

Further, the present invention also provides a resin film obtained by molding the above resin composition alone, or by laminating or applying the resin composition in combination with another resin composition and / or an adhesive. . Furthermore, the present invention provides a method for coating a resin film as described above on one side and / or both sides of a metal plate, in a single layer or in a multilayer in combination with another resin composition and / or an adhesive. The present invention also provides a resin-coated metal plate.

Further, the present invention provides a resin-coated metal container formed by molding the above-described resin-coated metal plate. Further, the present invention provides a polyester resin (A), and a vinyl polymer (B) containing 1% by mass or more of a unit having a polar group.
And preferably further comprising a step of mixing a resin composition (I) containing a rubber-like elastic resin (C), and
The polyester resin (A) contains a metal compound, and the radical inhibitor is added to 100 parts by mass of the resin composition (I).
The present invention also provides a production method in which 001 to 7 parts by mass and 0.001 to 7 parts by mass of polytetrafluoroethylene-containing powder are added to prevent decomposition of the resin composition (I) and generation of gel-like foreign matter in the mixing step. In the mixing step of this method, the polytetrafluoroethylene-containing powder has a particle size of 10 μm or less, and more preferably a mixture of polytetrafluoroethylene (a) and an organic polymer (b) having a particle size of 10 μm or less. It is desirable to add 0.005 to 1 part by mass to 100 parts by mass of the composition (I). More preferably an organic polymer
It is preferable that (b) is a monomer or polyester resin containing 1% by mass or more of a (meth) acrylate monomer having an epoxy group.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A resin composition to which a radical inhibitor and a polytetrafluoroethylene-containing powder of the present invention are added, and a resin film, a resin-coated metal plate and a resin-coated metal container using the same will be described below. . (1) Introduction The resin composition of the present invention comprises a polyester resin (A), a vinyl polymer containing at least 1% by mass of a unit having a polar group.
(B) and a radical inhibitor and polytetrafluoroethylene-containing powder. In the resin composition of the present invention, mixing the vinyl polymer (B) containing at least 1% by mass of a unit having a polar group with the polyester resin (A) imparts impact resistance to the polyester resin (A). That's why. As described above, in the resin composition containing the polyester resin (A) and the vinyl polymer (B) containing the polar group-containing unit in an amount of 1% by mass or more, the metal contained in the polyester resin (A) may be included. In order to prevent the generation of low molecular weight substances due to the decomposition of the vinyl polymer (B) due to the compound, a radical inhibitor is added. Further, as described above, polytetrafluoroethylene-containing powder is added in order to prevent the resin from staying in the kneading / molding apparatus and to suppress the generation of gel-like heat-degraded resin foreign matter.

The composition of these resins is not particularly limited, but preferably contains 1 to 50 parts by mass of the vinyl polymer (B) based on 100 parts by mass of the polyester resin (A). Vinyl polymer (B) based on 100 parts by mass of polyester resin (A)
If less than 1 part by mass, impact resistance may decrease,
If the amount is more than parts by mass, heat resistance may decrease. Further, in the present invention, 0.001 to 7 parts by mass of a radical inhibitor and 0.001 to 7 parts by mass of a polytetrafluoroethylene-containing powder are added to 100 parts by mass of the resin composition (I). Polyester resin
When the radical inhibitor is less than 0.001 part by mass with respect to the resin composition (I) containing (A) and the vinyl polymer (B), the metal compound and the vinyl polymer ( The generation of low molecular weight substances due to the reaction with B) cannot be effectively suppressed, and even if the radical inhibitor exceeds 7 parts by mass, the effect of reducing the elution amount is substantially saturated and the effect is uneconomical. In addition, problems such as deterioration of resin characteristics occur. In addition, polytetrafluoroethylene-containing powder
If the amount is less than 0.001 part by mass, the melt tension of the resin composition (I) cannot be sufficiently increased, and the gel-like foreign matter cannot be reduced. Further, when the polytetrafluoroethylene-containing powder is added in an amount of more than 7 parts by mass, a large amount of polytetrafluoroethylene migrates to the surface, and the adhesion to the metal plate is reduced. The dispersibility of (B) may change, and the non-uniformity may increase.

(2) Polyester Raw Material The polyester resin (A) used in the present invention includes only a hydroxycarboxylic acid compound residue, a dicarboxylic acid residue and a diol compound residue, or a hydroxycarboxylic acid compound residue. It is a thermoplastic polyester having a group, 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 serving as a raw material for 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) 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, 4,4'-biphenol, 3,3 ', 5,5'-tetramethyl
-4,4'-dihydroxybiphenyl, aromatic diols such as 4,4'-dihydroxybenzophenone and ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,4-butanediol,
Pentamethylene glycol, neopentyl glycol,
Hexamethylene glycol, dodecamethylene glycol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, polyethylene glycol,
Examples thereof include aliphatic diols such as hydrogenated bisphenol A, and alicyclic diols such as cyclohexane dimethanol. These can be used alone or as a mixture of two or more.

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, among which an aromatic polyester resin composed of an aromatic dicarboxylic acid residue and a diol residue. Is preferred from the viewpoint of processability and thermal stability.

Also, the polyester resin used in the present invention
(A) contains a small amount of a structural unit derived from a polyfunctional compound such as trimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, and pentaerythritol, for example, an amount of 2 mol% or less. May be. From the viewpoint of heat resistance and processability, the most preferable combination of these dicarboxylic acid compounds and diol compounds is terephthalic acid 50 to 95 mol%,
It is a combination of a dicarboxylic acid compound having 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 are, for example, polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene.
-2,6- naphthalate and the like, among which moderate mechanical properties, gas barrier properties, and metal adhesion polyethylene terephthalate, polybutylene terephthalate,
Polyethylene-2,6-naphthalate, polybutylene-2,6-
Naphthalate is most preferred.

The polyester resin contained in the resin composition of the present invention contains a metal compound such as germanium, antimony or titanium which is a residue of a polyester production catalyst. Such a polyester resin containing no metal compound can be used under ordinary kneading and molding steps, more specifically, under a temperature lower than the decomposition temperature of the vinyl polymer (B). Does not cause decomposition. The content of the metal compound in the polyester resin used in the resin composition of the present invention is not particularly limited,
Generally, the metal compound as a residue of the polymerization catalyst is 1p
In some cases, pm to about 500 ppm or even 1000 ppm remains, and the present invention is directed to such a case.

(3) Physical Properties of Polyester Resin The polyester resin (A) used in the present invention is usually from 0.3 to
It preferably has an intrinsic viscosity of 2.0 dl / g, more preferably 0.40 to 1.7 dl / g, even more preferably 0.50 to 1.5 dl / g. When the intrinsic viscosity is less than 0.3 dl / g, it does not mix uniformly with the polar monomer-containing vinyl polymer (B), resulting in low mechanical strength and impact resistance. Moldability is 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). Wherein, C is the concentration, expressed in g of resin per solution 100 ml, t _o is the flow time of the solvent, t represents each a flow time of the solution. Intrinsic viscosity = ｛ln (t / t _o ｝ / C The temperature is preferably 50 to 120 ° C, more preferably 60 to 100 ° C.

The polyester resin (A) may be either amorphous or crystalline.
The crystal melting temperature (Tm) is usually 210 to 265 ° C, preferably 21 to
0 to 245 ° C., and the low temperature crystallization temperature (Tc) is usually 110 to 2
It is desirable that the temperature is 20 ° C, preferably 120 to 215 ° C.
If Tm is less than 210 ° C or Tc is less than 110 ° C,
In some cases, the film shape cannot be maintained during drawing because of insufficient heat resistance. Also, Tm is over 265 ° C or Tc is
If the temperature is higher than 220 ° C., the resin may not sufficiently enter the surface irregularities of the metal plate, resulting in poor adhesion.

(4) Polar Group of Vinyl Polymer (B) The difference in Pauling electronegativity from the vinyl polymer (B) containing 1% by mass or more of the unit having a polar group used in the present invention is 0.39%. (eV) A vinyl polymer containing 1% by mass or more of a unit containing a group having a bond between ^0.5 or more elements. If the unit having a polar group is less than 1% by mass,
Impact resistance may decrease.

The difference in the electronegativity of Pauling is 0.39 (eV)
^0.5Specific examples of the groups to which the above-mentioned elements are bonded include:
-C-O-, -C = O, -COO-, epoxy group, C_TwoO_Three, C_TwoO_TwoN-, -C
N, -NH_Two, -NH-, -X (X; F, Cl, Br), -SO_Three-, Etc.
Can be Acid groups neutralized with metal ions as polar groups
It may have ions. In this case, an example of a metal ion
As Na⁺, K⁺, Li⁺, Zn²⁺, Mg²⁺, Ca²⁺, C
o²⁺, Ni²⁺, Pb²⁺, Cu²⁺, Mn ²⁺, Ti³⁺, Zr³⁺, Sc³⁺Etc. 1
 And valent, divalent or trivalent metal cations.

(5) Examples of units having a polar group Examples of units having a polar group include vinyl alcohol as an example having a -CO- group, vinyl chloromethyl ketone as an example having a -C = O group, and -COO- Examples of a group having a group include acrylic acid, methacrylic acid, vinyl acetate, vinyl acid such as vinyl propionate and its metal salts or ester derivatives, and examples having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itacrylic acid. Glycidyl esters of α, β-unsaturated acids such as glycidyl, maleic anhydride with C ₂ O ₃ groups, imide derivatives of maleic anhydride with C ₂ O ₂ N-groups, and -CN groups Acrylonitrile as an example,
Acrylamine as an example having an -NH ₂ group, acrylamide as an example having an -NH- group, vinyl chloride as an example having a -X (X: F, Cl, Br) group, and styrene as an example having an -SO ₃ -group Sulfonic acid, etc., and compounds in which all or a part of these acidic functional groups are neutralized with the above-mentioned metal ions.Examples of these compounds are contained alone or in plural in the vinyl polymer (B). May be. The unit having a polar group contained in the vinyl polymer (B) may be a unit having a group in which an element having a Pauling electronegativity difference of 0.39 (eV) ^0.5 or more is bonded. It is not limited.

(6) Vinyl polymer (B) The vinyl polymer (B) used in the present invention is a vinyl polymer containing 1% by mass or more of a unit having a polar group,
Examples of such a vinyl polymer include the above-mentioned polar group-containing vinyl unit alone or two or more polymers, and the above-mentioned polar group-containing vinyl unit and the following general formula:
Copolymers with the non-polar vinyl monomer shown in (ii) and the like.

-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, and R ² represents an alkyl group having 1 to 12 carbon atoms. Group, a phenyl group or hydrogen.) Specific examples of the nonpolar vinyl monomer of the general formula (ii) include:
Ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,
Α-olefins such as 1-dodecene, aliphatic vinyl monomers such as isobutene and isobutylene, styrene monomers, o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene and t-butylstyrene Alkylated styrene, α-
An aromatic vinyl monomer such as an addition polymer unit of a styrene-based monomer such as methylstyrene is exemplified.

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

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

As an example of the metal cation to be neutralized, N
a ⁺ , K ⁺ , Li ⁺ , Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Co ²⁺ , Ni ²⁺ , Pb
^Monovalent , divalent or trivalent metal cations such as ²⁺ , Cu ²⁺ , Mn ²⁺ , Ti ³⁺ , Zr ³⁺ , Sc ^{3+ and the} like. In addition, some of the remaining acidic functional groups that have not been neutralized with the metal cation may be esterified with a lower alcohol. Specific examples of 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 these, ethylene and acrylic acid or methacrylic acid are most preferred for the purpose of improving the impact resistance and improving the compatibility between the polyester resin (A) and the rubbery elastic resin body (C). An acid copolymer (2 to 15 mol% of structural units having a carboxyl group), in which 30 to 70% of the carboxyl groups in the polymer are neutralized with metal cations such as Na and Zn. .

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

[0040] In particular, in view of high impact resistance, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and one of acidic functional groups in these copolymers are more preferable. Part or all of an ionomer resin neutralized with metal ions, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, 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-glycidylua Relate copolymer, ethylene - anhydride Maren'i acid copolymer, butene - ethylene - glycidyl methacrylate copolymer, butene - ethylene - glycidyl acrylate copolymers.

(7) Physical Properties of Vinyl Polymer (B) From the viewpoint of ensuring barrier properties, a copolymer of an α-olefin and a unit having a polar group is a preferred combination. The vinyl polymer (B) used in the present invention may be any vinyl polymer containing at least 1% by mass of a unit having a polar group, and is not limited to the above specific examples.

The molecular weight of the vinyl polymer (B) is not particularly limited, but the number average molecular weight is 2,000 to 500,000.
The following is preferred. If it is less than 2000 or more than 500,000, the impact resistance may be low. (8) Third resin component (ternary resin composition of the present invention) In the resin composition of the present invention, in addition to the polyester resin (A) and the vinyl polymer having polarity (B), the third resin component is used to improve impact resistance. Or for other purposes, a resin of the third component which does not inhibit the action of the radical inhibitor may be added, but in particular, in order to improve the impact resistance, the rubber-like elastic resin (C) Is preferably added to form a ternary resin composition.

(9) Rubbery Elastic Body (C) As the rubbery elastic body resin (C) used in the present invention, known rubbery elastic body resins can be widely used. Among them, the glass transition temperature (Tg, sample amount about 10 mg,
(Measured by a differential thermal analyzer (DSC) at 10 ° C / min), 50 ° C or less, Young's modulus at room temperature
A rubber-like elastic resin of 50% or more is preferable. The Tg of the rubber elasticity manifestation part exceeds 50 ° C, the Young's modulus at room temperature exceeds 1000MPa,
If the elongation at break is less than 50%, sufficient impact resistance cannot be exhibited.

To ensure impact resistance at low temperatures, Tg
Is preferably 10 ° C. or lower, more preferably -30 ° C. or lower. Further, in order to ensure more reliable impact resistance, the Young's modulus at room temperature is 100 MPa or less, more preferably 10 MPa.
It is preferable that the elongation at break is 100% or more, more preferably 300% or more. (10) Examples of rubber-like elastic body (C) 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. Polymer (NBR), polyisoprene (IPR), polybutadiene (BR)
Such as diene elastomers, styrene-butadiene-styrene copolymer (SBS) and its hydrogenated product (SEBS), rubber-modified styrene (HIPS), acrylonitrile-styrene-butadiene copolymer (ABS) and other styrene elastomers, Examples thereof include silicone elastomers containing dimethylsiloxane as a main component, polyester elastomers such as aromatic polyester-aliphatic polyester copolymer or aromatic polyester-polyether copolymer, and nylon elastomers.

Among them, polyolefin resins are preferred because of their low water vapor permeability. The polyolefin resin has the following general formula (iii) -R ¹ CH-CR ² R ^3- (iii) (wherein, R ¹ and R ³ each independently represent an alkyl group having 1 to 12 carbon atoms or hydrogen; ² is a resin having a repeating unit represented by an alkyl group having 1 to 12 carbon atoms, a phenyl group or hydrogen.

The polyolefin resin used in the present invention is
It may be a homopolymer of these constituent units, a copolymer of two or more 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 the polyolefin resin include polyethylene, polypropylene, polybutene, polypentene, polyhexene and polyoctenylene, which are homopolymers of α-olefin. 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 may be a vinyl monomer, a polar vinyl monomer,
A diene monomer may be copolymerized in a monomer unit or a resin unit. The copolymer composition is at most 50 mol%, preferably at most 30 mol%, based on the above units. If it exceeds 50 mol%, the properties as a polyolefin resin, such as dimensional stability, deteriorate.

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

The most preferred 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 It consists 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 dienes. It is an original copolymer. Among them, from the ease of handling, ethylene-propylene copolymer and ethylene-1-butene copolymer binary copolymer, or ethylene-propylene copolymer and ethylene-1-butene copolymer, Using 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, cyclopentadiene and 1,4-hexadiene as the non-conjugated diene, the α-olefin content is 20 to 60 mol%, and the non-conjugated diene is 0.5 to 10 Molar% copolymerized resins are most preferred.

As for the polyester resin (A) and the polar vinyl polymer (B) used in the preferred ternary resin composition of the present invention, the resins (A) and (B) ) Is used. (11) Higher order structure of ternary resin composition: finely dispersed encapsulated structure According to the present invention, rubber-like elastic resin (C) is used as the third component as a third component
The resin composition contains a polyester resin (A), a vinyl polymer (B) containing 1% by mass or more of a unit having a polar group, a rubber-like elastic resin (C), and a radical inhibitor, Further, the rubber-like elastic resin (C) is finely dispersed in the polyester resin (A), and the rubber-like elastic resin
A resin composition having a structure in which at least a part of (C) is encapsulated with a vinyl polymer (B) is preferable in terms of higher impact resistance and higher adhesion to a metal plate.

By having such an encapsulated finely dispersed high-order structure, a biaxially stretched film having a conventional double-layer structure of a crystal layer and a polycrystalline layer can be laminated by strict temperature control. Unlike the complicated and expensive process of performing the process, it is possible to realize a high impact resistance and a high adhesion to metal, which are superior to conventional products, without the need for strict temperature control, even for an unstretched film. As described above, the high impact resistance and the adhesion make it possible to improve the quality, reduce the cost by reducing the thickness, and make a more severe can (lighter can) than before. Further, since the stretching step is unnecessary, it is possible to omit the film forming step by directly laminating the metal plate, and it is possible to realize higher impact resistance by stretching. In addition, since strict temperature control is not required, thinning, cost reduction by high-speed manufacturing, and quality improvement by stabilizing film thickness and performance can be achieved.

(12) Tertiary higher-order structure: definition of fine dispersion In the present invention, the term "fine dispersion" in which the rubber-like elastic resin (C) is contained in the polyester resin (A) means that the rubber-like elastic resin ( C)
In this state, 70% by volume or more of the particles are dispersed in the polyester resin (A) with an equivalent sphere-equivalent diameter of 100 μm or less. Equivalent sphere equivalent diameter of rubber-like elastic resin (C) is 100
If it exceeds μm, the impact resistance decreases, and the film forming property of the resin composition of the present invention decreases. It is desirable that the equivalent spherical equivalent diameter is preferably 1 μm or less, more preferably 0.5 μm or less. If it exceeds 1 μm, sufficient impact resistance may not be exhibited.

(13) Tertiary higher-order structure: definition of encapsulation The rubber-like elastic resin (C) “encapsulated” with the vinyl polymer (B) is the rubber-like elastic resin (C). ) 80% of interface
The structure is such that the vinyl polymer (B) covers at least 95%, preferably at least 95%, and the direct contact area between the polyester resin (A) and the rubber-like elastic resin (C) is less than 20%. With such a structure, the fine dispersion of the rubber-like elastic resin body (C) encapsulated by the vinyl polymer (B) is facilitated,
Improved impact resistance and film-forming properties, and rubber-like elastic resin (C)
Generally has low adhesion to the metal plate, but since the vinyl polymer (B) having a polar group has adhesion to the metal plate, the resin composition and the metal This has the effect of ensuring adhesion to the substrate.

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 by volume of the rubber-like elastic resin (C) is a vinyl polymer. What is necessary is just to be encapsulated by union (B). If the unencapsulated rubber-like elastic resin body (C) is present in a volume ratio of more than 30%, it becomes difficult to finely disperse and the impact resistance is reduced,
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, making it difficult to secure the adhesion between the resin composition and the metal plate. Become.

Rubber-like elastic resin not encapsulated
The equivalent spherical equivalent diameter of (C) is not particularly specified, but from the viewpoint of impact resistance and workability, it is 100 μm or less, especially 1.0 μm.
The following is desirable. Also, an excessive amount of the vinyl polymer (B) is
The rubber-like elastic resin body (C) may be dispersed alone in the polyester resin (A) without being encapsulated. The amount and diameter of the non-encapsulated vinyl polymer (B) are not particularly limited, but may be 20% or less in volume ratio of all vinyl polymers (B) and 1.0 μm or less in terms of equivalent sphere. desirable. If the volume ratio exceeds 20%, the basic properties such as heat resistance of the resin composition may change. The equivalent spherical equivalent diameter is 1.0
If it exceeds μm, workability may decrease.

(14) Principle of Encapsulation by Mixing The rubber-like elastic resin (C) obtained by mixing the ternary resin composition as described above and encapsulating the polyester resin (A) with the vinyl polymer (B). In order to finely disperse
(B) and polyester resin (A) and rubber-like elastic resin body (C)
It is important to make the balance of the interfacial tension with the appropriate.

Preferably, the Spread Parameter (λ) for the rubbery elastic resin body (C) of the vinyl polymer (B)
It is desirable to control the content of the unit having a polar group so that _{(Resin C) / (Resin B)} ) becomes positive. λ
By setting _{(Resin C) / (Resin B)} to be positive, thermodynamic stability can be ensured even when the rubber-like elastic resin body (C) is encapsulated with the vinyl polymer (B). Spread Par between different polymers
ameter is SY Hobbs; Polym., Vol. 29, p1598 (198
(Iv) λ _{(Resin C) / (Resin B)} = Υ _{(Resin C) / (Resin A)} -Υ _{(Resin C) / (Resin B)} -Υ _{(Resin B) / (Resin A)} (iv) (wherein, Resin A is a polyester resin (A),
sin B indicates a rubber-like elastic resin body (C), Resin C indicates a vinyl polymer (B), and Υ _{i / j} is the interfacial tension between resin i and resin j. parameter indicating the compatibility between i and resin j chi _{i / j} compatibility is proportional to the square root of the more favorable shows a small value). ].

Polyester resin (A) and rubber-like elastic resin body
(C) has a low compatibility with Υ _{(Resin B ) / (Resin A)} > 0, so that the non-polar vinyl monomer (Mon
omerV) and the polar group-containing unit (Monomer U) by adjusting the mixing ratio, and the following formulas (v) and (vi) χ _{A / C} = φχ _{(Resin A) / (Monomer V)} + (1-φ) χ _{(Resin A) / (Monomer U)} -φ (1-φ) χ _{(Monomer V) / (Monomer U)} (v) χ _{B / C} = φχ _{(Resin C) / (Monomer V)} + (1-φ ) χ _{(Resin C) / (Monomer U)} -φ (1-φ) χ _{(Monomer V) / (Monomer U)} (vi) [However, φ is the mixing ratio of non-polar vinyl monomer (volume ratio)
Is shown. Rubber-like elastic resin body given by] (C) a vinyl polymer _(B) χ B _/ shows the compatibility with the _C and the polyester resin (A) and shows the compatibility with the vinyl polymer (B) chi _{A / B} 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 in an amount of 1% by mass or more is preferable. By appropriately controlling the mixing ratio between ethylene and a 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.

(15) Examples of Resin Usable for Encapsulation A copolymer of ethylene and a unit having a polar group suitable for forming an encapsulated structure by mixing a ternary resin composition is more specifically described. The ethylene-vinyl acid copolymer, ethylene-vinyl acid ester copolymer and their ionomer resins, copolymers of ethylene with glycidyl esters of α, β-unsaturated acids, ethylene and vinyl acid or vinyl Terpolymers of acid 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.

(16) Method for Producing Encapsulated Ternary Resin Composition A resin composition containing the polyester resin (A), the vinyl polymer (B) and the rubbery elastic resin body (C) of the present invention is prepared. The encapsulated structure can be manufactured by a known mixing method. Specifically, after selecting a polyester resin (A), a vinyl polymer (B) and a rubber-like elastic resin body (C) having an appropriate difference in interfacial tension, a predetermined temperature, for example, 20
If the mixture is melt-kneaded at 0 to 350 ° C. using various known mixers, it can be produced by forming a capsule structure by utilizing a difference in interfacial tension.

(17) Method for producing ternary resin composition using core-shell type rubber-like elastic material Rubber-like elastic resin material (C) encapsulated in vinyl resin (B) in polyester resin (A) As a method for finely dispersing the rubber, other than the above-described method utilizing the difference in interfacial tension, a core-shell type rubber in which a rubber-like elastic resin body (C) is encapsulated in advance with a vinyl polymer (B) is used. There is also a method of adding an elastic body to the polyester resin (A).

The core-shell type rubbery elasticity is as follows.
It has a two-layer structure composed of a core part and a shell part, and 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. And a 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.

The core-shell type rubber-like elastic material has high impact resistance, dispersibility in polyester resin, and high adhesion to metal.
It is preferable to use a shell type rubber-like elastic body. (18) Core part of core-shell type rubber-like elastic body Specific examples of the rubber-like elastic body constituting the core part include an acrylate polymer composed of a unit having a structure represented by the general formula (vii), or , A diene polymer, or a rubber-like elastic body mainly composed of dimethylsiloxane.

CH ₂ CRCR ¹ —CO—OR ² (vii) (19) Examples of Core Elastomer Specific examples of the constituent units of the acrylate polymer include alkyl acrylate, alkyl methacrylate, and alkyl ethacrylate. R ¹ is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R ² is a carbon atom having 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 mass 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 mass or less, preferably 20% by mass or less, more preferably 5% by mass or less. If it exceeds 30% by mass, it is often hardened to 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. (20) Physical Properties of Core Portion The molecular weight of the polymer constituting the core portion is not particularly limited, but is preferably 2000 or more in number average molecular weight. 2000
If it is less than 3, 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 the polymer constituting the core part (heating rate 10 ° C / min, differential thermal analyzer (DS
C) is preferably 30 ° C. or lower, more preferably 10 ° C. or lower, even 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.

(21) Definition of Shell Portion 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.

(22) Examples of Shell Portion The acrylate polymer constituting the shell portion is represented by the general formula (v
It is a polymer consisting of the unit of ii). 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 mass or more.
When copolymerized with another vinyl monomer, the composition ratio of the acrylate component is preferably 70% by mass or more. If it is less than 70% by mass, the polarity of the acrylate unit cannot be sufficiently utilized, and the fine dispersion and the adhesion to the metal plate may be insufficient.

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

The most preferred acrylate polymer unit constituting the shell portion is methyl methacrylate because the glass transition temperature is in the above range and the polymerization rate can be easily controlled. (24) Improving the compatibility of core-shell type rubber-like elastic material (terminal modification type) Further, acrylate-based polymers constituting the shell portion include:
In order to improve compatibility with the 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 of the polyester resin (A) 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 a
l .; J. Polym. Sci. Part A Vol. 31, 435 (1993) can introduce a linking group by using an initiator having these bonds. Among these functional groups and bonding groups, the most preferable from the viewpoint of reactivity are an epoxy group and an aromatic-aromatic ester bond, and when polymerizing the shell portion, glycidyl methacrylate and TO Ahnet, respectively. al .; J. Polym. Sci. Part A Vol.
31, 435 (1993), the epoxy groups and ester linkages described above can be introduced.

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 and polymethyl methacrylate in the shell, 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 introduction amount of the functional group-containing unit is preferably 15% by mass or less, more preferably 5% by mass or less. If it exceeds 15% by mass, a comb polymer is generated in the kneading step, and the compatibility with the polyester resin (A) may not be sufficiently improved. When the compound is a bonding group, the amount of the bonding group-containing unit to be introduced is preferably 15% by mass or less. If it exceeds 15% by mass, the unit having a binding group forms a domain, and the compatibility with the polyester resin (A) may not be improved.

The core-shell type rubber-like elastic body desirably contains the rubber-like polymer core portion in an amount of 20% by mass or more, preferably 50% by mass or more, more preferably 80% by mass or more. If the content is less than 20% by mass, 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, the emulsion polymerization method described in U.S. Pat. No. 4,096,202 is preferred 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 mass of a monomer having polyethylenic 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. .

(25) Improvement of compatibility of core-shell type rubber-like elastic material (additive type) The resin composition comprising the polyester resin (A) and the core-shell type rubber-like elastic material used in the present invention includes: A known compatibilizer may be added for the purpose of improving the compatibility between the polyester resin (A) and the core-shell type rubber-like elastic material. The added amount of the compatibilizer is preferably 15% by mass or less, more preferably 5% by mass or less. If it exceeds 15% by mass, the compatibilizing agent may form its own phase structure in some cases, and it is difficult to exhibit 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 polyesters compatible with the core-shell type rubber-like elastic material. Examples of the polymer include a functional group capable of reacting with a terminal residual functional group or a bond of the resin (A) 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. Also,
Examples of the non-reactive compatibilizer include a block and a graft copolymer of a polymer constituting the shell portion of the core-shell type rubbery elastic body and the polyester resin (A).

(26) Method for Producing Resin Composition (Binary and Ternary) For mixing the resin composition of the present invention, known resin mixing methods such as a resin kneading method and a solvent mixing method are widely used. Can be used. Examples of the resin kneading method include a method of mixing by dry blending using a tumbler blender, a Henschel mixer, a V-type blender or the like, and then performing melt kneading using a single-screw or twin-screw extruder, a kneader, a Banbury mixer, or the like. Also,
As an example of the solvent mixing method, there is a method of dissolving each resin in a common solvent of the raw material resins contained in the resin composition, evaporating the solvent, and collecting a precipitated mixture by adding to a common poor solvent. .

The mixing temperature of the resin composition of the present invention is not particularly limited, as long as the binary or ternary resin composition comprising the resins (A), (B) and (C) is sufficiently mixed. Usually resin (A)
(B) The resin can be sufficiently mixed at a temperature lower than the decomposition temperature of each resin. According to the findings of the present invention, even when mixing under such low temperature conditions, if the metal compound remains even in a trace amount in the polyester resin (A), vinyl containing a unit having a polar group is contained. The decomposition reaction of the system polymer (B) occurs to generate an organic low molecular weight substance, which causes a reduction in flavor. In addition, the gel-like foreign material is caused by the resin adhering and staying at the flow stopping portion when the foreign material is heated and mixed or molded, and the vinyl polymer (B) and the rubber-like elastic material (C) are thermally deteriorated. ing. Therefore,
According to the present invention, the resin (A) and the resin (A) and (B) further under the temperature conditions lower than the decomposition temperature of each resin (C)
(B) further mixing the resin composition comprising (C) under heating,
Further, by adding a radical inhibitor together with these resin compositions, it is possible to substantially eliminate organic low molecular weight substances generated during molding. Further, by adding the polytetrafluoroethylene-containing powder together, the melt tension at the time of heating can be increased to prevent the resin from adhering to the flow stopping portion and to reduce the generation of gel-like foreign matter.

The decomposition temperature of each of the resins (A), (B) and (C) is determined by the type of the resin.
℃ or more, resin (B) is about 200 ℃ or more, resin (C) is 25
It is about 0 ° C or more. Further, according to the present invention, the resin composition of the present invention is mixed under heating, the amount of gel-like foreign matter generated when manufactured through steps such as molding, the resin composition extracted by hot water extraction thereafter The amount of organic low molecular weight substances in each can be reduced to 5 ppm or less, preferably 2 ppm or less. Further, each of them can be reduced to 1 ppm or less.

Further, for the same reason, the resin composition of the present invention can be prevented from generating an organic low molecular weight substance even by heating when coating the surface of a metal plate. (27) Amount of Radical Inhibitor The resin composition of the present invention has a resin
0.001 to 7 parts by weight of a radical inhibitor must be added. Addition of 0.001 part by mass or less is not preferable because a remarkable effect cannot be obtained. On the other hand, radical inhibitors
Even if it is added in excess of parts by mass, the effect of reducing the elution amount is substantially saturated, so that excessive addition is uneconomical, and furthermore, the resin properties such as the elastic modulus of the resin and the decrease in adhesion are preferably reduced. Absent. In order to achieve a higher effect, a radical inhibitor is added to 100 parts by mass of the resin composition (I).
It is preferable to add 0.005 to 1 part by mass.

(28) Kinds of Radical Inhibitors The organic low molecular weight substance generated from the resin composition (I) used in the present invention is an action of a metal compound containing a vinyl polymer having a polar group in a polyester resin. It is generated by radical decomposition at Therefore, the radical inhibitor used in the present invention is a phenolic radical inhibitor or a nitrogenous radical inhibitor having an effect of stopping a radical reaction by trapping a radical, and reacts with a peroxide to form a radical reaction. Phosphorus-based and sulfide-based radical inhibitors having the function of suppressing the initiation of the reaction and inactivating the reaction intermediate are preferred.

(29) Definition of phenolic radical inhibitor A phenolic radical inhibitor refers to a compound having one or more phenolic hydroxyl groups in the molecule. A compound having a sterically bulky t-butyl group or the like in the vicinity of the phenolic hydroxyl group is preferable in order to improve the efficiency of terminating the radical reaction chain. 350 molecular weight due to low volatilization of the agent
It is preferable that it is above. Further, from the viewpoint of the diffusibility of the radical inhibitor in the resin, the molecular weight is preferably 5,000 or less. From the viewpoint of improving the reactivity and the molecular weight, it is also preferable to use a compound having a plurality of phenolic hydroxyl groups in one molecule.

(30) Examples of phenolic radical inhibitors Examples of phenolic radical inhibitors include tetrakis
[Methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, 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.

(31) Definition of phosphorus radical inhibitor The phosphorus radical inhibitor refers to a compound having one or more phosphite groups and / or phosphonate groups in the molecule. Further, the molecular weight is preferably 350 or more from the viewpoint that the radical inhibitor is less volatilized in the resin kneading, film forming, and can forming steps. 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.

(32) Examples of phosphorus radical inhibitors Examples of phosphorus radical inhibitors include 2,2-methylenebis
(4,6-di-t-butylphenyl) octyl phosphite,
Tris (2,4-di-t-butylphenyl) phosphite and the like. (33) Definition of sulfide radical inhibitor 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.

(34) Examples of Sulfide Radical Inhibitors Examples of the sulfide radical inhibitors include tetrakis
[Methylene-3- (dodecylthio) propionate] Methane, bis (tridecyloxycarbonylethyl) sulfide and the like. (35) Definition of nitrogen-based radical inhibitor A nitrogen-based radical inhibitor is a compound in which an amino group is bonded to an aliphatic hydrocarbon or aromatic hydrocarbon group and the generated radical is donated with hydrogen to eliminate the radical. To the compound.

(36) Examples of nitrogen radical inhibitors Examples of nitrogen radical inhibitors include bis (2-dodecylphenyl) amine, bis (3-octylphenyl) amine and bis (4-octylphenyl) amine. Is mentioned. (37) Use form of radical inhibitor: mixed use The radical inhibitor used in the present invention may be used alone or in combination.

The radical decomposition of the vinyl polymer (B) observed in the resin composition (I) of the present invention is one of the main factors of ordinary thermal radical decomposition, which is caused by thermal decomposition of accumulated peroxide groups. Unlike radical reactions caused by
The main factor is the generation of radicals by an electron transfer reaction from a metal compound such as a residual catalyst.Therefore, when using a single radical inhibitor alone, the phenolic compound has the effect of trapping radicals and breaking the chain. It is preferable in that it is high and, as a result, has a high effect of suppressing the decomposition of the resin.

Since phosphorus-based and sulfide-based radical inhibitors have the effect of decomposing peroxides that are radical generating sources and intermediates for radical reactions, they can be used in combination with phenolic radical inhibitors. Demonstrate high effect. 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.

(38) Amount of Addition of Polytetrafluoroethylene-Containing Powder The resin composition of the present invention contains:
0.001 to 7 parts by weight of polytetrafluoroethylene-containing powder must be added. The polytetrafluoroethylene-containing powder may contain polytetrafluoroethylene, but preferably contains at least 50 parts by mass of polytetrafluoroethylene in order to efficiently increase the melt tension. Further, the polytetrafluoroethylene-containing material is in powder form when added. Here, the powder shape is a solid having a shape in which the minor axis of the equivalent ellipsoid is at most 10 mm or less. The powder is 0.001 to
7 parts by weight must be added. If the polytetrafluoroethylene-containing powder is less than 0.001 part by mass, the resin composition
The melt tension of (I) cannot be sufficiently increased and gelled foreign matter cannot be reduced. Further, when the polytetrafluoroethylene-containing powder is added in an amount of more than 7 parts by mass, a large amount of polytetrafluoroethylene migrates to the surface, and the adhesion to the metal plate is reduced. The dispersibility of (B) may change, and the non-uniformity may increase. It is preferable to add 0.005 to 1 part by mass of a polytetrafluoroethylene-containing powder to 100 parts by mass of the resin composition (I). More preferably, the polytetrafluoroethylene-containing powder is added so that the addition amount of polytetrafluoroethylene is 0.005 to 1 part by mass.

(39) Definition of polytetrafluoroethylene contained in the mixture The polytetrafluoroethylene contained in the mixed powder of the present invention may be a polytetrafluoroethylene as a main component. During the emulsion polymerization of the particles, a fluorinated olefin such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, or perfluoroalkylvinyl ether, or a perfluoroalkyl (meth) acrylate, as long as the properties of polytetrafluoroethylene are not impaired. And vinyl monomers such as fluorinated alkyl (meth) acrylates. The content of the copolymer component is preferably 10% by weight or less based on tetrafluoroethylene. (40) Preferred Form of Polytetrafluoroethylene-Containing Powder The gel-like foreign matter generated from the resin composition (I) used in the present invention is obtained by mixing the resin (B) or the rubber-like elastic body (C) by heating and mixing. The reason is that the resin sometimes adheres and stays at the flow stopping portion in the barrel, and it is necessary to increase the melt tension of the resin composition (I) in order to prevent the adhesion and staying. For this reason, it is preferable that the polytetrafluoroethylene resin used in the present invention is dispersed in a microfibril shape during heat mixing or heat processing. A microfibril is a state in which the fiber is dispersed in a fibrous form with a thickness of 1 μm or less and a length of 10 μm or more. More preferably, it is 100 μm or more. In order to realize such a dispersion, it is preferable that the polytetrafluoroethylene (a) particles have a particle diameter of 10 μm or less. Polytetrafluoroethylene (a) particles having such a particle size can be obtained by polymerizing a tetrafluoroethylene monomer by emulsion polymerization using a fluorinated surfactant. More preferably, a mixture of polytetrafluoroethylene (a) and organic polymerization (b) is preferably added. By mixing (a) and (b), the compatibility between the resin composition (I) and the polytetrafluoroethylene-containing powder is improved, and microfibrillation is facilitated.

(40) Types of Organic Polymer (b) Added to Polytetrafluoroethylene-Containing Powder The organic polymer (b) is an organic resin (b) and is a polyester resin (A) or a vinyl polymer. It is desirable to have an affinity for (B). Therefore, it is desirable that the difference between the solubility parameters calculated by the Fedors method is 10 (MJ / m ³ ) ^1/2 or less between these resins and the organic polymer (b). Specific examples of the organic polymer (b) include styrene, p-methylstyrene, o-methylstyrene, p-chlorostyrene, and o-
Styrene monomers such as chlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, α-methylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid Butyl, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate,
(Meth) acrylate monomers such as tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene; butadiene, isoprene and dimethylbutadiene And a plurality of polymers such as diene monomers. Furthermore, the above-mentioned polyester resins can be exemplified. Among these, polyester resin (A) and vinyl polymer
Most preferred from the viewpoint of affinity with (B) are styrene-based monomers, (meth) acrylate-based monomers, and polyester resins. Particularly preferred examples include a monomer containing 1% by mass or more of a (meth) acrylate monomer having an epoxy group or the above-mentioned polyester resin.

(41) Method for Producing Polytetrafluoroethylene-Containing Powder An example of the method for producing the polytetrafluoroethylene-containing powder of the present invention is as follows. The polymer (b) is obtained by mixing with a particle dispersion and pulverizing by coagulation or spray drying. As a method of mixing the polytetrafluoroethylene particle dispersion (a) and the organic polymer (b) particle dispersion, the above-mentioned emulsion-polymerized polytetrafluoroethylene particle dispersion and the above-mentioned vinyl monomer are emulsified. A method of simply mixing a polymerization liquid with an organic polymer (b) particle dispersion obtained by polymerization or the like, and further adding a vinyl monomer as described above to these mixed liquids to carry out a known emulsion polymerization for copolymerization. And the like. Examples of commercially available raw materials that can be used as the polytetrafluoroethylene particle dispersion include Fluon AD-1, AD-936 manufactured by Asahi ICI Fluoropolymer, Polyflon D-1, D-2 manufactured by Daikin Industries, and Mitsui Dupont Fluoro. Examples include Teflon 30J manufactured by Chemical Company. As the organic polymer (b) particle dispersion,
Examples thereof include a liquid obtained by emulsion-polymerizing the above-mentioned vinyl monomer using an ionic emulsifier or a liquid obtained by soap-free emulsion-polymerizing the above-mentioned vinyl monomer using an ionic polymerization initiator. In these mixing, a known nonionic emulsifier is mixed with polytetrafluoroethylene particles / or an organic polymer (b) for the purpose of controlling the aggregation rate.
Can also be adsorbed on the surface of the substrate. Further, when coagulating the mixed solution, it is also possible to carry out salting out in advance by a known method and then coagulate. Further, as another method of producing the polytetrafluoroethylene-containing powder, an organic polymer (b) crushed and pulverized into polytetrafluoroethylene particles pulverized by coagulation or spray drying is mixed by a known method such as a ball mill. Methods are also included. This method can be suitably applied when the organic polymer (b) is a polyester resin.

(42) Method for Adding Radical Inhibitor or Polytetrafluoroethylene-Containing Powder As a method for adding the radical inhibitor or polytetrafluoroethylene-containing powder used in the present invention to the above resin composition (I). Is a polyester resin (A) as a raw material resin,
In any one or more of the vinyl polymers (B), and when the resin composition (I) contains a rubber-like elastic resin (C),
A radical inhibitor and a polytetrafluoroethylene-containing powder are added in advance to at least one of the polyester resin (A), the vinyl polymer (B), and the rubber-like elastic resin (C) to obtain a resin composition. Thus, a radical inhibitor may be contained in the resin composition (I). At this time, a radical inhibitor and polyester resin are added to the raw material resin (B).
By adding a polytetrafluoroethylene-containing powder to (A) in advance, the decomposition of the raw material resin (B) can be efficiently suppressed, and the melt tension of the matrix resin can be efficiently increased. As a result, with the addition of smaller amounts of radical inhibitors and polytetrafluoroethylene-containing powders,
This is preferable in that the effect of reducing eluted substances and gel-like foreign substances can be exhibited.

When a radical inhibitor or polytetrafluoroethylene-containing powder is added to a plurality of raw materials,
As a result, the amount of the radical inhibitor or the polytetrafluoroethylene-containing powder contained in the resin composition may satisfy the above-mentioned required amount of the radical inhibitor. Raw material resin
Other methods of adding a radical inhibitor or a polytetrafluoroethylene-containing powder to (A), (B) and / or (C) include a method of directly adding them to a reaction tank during polymerization of a resin. And a method of blending after polymerization using a heating roll, a Banbury mixer, a kneader, an extruder, or the like.

As another method of adding a radical inhibitor or polytetrafluoroethylene-containing powder, (A) and (B) which do not contain them, or (A), (B) and
It may be added when preparing the above resin composition or film by mixing the raw resin composed of (C). At this time, the radical inhibitor or the polytetrafluoroethylene-containing powder may be directly added, or may be added by a master batch method. Further, once the raw material resin containing no radical inhibitor or polytetrafluoroethylene-containing powder is mixed to prepare the above resin composition (I), these are put into a hopper of a film forming machine when preparing the film into a film. You may add by adding.

(43) Reinforcing Agent The resin composition of the present invention may contain a fiber reinforcing agent such as glass fiber, metal fiber, potassium whisker or carbon fiber for the purpose of improving rigidity and linear expansion characteristics. And fillers such as talc, calcium carbonate, mica, glass flakes, milled fiber, metal flakes and metal powder. 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. The amount of these additives is desirably 0.5 to 50 parts by mass based on the total amount of the resin composition.

(44) Additives Further, according to the purpose, the present resin composition may contain a heat stabilizer, a light stabilizer, a release agent, a lubricant, a pigment, a flame retardant, a plasticizer, an antistatic agent, an antibacterial agent. It is also possible to add an appropriate amount of a fungicide or the like. (45) Multilayering In addition to the present resin composition, it may be used in combination with another resin composition and / or an adhesive for the purpose of improving flavor and impact resistance.

(46) Applications (Uncoated Material) The resin composition of the present invention can be widely used as a resin molded product. Specifically, it can be used for automobile interior and exterior parts such as bumpers, hoods, door materials, wheel covers, oil tanks, instrument panels, toys, containers, and housings for home appliances, computers, mobile phones, and the like. The method for processing the present resin composition into a molded article is not particularly limited, but widely known injection molding, blow molding and extrusion molding can be applied.

(47) Examples of Metal Plates Used for Coating The resin composition of the present invention can be widely used as a coating material for metal plates. Although the metal sheet 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-silicon alloy coated steel sheet,
Surface treatment of hot-dip galvanized steel sheet such as hot-dip-tin alloy coated steel sheet, electro-galvanized steel sheet, electro-zinc-nickel coated steel sheet, electro-zinc-iron alloy coated steel sheet, electro-zinc-chromium alloy coated steel sheet, etc. Examples include a steel plate, a cold-rolled steel plate, and a metal plate of aluminum, copper, nickel, zinc, magnesium, or the like. Further, the coating on the metal plate may be either one side or both sides. 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 preferably 1 to 300 μm.
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.

(48) Method of coating metal plate: Film pressing (indirect / direct), direct lamination Known methods can be used for coating the metal plate. Specifically, (1) a method in which the resin composition prepared by melt-kneading the raw material resin in advance with a kneading machine is formed into a film with an extruder equipped with a T-die, and this is thermocompression-bonded to a metal plate (in this case, The film may be unstretched or stretched in one or two directions), and (2) a method of directly thermocompression-bonding a film coming out of a T-die. Another method of directly thermocompression bonding a film is as follows: (3) Instead of the present resin composition, a resin and a radical inhibitor, which are raw materials of the present resin composition, are put into a hopper of an extruder equipped with a T die, There is a method in which the present resin composition is kneaded in an extruder and directly thermocompressed. Furthermore, the resin composition of the present invention can exhibit sufficient impact resistance without inclining the crystallinity inside the coated film. Therefore, (4) a method of melting the resin composition and coating it with a bar coater or a roll, (5) a method of immersing a metal plate in the molten resin composition, and (6) a method of dissolving the resin composition in a solvent and spin coating. It is also possible to coat the metal plate by a suitable method, and the coating method is not particularly limited.

The methods (1), (2) and (3) described above are the most preferable as the method of coating a metal plate from the viewpoint of work efficiency. When coating is performed using the method (2), the film thickness is preferably 1 to 300 μm for the same reason as described above. Further, as for the surface roughness of the film, it is preferable that the result of arbitrarily measuring the length of the film surface by 1 mm is 500 nm or less in Rmax. If it exceeds 500 nm, bubbles may be involved when coating by thermocompression bonding. In addition, due to the high impact properties of the present resin composition, it exhibits high impact properties even when used without stretching. Therefore, it can be used as a metal coating material without stretching, and the number of steps can be reduced. In addition, when used as a metal coating material without stretching, it is not necessary to control the crystallinity in the thin film by controlling the temperature, the passing speed, and the like, so that the process window can be enlarged and high-speed production can be performed. Further, temperature control for controlling the degree of crystallinity at the time of film formation and coating is easy, so that a product with stable performance can be manufactured.

(49) Use of a Lubricant The resin film of the present invention is a resin film comprising the resin composition of the present invention.
A resin film formed after coating by the methods (4) to (6) or the like may be used. Further, a known lubricant as disclosed in JP-A-5-186613 may be added for the purpose of improving the lubricating property in the step of coating the metal plate or processing the metal plate.

The lubricant may be any of inorganic materials such as silica, alumina, titania, calcium carbonate and barium sulfate, and organic materials such as crosslinked polystyrene particles and silicone particles, but inorganic materials are preferred. 2.5 μm lubricant particle size
The following is preferred. If it exceeds 2.5 μm, the mechanical properties of the resin film deteriorate. The amount of the lubricant to be added is determined according to the winding property and deep drawing workability of the metal sheet, but is preferably 0.05 to 20%.

In particular, a monodispersed lubricant having an average particle size of 2.5 μm or less and a particle size ratio (major axis / minor axis) of 1.0 to 1.2 is preferable in terms of pinhole resistance. , Spherical titanium oxide, spherical silicone, and the like. The average particle size and the particle size ratio of the lubricant can be determined by observing the particles with an electron microscope. The particle size distribution of the lubricant is sharp and the standard deviation is preferably 0.5 or less.

Since the amount of the lubricant added is related to the winding property in the film production process, it is generally preferable to use a small amount when the particle size is large and a large amount when the particle size is small. For example, depending on the type of lubricant, 0.02-0.
It is about 5% by mass. (50) Use of Pigment The resin film of the present invention may contain a pigment. For example, examples of white pigments include inorganic pigments such as alumina, titanium dioxide, calcium carbonate, and barium sulfate. The average particle size of the pigment is preferably 2.5 μm or less for the same reason as the particle size of the lubricant. The amount of the pigment added is the amount required to achieve the coloring function, and is 3 to 50%
Used within a range. A known method can be used for adding the pigment.

(51) Use of plasticizers, antistatic agents, antibacterial agents, etc. As the plasticizer of the polyester resin, for example, a compound having 2 carbon atoms
These polybasic acid components having a molar ratio of 0 to 2.0 of an aromatic polybasic acid having 8 to 20 carbon atoms or an ester-forming derivative thereof to a fatty acid polybasic acid or an ester-forming derivative thereof having a carbon number of 0 to 2.0; A polyester obtained by condensation polymerization of an aliphatic alcohol having 2 to 20 carbon atoms with a monobasic acid having 2 to 20 carbon atoms or an ester-forming derivative thereof and / or a polyester terminally esterified with a monohydric alcohol having 1 to 18 carbon atoms. Plasticizers for polyester resins can be mentioned.

For the purpose of preventing static electricity damage such as winding of a film around a roll in the film forming step and adhesion of dirt to the film surface, a resin such as an antistatic agent disclosed in JP-A-5-222357 is disclosed. A method of kneading into the composition or a method of applying an antistatic agent described in JP-A-5-164164 to the surface of the film can be applied as necessary.

JP-A-11-48431, JP-A-11-138702
Conventionally known antibacterial agents disclosed in Japanese Patent Application Laid-Open Publication No. H10-163, etc. can be used as necessary. (52) Lamination method (multi-layer / single-layer, single-sided / double-sided, metal thickness) When coating the metal plate with the resin film of the present invention, at least the resin film is coated on one and / or both sides of the metal plate. It can be used for coating in a single layer or a multilayer. At this time, one or two or more types of resin films may be used to form a single-layer or multilayer structure on one side and / or both sides of the metal plate.If necessary, a PET film, a polycarbonate film, etc. Polyester film, polyolefin film such as polyethylene film, polyamide film such as 6-nylon film, other known resin films such as ionomer film, or crystalline / non-crystalline polyester composition film, polyester / ionomer composition A known resin composition film such as a film or a polyester / polycarbonate composition film may be laminated and coated on the lower layer and / or the upper layer. As a specific laminating method, when the above-mentioned methods (1), (2) and (3) are used, the resin film of the present invention and other resin films or resin compositions can be formed using a multilayer T-die. There is a method of manufacturing a multilayer film with a film and thermocompression bonding the film. In addition, the above (4)
When the method of (6) is used, the resin composition of the present invention is coated after coating the other resin composition, or conversely, the other resin composition is coated after coating the resin composition of the present invention. By doing so, it is possible to laminate in multiple layers. The resin-coated metal plate of the present invention is a metal plate coated with the resin film of the present invention, and the coating may be on one side or both sides. The thickness of the metal plate is not particularly limited, but may be 0.01
It is preferably about 5 mm. If it is less than 0.01 mm, it is difficult to develop strength, and if it exceeds 5 mm, it is difficult to process.

(53) Adhesive 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 used as the lower layer and / or upper layer of the resin film of the present invention. To cover the metal plate. 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-based aqueous dispersant disclosed in JP-B-60-12233, JP-B-63
Epoxy adhesive disclosed in JP-13829 A
Polymers having various functional groups disclosed in JP-A-149341.

(54) Can Production Method The resin-coated metal container of the present invention can be formed by a known processing method using a resin-coated metal container made of the resin-coated metal plate of the present invention. Specific examples include draw ironing molding, draw redraw molding, stretch draw molding, and stretch draw ironing molding.A resin-coated metal container using the resin-coated metal plate of the present invention may be used. It is not limited to the above-mentioned molding method.

The resin composition of the present invention comprises a polyester resin
(A), a vinyl polymer (B) containing a unit having a polar group in an amount of 1% by mass or more, a radical inhibitor and a quaternary component of a polytetrafluoroethylene-containing powder, and a resin composition (I) of 100% by mass. Parts of the radical inhibitor from 0.001 to
7 parts by weight and polytetrafluoroethylene-containing powder
It is a resin composition containing 0.001 to 7 parts by mass. 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 and the powder containing polytetrafluoroethylene suppresses the decomposition of the resin composition and the generation of gel-like foreign substances, and reduces the dissolution of decomposition products and the occurrence of film defects when coated on a metal plate. Can supply things.

The resin composition of the present invention may further comprise a polyester resin (A), a vinyl polymer (B) containing 1% by mass or more of a unit having a polar group, a radical inhibitor and a polytetrafluoroethylene-containing powder. , Rubber-like elastic resin body
It is a resin composition containing (C). In particular, 100 parts by weight of a resin composition (I) having a structure in which a rubber-like elastic resin body (C) encapsulated with a vinyl polymer (B) is finely dispersed in a polyester resin (A), 0.001 to inhibitor
7 parts by weight and polytetrafluoroethylene-containing powder
The resin composition containing 0.001 to 7 parts by mass can improve the impact resistance of the polyester resin (A) by the rubber-like elastic resin body (C), and can further improve the rubber-like elastic resin body by the vinyl polymer (B). (C) is encapsulated, so polyester resin
(A) Improves the compatibility of the rubber-like elastic resin body (C), improves the impact resistance, and improves the metal plate and rubber-like elastic resin body.
It is excellent in that direct contact with (C) can be prevented and the adhesion between the metal plate and the resin composition can be ensured. Furthermore, the addition of a radical inhibitor and polytetrafluoroethylene suppresses the decomposition of the resin composition and the generation of gel-like foreign substances, and supplies the resin composition with less elution of decomposition products and less film defects when coated on a metal plate. it can.

As a result, the resin composition of the present invention is excellent in moldability, heat resistance, impact resistance, chemical resistance, mechanical strength, gas barrier properties, adhesion to metals, uniformity, etc., and has excellent flavor properties. Therefore, it can be suitably used for a resin molded article or the like. Further, the resin film of the present invention is a film mainly composed of the resin composition of the present invention, and can be suitably used as a resin film for metal coating because it is particularly excellent in adhesion and flavor. Further, in the resin-coated metal plate of the present invention, since the above resin composition or the resin film covers one or both surfaces of the metal plate, adhesion between the resin and the metal plate, corrosion resistance, impact resistance, workability. It has excellent coating and printing properties, and it is easy to impart design properties.Addition of a radical inhibitor suppresses the decomposition of resin, so metal containers such as metal cans, housings for home appliances, etc. It can be widely used for members such as 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.

Furthermore, since 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 an impact resistance that can withstand the impact during canning, canning, and transportation. It has heat resistance enough to withstand drying, printing, baking and the like, and particularly has a long-term storage property with excellent flavor properties (perfume retention properties).
Therefore, it can be suitably used as a container for soft drinks and foods.

(55) Performance and Mechanical Properties of Resin Coating Layer When molding such as draw ironing molding, draw redraw molding, stretch draw molding, and stretch draw ironing molding, cracks may occur in the resin coating layer. However, the mechanical properties of the resin are one of the important factors for crack generation. In particular, it is desirable that the resin coating layer has a breaking elongation of 20% or more, preferably 50% or more, and a breaking strength of 2 kgf / mm ² or more.

Here, the elongation at break and the strength at break of the resin coating layer can be determined by an ordinary tensile tester. The tensile test method can be determined by setting a resin coating layer of 5 mm × 60 mm at a distance between the chucks (reference points) of 30 mm and performing a tensile test at a constant temperature of 25 ° C. at a tensile speed of 20 mm / min. When the tensile properties at a low temperature are determined, they can be determined by performing a similar tensile test at a constant temperature of 5 ° C. The resin coating layer may be collected from any of a film, a resin-coated steel plate, and a molded product. As a method of collecting only the resin-coated layer from the resin-coated steel sheet or the molded body, the resin-coated steel sheet or the molded product can be peeled by the following method and provided as a film-like specimen.

A sample was cut out from a resin-coated steel sheet or its molded product to a tensile test piece size, immersed in 18% hydrochloric acid at 40 ° C. for about 10 hours, and only the steel sheet was eluted to leave only the resin coating layer. The film-shaped test piece can be obtained by washing and drying. If there is a resin coating layer on both sides of the resin-coated steel sheet or its molded body, use a cutter knife or the like to insert a grid-shaped flaw in the resin coating layer on the opposite side of the resin coating layer to be sampled into hydrochloric acid. By dipping, a film-like test piece can be obtained. Since the resin coating layer obtained from the molded body has already been stretched by molding, the elongation of the resin is smaller than the elongation of the resin coating layer collected from the film or the resin-coated steel sheet, but the resin collected from the molded body If the elongation of the coating layer is 20% or more and the breaking strength is 2 kgf / mm ² , the impact resistance as a molded article is in a favorable state. The elongation of the resin coating layer collected from the molded article is less than 20%, or the breaking strength is 2 kgf / mm ²
If it is less than 100%, the impact resistance of the resin film of the molded article, particularly the impact resistance at low temperatures, becomes low, and cracks tend to occur on the film surface at the time of impact, which is not preferable.

(56) Degree of Stretching of Resin Coating Layer The fine dispersion of the rubber-like elastic resin (C) in the polyester resin (A) has been defined above, but the resin composition of the present invention is After being coated, if the metal plate is subjected to drawing or other processing, the state of fine dispersion changes after the processing. Generally speaking, when the coated metal plate is stretched in one direction, the size of the finely dispersed particles in the stretching direction is elongated in proportion to or less than the stretching ratio, and the finely dispersed particles in the direction perpendicular to the stretching direction are stretched. It can be said that the dimensions remain intact after stretching or tend to decrease somewhat. When two-way processing or complicated processing is performed, it deforms accordingly.

In the examples described later, deformation of the finely dispersed rubber-like elastic resin (C) when the steel plate is coated with a steel plate and then deep drawn to produce a can is shown.

[0127]

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 1% by mass or more units
As an ethylene ionomer [Himilan 1706, 1707 manufactured by DuPont-Mitsui Co., Ltd.], an ethylene-methacrylic acid copolymer [Nucrel N1035 manufactured by DuPont-Mitsui Co., Ltd.], and polybutyl acrylate as a core-shell type rubbery elastic material. Polymethyl methacrylate copolymer (MBA) [Kuraha Chemical Co., Ltd. paraloid EXL2314], rubber-like elastic resin
(C) as ethylene-propylene rubber (EPR) [JSR Corporation
EP07P], ethylene-butene rubber (EBM) [EBR manufactured by JSR Corporation]
M2041P] was used. A mixture of polytetrafluoroethylene powder (average particle size: 1 μm) and dodecyl methacrylate powder modified with glycidyl methacrylate (5 wt%) (mixing weight ratio 80/20) “TF-1” as the polytetrafluoroethylene-containing powder , A mixture of polytetrafluoroethylene powder (average particle size: 1 μm) and powder obtained by pressing and grinding the above PET pellets (mixing weight ratio: 80/20) “T
F-2 ", polytetrafluoroethylene powder (average particle size: 1 μm) simple substance" TF-3 "was used. TF-1, TF-
The maximum minor axis of the equivalent ellipsoid of 2, TF-3 is 50,150,
It was 30 μm.

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, TF-1
Were dry blended at the respective composition ratios shown in Table 1 using a V-type blender. The composition of each resin is as shown in Table 1. In each case of the radical inhibitor and TF-1, 0.1 part by mass was added to 100 parts by mass of the resin composition (I). This mixture was melt-kneaded at 260 ° C. with a twin-screw extruder to obtain resin composition pellets containing a powder containing a radical inhibitor and polytetrafluoroethylene.

An ultrathin section was 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. When rubber-like elastic resin (C) is added, vinyl polymer (B) in polyester resin (A)
The state of dispersion of the rubber-like elastic resin (C) was analyzed by a transmission electron microscope. As a result, when the rubber-like elastic resin (C) was not added, the equivalent spherical equivalent diameter of the vinyl polymer (B) was as shown in Table 1.
As shown in the figure, it was finely dispersed in the polyester resin (A) at 1 μm or less. When the rubber-like elastic resin (C) is added, the rubber-like elastic resin (C) is a vinyl polymer.
As shown in Table 1, the rubber-like elastic resin (C) was finely dispersed in the polyester resin (A) at an equivalent sphere equivalent diameter of 1 μm or less as shown in Table 1.

[0130]

[Table 1]

The pellets were extruded using a T die and extruded.
A film having a thickness of μm was obtained (extrusion temperature: 280 ° C.). This film is laminated on both sides of 2.5mm thick tin-free steel heated to 250 ° C, and cooled to 100 ° C within 10 seconds by water cooling.
It was quenched to the following. The room temperature resin-coated metal sheet thus obtained was evaluated for its flavor retention, taste retention, adhesion, room temperature impact resistance, low temperature impact resistance, and film uniformity by the following evaluation methods. Was evaluated. In addition, the evaluation of fragrance retention and taste retention was performed using the same test piece, and the adhesion, room temperature impact resistance, low temperature impact resistance, and film uniformity were evaluated for fragrance retention and taste retention. Evaluation was performed using a test piece different from the evaluated test piece.

<Scent 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 heated 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

[0133]

[Table 2]

<Adhesiveness, Impact Resistance at Room Temperature, Impact Resistance at Low Temperature, and Uniformity of Film> The above resin-coated metal plate was treated with citric acid 1.
The film was immersed in an aqueous solution (UCC solution) of 5% by mass-1.5% by mass of sodium chloride (UCC solution) for 24 hours at room temperature, and then evaluated by the length (mm) (average of 10 samples) of the film. Evaluation: ◎: 0.0mm, ○: 0.0 to 0.5
mm, Δ: 0.5 to 2.0 mm, and ×: more than 20 mm. Table 3 shows the results of the adhesion test.

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 evaluation was performed.
The impact resistance at low temperature was evaluated. Evaluation: ◎: All samples are less than 0.01 mA, ○: 1 to 3 samples are 0.01 mA or more, Δ: 3 to
6 samples were 0.01 mA or more, and x: 7 samples or more were 0.01 mA or more. Table 3 shows the results.

The uniformity of the coating is determined by detecting gel-like foreign matter that is visible.
And evaluate by converting to the number of occurrences per unit area.
Was. Rating ◎: 0.01 pieces / cm^TwoBelow, ○: 0.1 pieces /
cm ^TwoBelow, Δ: 0.3 pieces / cm^TwoBelow, ×: 0.3
/ Cm^TwoSuper.

[Table 3] (Examples 16 to 30) The polytetrafluoroethylene-containing powder of Examples 1 to 15 was changed from TF-1 to TF-2 and kneaded,
Film formation, lamination, and flavor retention, flavor retention adhesion, room temperature impact resistance, low temperature impact resistance, and film uniformity were evaluated. As a result, almost the same results as in Examples 1 to 15 were obtained.

(Examples 31 to 43) Composition ratio of each resin shown in Example 2 (polyester resin (A): vinyl polymer (B) =
92: 8, TF-1 to the resin composition (I) 100: 0.1 part by mass added)
When preparing the resin composition of the above, various radical inhibitors shown in Table 4 were used instead of tetrakismethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane as a radical inhibitor. Resin composition pellets were prepared by adding 0.1 parts by mass to 100 parts by mass of composition (I).

An ultrathin section was cut from the resin composition with a microtome, stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) in the polyester resin (A) was analyzed with a transmission electron microscope. As a result, the equivalent spherical equivalent diameter of the vinyl polymer (B) was the same as that of Example 2, and it was finely dispersed in the polyester resin (A) at 1 μm or less. Using the pellets thus prepared, a resin-coated metal plate is prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion, room temperature impact resistance, low temperature impact resistance, coating uniformity are obtained. Each item was evaluated. Table 4 shows the results.

[0139]

[Table 4] (Examples 44 to 56) The polytetrafluoroethylene-containing powders of Examples 31 to 43 were changed from TF-1 to TF-2, and kneading, film formation, laminating, flavor preserving property, and fragrance preserving adhesiveness , Room temperature impact resistance, low temperature impact resistance and coating uniformity were evaluated. As a result, almost the same results as in Examples 31 to 43 were obtained.

(Examples 57 to 58) Composition ratio of each resin shown in Example 5 (polyester resin (A): vinyl polymer (B):
Rubber pellets (C) = 87: 3: 10) resin pellets, tetrakis [methylene (3,5-di-t-butyl) radical inhibitor
-4-Hydroxyhydrocinnamate)] powder containing methane and polytetrafluoroethylene: TF-1 (Example 5
7) or TF-2 (Example 58) was added and dry blended using a V-type blender. The amounts of the radical inhibitor and the polytetrafluoroethylene-containing powder were 0.1 parts by mass with respect to 100 parts by mass of the resin pellets. This mixture is heated to 260 ° C in a twin screw extruder with a T-die.
To form a film having a width of 30 mm and a thickness of 25 microns.

An ultrathin section was cut from the film with a microtome, stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) in the polyester resin (A) was analyzed with a transmission electron microscope. When the rubber-like elastic resin (C) was added, the dispersion state of the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A) was analyzed by a transmission electron microscope. As a result, the rubber-like elastic resin (C) is almost 100% encapsulated in the vinyl polymer (B), and the equivalent spherical equivalent diameter of the rubber-like elastic resin (C) is 0.6 μm and the polyester resin (A) It was finely dispersed inside.

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.

[0143]

[Table 5]

(Examples 59 to 71) Composition ratio of each resin shown in the above Example 57 (polyester resin (A): rubber-like elastic resin)
(C): vinyl polymer (B) = 87: 10: 3, TF-1 to the resin composition (I) 100: 0.1 parts by mass added) When preparing a resin composition, as a radical inhibitor Tetrakis [methylene (3,5-
Instead of di-t-butyl-4-hydroxyhydrocinnamate)] methane, 0.1 parts by mass of each of the various radical inhibitors shown in Table 6 was added to 100 parts by mass of the resin composition (I) to give a resin composition. A product pellet was prepared.

An ultrathin section was cut out from the resin composition with a microtome, dyed with ruthenic acid, and the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A) were cut out.
Was analyzed with a transmission electron microscope. As a result,
In each case, the rubber-like elastic resin (C) is a vinyl polymer (B) and almost 1
The rubber-like elastic resin (C) was equivalent to the equivalent sphere diameter of Example 1 and was finely dispersed in the polyester resin (A) at 1 μm or less.

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

[0147]

[Table 6] (Examples 72 to 84) The polytetrafluoroethylene-containing powders of Examples 59 to 71 were changed from TF-1 to TF-2, and kneaded, formed into a film, laminated, dispersed, preserved, and flavored. Adhesiveness,
The room-temperature impact resistance, low-temperature impact resistance, and coating uniformity were evaluated. As a result, substantially the same results as in Examples 59 to 71 were obtained.

(Examples 85 to 89) Composition ratio of each resin shown in Example 2 (polyester resin (A): vinyl polymer (B) = 9)
In preparing the resin composition of 2: 8), tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane was used as a radical inhibitor and a polytetrafluoroethylene-containing powder, respectively. And TF-1 were added at the ratios shown in Table 7 to prepare resin composition pellets.

[0149] Ultrathin sections were cut out from the resin composition with a microtome, stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) in the polyester resin (A) was analyzed with a transmission electron microscope. As a result, the equivalent sphere equivalent diameter of the vinyl polymer (B) was 0.5 μm or more and 1 μm or less, and the polyester resin
(A) Finely dispersed therein. Using the pellets thus prepared, a resin-coated metal plate is prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion, room temperature impact resistance, low temperature impact resistance, and film uniformity are obtained. Each item of gender was evaluated. Table 7 shows the results.

[0150]

[Table 7] (Examples 90 to 94) The polytetrafluoroethylene-containing powder of Examples 85 to 89 was changed from TF-1 to TF-2, and kneaded, formed into a film, laminated, dispersed, preserved, and perfumed. The adhesiveness, room temperature impact resistance, low temperature impact resistance and uniformity of the coating were evaluated. As a result, substantially the same results as in Examples 85 to 89 were obtained.

(Examples 94 to 98) Composition ratio of each resin shown in Example 5 (polyester resin (A): rubber-like elastic resin)
(C): When preparing a resin composition of a vinyl polymer (B) = 87: 10: 3), tetrakis [methylene (3,5-di-t) as a radical inhibitor and polytetrafluoroethylene-containing powder -Butyl-4-hydroxyhydrocinnamate)] methane and TF-1 were added in the proportions shown in Table 8 to prepare resin composition pellets.

An ultrathin section was cut out from the resin composition with a microtome, dyed with ruthenic acid, and a vinyl polymer (B) and a rubber-like elastic resin (C) in a polyester resin (A) were cut.
Was analyzed with a transmission electron microscope. As a result,
In each case, the rubber-like elastic resin (C) is a vinyl polymer (B) and almost 1
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 each of the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and the fragrance retention, taste retention, adhesion, room temperature impact resistance, low temperature impact resistance, Each item of coating uniformity was evaluated. Table 8 shows the results.

[0154]

[Table 8] (Examples 99 to 103) The polytetrafluoroethylene-containing powders of Examples 94 to 98 were changed from TF-1 to TF-2, and kneaded, formed into a film, laminated, dispersed, preserved, and perfumed. The adhesiveness, room temperature impact resistance, low temperature impact resistance and uniformity of the coating were evaluated. As a result, almost the same results as in Examples 94 to 98 were obtained.

(Example 104) Composition ratio of each resin shown in Example 2 (polyester resin (A): vinyl polymer (B))
= 92: 8) when preparing the resin composition, polyester resin
As (A), PET to which TF-1 was added in advance as a polytetrafluoroethylene-containing powder was used, and as vinyl polymer (B), 1706 to which a radical inhibitor had been added in advance was used. That is, 100 parts by mass of PET and 0.1 parts by mass of TF-1 and 100 parts by mass of 1706 and tetrakis [methylene (3,5-
0.1 part by mass of di-t-butyl-4-hydroxyhydrocinnamate)] methane was dry blended using a V-type blender, and the mixture was mixed in a twin-screw extruder at 260 parts each.
The mixture was melt-kneaded at 150 ° C. and 150 ° C. to obtain pellets of PET containing TF-1 and vinyl polymer (B) containing a radical inhibitor.
These pellets were dry-blended using a V-type blender, and this mixture was melt-kneaded at 260 ° C. with a twin-screw extruder to prepare resin composition pellets.

An ultrathin section was cut out from the resin composition with a microtome, stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) in the polyester resin (A) was analyzed with a transmission electron microscope. As a result, the equivalent spherical equivalent diameter of the vinyl polymer (B) was 0.7 μm, and it was finely dispersed in the polyester resin (A). Using the pellets thus prepared, a resin-coated metal plate is prepared in the same manner as described above, and evaluation of each item of fragrance retention, taste retention, adhesion, room temperature impact resistance and low temperature impact resistance is performed. Was done. Table 9 shows the results.

[0157]

[Table 9] (Example 105) The polytetrafluoroethylene-containing powder of Example 104 was changed from TF-1 to TF-2, and kneaded, formed into a film, laminated, dispersed, taste-retaining, flavor-retaining and adhesive,
The room-temperature impact resistance, low-temperature impact resistance, and coating uniformity were evaluated. As a result, almost the same results as in Example 104 were obtained.

(Example 106) Composition ratio of each resin shown in Example 5 (polyester resin (A): rubber-like elastic resin)
(B): When preparing a resin composition of the vinyl polymer (C) = 87: 10: 3), PET containing 0.1 parts by mass of TF-1 previously added as the polyester resin (A) was rubber-like. EBM was used as the elastic resin (B) and 1706 to which a radical inhibitor had been added in advance as the vinyl polymer (C). Ie PET: 100
Parts by mass and TF-1: 0.1 parts by mass, 100 parts by mass of 1706 and 0.1 part by mass of tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane using a V-type blender The mixture was melt-kneaded at 260 ° C. and 150 ° C. in a twin-screw extruder to obtain pellets of PET containing TF-1 and vinyl polymer (B) containing a radical inhibitor. . These pellets and rubbery elastic resin
The pellets of (C) were dry-blended using a V-type blender, and this mixture was melt-kneaded at 260 ° C. with a twin-screw extruder to prepare resin composition pellets.

An ultrathin section was cut out from the resin composition with a microtome, dyed with ruthenic acid, and a vinyl polymer (B) and a rubber-like elastic resin (C) in a polyester resin (A).
Was analyzed with 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 0.5 μm, which is finely divided in the polyester resin (A). Was dispersed.

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

[0161]

[Table 10] (Example 107) The polytetrafluoroethylene-containing powder of Example 106 was changed from TF-1 to TF-2, and kneaded, formed into a film, laminated, dispersed, flavor-retaining, flavor-retaining adhesive,
The room-temperature impact resistance, low-temperature impact resistance, and coating uniformity were evaluated. As a result, almost the same results as in Example 106 were obtained.

Examples 108 to 111 Each resin, polytetrafluoroethylene-containing powder and TF-1, tetrakis [methylene (3,5-di-t) as a radical inhibitor shown in Table 11 were used.
-Butyl-4-hydroxyhydrocinnamate)] methane was dry blended using a V-type blender. The composition of each resin is as shown in Table 11. In each case, 0.1 parts by mass of the polytetrafluoroethylene-containing powder and the radical inhibitor were added to 100 parts by mass of the resin composition (I).
This mixture was melt-kneaded at 230 ° C. with a twin-screw extruder to obtain resin composition pellets.

As a result of analyzing the dispersion state in the same manner as in Examples 1 to 15, the equivalent spherical equivalent diameter of the dispersed particles was as shown in Table 11.
It was finely dispersed in the polyester resin (A) at a size of 0.3 μm or more and 1 μm or less. When rubber-like elastic resin (C) is added, rubber-like elastic resin (C) is 100% of vinyl polymer (B).
% Encapsulated.

[0164]

[Table 11]

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

[0166]

[Table 12]

(Examples 112 to 115) The above Examples 108 to 111
TF-1 to TF-2
And kneaded, formed into a film, laminated, and evaluated for the dispersion state, the flavor retention, the fragrance retention adhesion, the room temperature impact resistance, the low temperature impact resistance, and the film uniformity. As a result, almost the same results as in Examples 108 to 111 were obtained. (Examples 116 to 118) Each of the resins shown in Table 13, TF-1, and tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane as a radical inhibitor were treated with V
Dry blending was performed using a mold blender. The mixing ratio of each resin is as shown in Table 13, and the radical inhibitor, TF
In each case, 0.1 part by mass was added to 100 parts by mass of each resin composition (I). The mixture is passed through a twin screw extruder for 240
The resulting mixture was melt-kneaded at a temperature of ° C. to obtain resin composition pellets.

As a result of analyzing the dispersion state in the same manner as in Examples 1 to 15, as shown in Table 13, the core-shell type rubber-like elastic body had an equivalent sphere-equivalent diameter of 1 μm or less and a polyester resin.
(A) Finely dispersed therein.

[0169]

[Table 13]

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

[0171]

[Table 14] (Examples 119 to 121) The polytetrafluoroethylene-containing powders of Examples 116 to 118 were changed from TF-1 to TF-2, and kneaded, formed into a film, laminated, dispersed, preserved, and perfumed. The adhesiveness, room temperature impact resistance, low temperature impact resistance and uniformity of the coating were evaluated. As a result, almost the same results as in Examples 116 to 118 were obtained. (Examples 122 to 125) Each resin shown in Table 15, polytetrafluoroethylene-containing powder, and TF-
3, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane was dry blended using a V-type blender. The composition of each resin is as shown in Table 11, the polytetrafluoroethylene-containing powder and the radical inhibitor in each case the resin composition (I) 100
0.1 parts by mass was added to the parts by mass. This mixture was melt-kneaded at 230 ° C. (when using PBT) and 260 ° C. (when using PET) using 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 as shown in Table 11.
It was finely dispersed in the polyester resin (A) at a size of 0.3 μm or more and 1 μm or less. When rubber-like elastic resin (C) is added, rubber-like elastic resin (C) is 100% of vinyl polymer (B).
% Encapsulated.

[0173]

[Table 15]

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

[0175]

[Table 16]

(Comparative Examples 1 to 8) Each resin shown in Table 17 was dry-blended using a V-type blender without adding a polytetrafluoroethylene-containing powder and a radical inhibitor. This mixture was melt-kneaded at 230 ° C. with a twin-screw extruder to obtain resin composition pellets. As a result of analyzing the dispersion state in the same manner as in Examples 1 to 15, as shown in Table 17, the particles were finely dispersed in the polyester resin (A) with an equivalent spherical equivalent diameter of 1 μm or less. The rubber-like elastic resin (C) was encapsulated 100% with the vinyl polymer (B).

[0177]

[Table 17]

Further, a film was prepared in the same manner as in Examples 1 to 15 and bonded to both sides of a tin-free steel having a thickness of 0.19 mm to obtain a scent-retaining property, a taste-retaining property, an adhesion property, an impact resistance and a coating uniformity. evaluated. The results are shown in Table 18.

[0179]

[Table 18]

In each case, the adhesion, room-temperature impact resistance and low-temperature impact resistance remain unchanged as compared with the case where the resin composition to which the radical inhibitor and the powder containing polytetrafluoroethylene are added is used. It was found to be inferior in terms of fragrance retention, flavor retention and coating uniformity. Comparative Example 9 PET was dry-blended with a mass ratio of 90:10 of PET as a polyester resin and MBA as a core-shell rubber-like elastic material without adding a radical inhibitor and polytetrafluoroethylene-containing powder. This mixture was melt-kneaded at 240 ° C. using a twin-screw extruder to obtain resin composition (I) 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 had an equivalent spherical equivalent diameter of 0.
It was finely dispersed in the polyester resin at 25 μm.

Further, a film was prepared 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 2.5 mm to evaluate the fragrance retention, taste retention, adhesion, impact resistance and coating uniformity. did. Table 19 shows the results.

[0182]

[Table 19]

Compared with the case where a resin composition to which a radical inhibitor and a polytetrafluoroethylene-containing powder are added is used, adhesion, room-temperature impact resistance, and low-temperature impact resistance are not changed. It was found to be inferior in terms of taste retention, coating uniformity. (Comparative Example 10) In preparing a resin composition of the polyester resin (A): vinyl polymer (B) = 92: 8 of Comparative Example 1, TF-1 and 3- (N- Salicyloyl) amino-1,
0.1 parts by mass of 2,4-triazole and 100 parts by mass of the resin composition (I) were added to prepare a resin composition pellet. 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 1.2 μm.

Using the pellets thus prepared, a resin-coated metal plate was prepared, and the fragrance retention, taste retention, adhesion,
The impact resistance at room temperature, impact resistance at low temperature, and uniformity of coating were evaluated. The results are shown in Table 20.

[0185]

[Table 20]

When a metal deactivator was used as an additive, no improvement in fragrance retention and flavor retention was observed. (Comparative Example 11) In preparing a resin composition of Comparative Example 3 having a polyester resin (A): rubber-like elastic resin (C): vinyl polymer (B) = 87: 10: 3, TF-1 and 3- as metal deactivator
(N-salicyloyl) amino-1,2,4-triazole was added in an amount of 0.1 part by mass with respect to 100 parts by mass of the resin composition (I) to prepare a resin composition pellet. As a result of analyzing the dispersion state in the same manner as in Examples 1 to 15, the rubber-like elastic resin (C) is 100% encapsulated with the vinyl polymer (B), and is equivalent to the rubber-like elastic resin (C). The particles had a sphere-converted diameter of 1.3 μm and were finely dispersed in the polyester resin.

Using the pellets thus prepared, a resin-coated metal plate was prepared, and the fragrance retention, taste retention, adhesion,
Each item of the normal temperature impact resistance and the low temperature impact resistance was evaluated. Table 21 shows the results.

[0188]

[Table 21]

When a metal deactivator was used as an additive, no improvement in fragrance retention and flavor retention was observed. (Comparative Examples 12 and 13) Composition ratio of each resin shown in Example 2 above
(Polyester resin (A): when preparing a resin composition of vinyl polymer (B) = 82: 8), 0.1 parts by mass of TF-1 based on the resin composition (I), a radical inhibitor As tetrakis [
Methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane was added in the following proportions to prepare resin composition pellets. Ultrathin sections were cut out from the resin composition with a microtome, stained with ruthenic acid, and the dispersion state of the vinyl polymer (B) in the polyester resin (A) was analyzed with a transmission electron microscope. The equivalent spherical equivalent diameter of the vinyl polymer (B) is 0.3 μm or more and 1 μm or less and is a polyester resin.
(A) Finely dispersed therein.

Using each of the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and a fragrance preserving property, a taste preserving property, an adhesive property, a normal temperature impact resistance, a low temperature impact resistance, Each item of coating uniformity was evaluated. The results are shown in Table 22.

[0191]

[Table 22]

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), TF-
1 in an amount of 0.1 part by mass with respect to the resin composition (I), and tetrakis [methylene (3,5-di-t-butyl-4) as a radical inhibitor.
-Hydroxyhydrocinnamate)] methane was added in the following proportions to prepare resin composition pellets.

Ultrathin sections were cut out from the resin composition with a microtome, stained with ruthenic acid, and the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A) were cut out.
Was analyzed with a transmission electron microscope. As a result,
In each case, the rubber-like elastic resin (C) is a vinyl polymer (B) and almost 1
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 each of the pellets thus prepared, a resin-coated metal plate was prepared in the same manner as described above, and a fragrance preserving property, a taste preserving property, an adhesion property, a normal temperature impact resistance, a low temperature impact resistance, Each item of coating uniformity was evaluated. The results are shown in Table 23.

[0195]

[Table 23]

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. (Example of confirming increase in melt tension) Examples 1 to 15 and Comparative Examples 1 to 1
The increase in the melt tension due to the polytetrafluoroethylene-containing powder was confirmed by the size of the neck-in when the resin composition of No. 5 was formed into a film having a thickness of 30 μm by a T-die. In Comparative Example 1, the neck-in was 10 to 15% of the T-die width, whereas in Example 1, the neck-in was reduced to 1 to 5%. This result is presumed to be due to the fact that the melt tension increased to suppress the heat shrinkage due to solidification. (Comparative Examples 16 to 18) Kneading, film forming, and kneading in the same manner as in Examples 3, 5, and 7 except that TF-1 was excluded from the resin compositions.
Laminating was performed, and each item of dispersibility, flavor retention, flavor retention, adhesion, impact resistance at room temperature, impact resistance at low temperature, and uniformity of the coating film was evaluated. It was almost the same as the example except the coating uniformity,
The coating uniformity was inferior to these (x or Δ). (Comparative Examples 19 to 20) All except that the addition amount of TF-1 was changed to 0.0009 parts by mass (Comparative Example 19) and 7.5 parts by mass (Comparative Example 20) with respect to the resin composition (I). In the same manner as in Example 7, kneading, film formation, lamination, dispersibility,
Each item of fragrance retention, taste retention, adhesion, impact resistance at room temperature, impact resistance at low temperature, and uniformity of the coating was evaluated. Comparative Example 20 was the same as Example 7 except for the coating uniformity, but the coating uniformity was poor (x or Δ). In Comparative Example 21, the adhesion was significantly reduced. From Comparative Examples 17 to 20, it is necessary to add an appropriate amount of polytetrafluoroethylene-containing powder in order to ensure uniformity of the coating, and that the adhesion is reduced when a certain amount or more of the powder is added. I understand. (Comparative Example 21) Based on an example of Japanese Patent Publication No. 2-9935, P
Biaxially stretched film consisting of two layers of BT and PET (PBT layer: 10
μm, PET layer: 20 μm, refractive index in the thickness direction of the PET layer: 1.526) on a tin-free steel under the same conditions as in Examples 1 to 15 (so that the PBT layer adheres to the tin-free steel). ), Adhesion and impact resistance in Example 1.
The evaluation was performed in the same manner as in the case of 1515.

Comparative Example 22 A biaxially stretched polyester film (terephthalic acid / isophthalic acid / ethylene glycol residue (78/22
/ 100), 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 The evaluation was performed in the same manner as 15.

(Comparative Example 23) 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. The results are shown in Table 24.

[0199]

[Table 24]

[0200] With the resins obtained by these conventional methods, sufficient adhesion and impact resistance could not be obtained. (Examples 125 to 130, Comparative Examples 24 to 26)
, 11, 110, 111, 117, and the resin-coated metal plates obtained in Comparative Examples 21 to 23 were cut into a disk shape having a diameter of 150 mm, and deep-drawn in four stages using a drawing die and a punch. (Hereinafter abbreviated as cans) were prepared in 10 cans.

The following observations and tests were performed on these cans, and the results of evaluation based on the following criteria are shown in Table 25. (1) Deep drawing processability I (evaluation of film surface layer);: For all 10 cans, the film was processed without any abnormality, and no whitening or breakage was observed in the film on the inner and outer surfaces of the can.

Δ: For 1 to 5 cans, whitening of the film was observed at the top of the can. C: Film breakage is 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.

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

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

[0205]

[Table 25]

From the above results, it can be seen that the resin composition to which the radical inhibitor and the tetrafluoroethylene-containing powder of the present invention are added has excellent adhesion to metal and impact resistance, and particularly impact resistance at low temperatures. It can be seen that they are excellent, and furthermore excellent in fragrance retention, taste retention, and film uniformity as compared with the prior art. In addition, it can be seen that the resin-coated metal plate of the present invention is excellent in processability of coating, and that the resin-coated metal container of the present invention is also excellent in impact resistance and heat embrittlement resistance.

(Reference Example 1: Correlation between TOC and fragrance retention) Polyester resin (A) and vinyl polymer (B) at a composition ratio of 92: 8
The pellets were dry blended using a V-blender. This mixture was melt-kneaded at 260 ° C. with a twin-screw extruder to obtain resin composition pellets. Using this pellet, a resin-coated metal plate was prepared in the same manner as in Examples 1 to 15.

This resin-coated metal plate (12.5 cm × 8 cm square) was put in a glass container together with distilled water (300 mL), sealed with a glass stopper, and after a predetermined time at 85 ° C., the TOC value of the content water (ppm ) 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 26.

[0209]

[Table 26]

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 TO of these pellets and raw resin pellets
The C value was measured 7 days later by the method shown in Reference Example 1. The results are shown in Table 27.

[0212]

[Table 27]

Under the conditions of melt-kneading at 260 ° C., the TOC value is low for the three kinds of raw material resins, the mixed resin of PET and EBM, and the mixed resin of EBM and 1706, and the mixed resin of PET + EBM + 1706 and PET + 1706 Then, the high TOC value revealed that TOC was not caused by mere thermal decomposition. (Reference Example 3: Analysis of metal elements 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 28) .

[0214]

[Table 28]

(Reference Example 4: Metal element content in PET resin and TO
C value) Using PET resin C shown in Table 26 and PET resin D obtained by adding 200 ppm of germanium oxide to PET resin C, 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.
5 ppm from resin pellets prepared using PET, PET resin
16 ppm TOC from resin pellets prepared using D
Was observed, and it was confirmed that germanium oxide accelerated the decomposition of the resin.

Example 14 (Observation of Cross Section of Ternary Resin Composition)
A film containing a radical inhibitor was prepared by the method described in (1). FIG. 1 shows an electron micrograph of a cross section of a sample of the ternary resin composition sheet thus obtained. Rubber-like elastic resin encapsulated with polar group-containing vinyl polymer (blackest part) in PET matrix (gray part)
Are dispersed in the order of submicrons.

(Example of Observing Degree of Stretching of Coating Resin) The resin composition of Example 7 was formed into a film having a thickness of 30 μm with a T-die, and this resin film was heated to 250 ° C. and had a thickness of 2.5 mm.
And then rapidly cooled to 100 ° C. or less within 10 seconds by water cooling. The obtained resin-coated steel sheet was drawn with a blank diameter of 179 mm, a first-stage drawing ratio of 1.6, a second-stage drawing ratio of 0.73, and a third-stage drawing ratio of 0.8 to obtain a can diameter of 6 mm.
It was molded into a 6 mm can and 122 mm can height. As shown in FIG. 2, the height of the can from the molded can was 20 mm, 50 mm and 90 mm from the bottom of the can.
Cut out a sample of the can body centered on the mm position, break it with liquid nitrogen so that the resin coating layer in the thickness direction on the inner side of the can comes out, and observe it from two directions: the can-slice direction and the can vertical direction. Samples were taken.

(B) and (C) in the resin coating layer of the collected sample
The morphological observation of the phase was performed by an electron microscope (SEM). (A)
(B) If the boundaries of the (C) phase are difficult to understand, the collected sample is subjected to ultrasonic cleaning in xylene solvent (B) (C)
Only the phases were selectively dissolved and removed. The photographs of FIGS. 3 to 6 are taken by an electron microscope in this way, and show the cross section of the resin coating layer in the direction of the wheel body upper section (FIG. 3), the cross section of the resin coating layer in the vertical direction of the upper part of the can body (FIG. 4), It is a SEM photograph of a section (FIG. 5) of the resin coating layer in the direction of the wheel lower section, and a section (FIG. 6) of the resin coating layer in the vertical direction of the lower can body.

Referring to FIGS. 3 to 6, the can body wall of the can molded body is deformed by drawing in such a manner that it shrinks in the circumferential direction and expands in the height direction, and the resin coating layer undergoes the same deformation. is recieving. For this reason, the main component in the resin coating layer (A)
Following the deformation of the phases, the (B) and (C) phases are also elongated in the can height direction. Thus, the form of the (B) and (C) phases has a shape close to a sphere when the film or the resin-coated plate is not deformed, but when the film or the resin-coated plate is plastically deformed due to formation or the like, The (B) and (C) phases are also deformed following the original sphere.

However, when a resin-coated metal plate using the resin composition of the present invention is formed into a can or the like, the (B) and (C) phases in the resin coating layer are also present in a deformed form according to the deformed form of the metal base layer. But present in the undeformed resin composition (B)
(C) It is not essentially different from the phase, but has the same function. Fig. 7 shows the height and position of the sampled cans, the maximum length (grain size in the vertical direction) and the minimum length (grain size in the cross section direction) of the morphology of the (B) and (C) phases obtained from the electron micrograph. ) Shows the relationship of the ratio (aspect ratio).

Note that, in addition to the deformation of this example, the (B) and (C) phases may be present in a deformed form due to deformation of the resin coating layer due to thermocompression during film stretching or lamination. It is confirmed that the resin composition is not different from the (B) and (C) phases existing in the resin composition which has not been essentially deformed and has the same functional effect.

[0222]

According to the resin composition of the present invention, the polyester resin (A) has heat resistance, workability, adhesion to a metal plate,
Polyester resin with vinyl polymer (B) while maintaining properties such as gas barrier properties, flavor properties, and film uniformity
Further elongation and impact resistance of (A) are improved. further,
By adding a radical inhibitor that suppresses the decomposition of the vinyl polymer (B) by the polyester resin (A), it is possible to suppress the deterioration of the resin and the generation of low molecular weight organic components.
Further, by further adding the tetrafluoroethylene-containing powder, the melt tension at the time of heating and mixing can be increased to prevent the resin from adhering and staying at the flow stopping portion in the barrel or the like, thereby suppressing the generation of gel-like foreign matter. Further, the impact resistance can be improved by adding a rubber-like elastic resin (C) that does not suppress the action of the radical inhibitor or the powder containing tetrafluoroethylene. In this case, the rubber-like elastic resin (C) is encapsulated by the polar vinyl polymer (B), so that the polyester resin (A) and the rubber-like elastic resin are encapsulated.
The compatibility with (C) is improved, and the direct contact between the metal plate and the rubber-like elastic resin (C) is prevented, so that the adhesion between the metal plate and the resin composition can be ensured. As a result, fragrance retention,
Excellent in various properties such as taste retention, moldability, heat resistance, impact resistance, coating uniformity, chemical resistance, mechanical strength, adhesion to metals, and barrier properties against corrosion factors such as water and oxygen. It can be suitably used as a coating material.

Further, the resin film, the resin-coated metal plate, and the resin-coated metal container of the present invention use the resin composition of the present invention. It can be suitably used as a member and a metal container excellent in storage stability and flavor. In addition, since the resin-coated metal plate of the present invention has the surface of the metal plate coated with resin in advance, it is possible to omit the painting process at the customer, which also contributes to the saving of the process and the cost at the customer. It has the effect that can be done.

[Brief description of the drawings]

FIG. 1 is an SEM photograph of a cross section of a sample for observation of a dispersion form of each resin phase in a ternary resin composition.

FIG. 2 is a perspective view of the can showing the positions of collecting samples for observing the dispersed form of the resin (B) and (C) phases in the resin coating layer after the can is formed.

FIG. 3 is an SE of a cross section of a resin coating layer in a direction of sectioning a top of a can body.
M photo.

FIG. 4 is an SEM of a cross section of a resin coating layer in a vertical direction of an upper portion of a can body.
Photo.

FIG. 5 SE of the cross section of the resin coating layer in the direction of sectioning the bottom of the can body.
M photo.

FIG. 6 is an SEM of a cross section of a resin coating layer in a vertical direction of a lower portion of a can body.
Photo.

FIG. 7 is a diagram showing the relationship between the aspect ratio of the resin (B) and (C) phases in the resin coating layer after the can formation and the height of the can wall.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 21/00 C08L 21/00 27/18 27/18 63/10 63/10 101/00 101/00 101 / 02 101/02 // B29K 27:18 B29K 27:18 67:00 67:00 (72) Inventor Masaharu Konno 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation Technology Development Division (72) Invention Person Yoshihiro Nomi 20-1 Shintomi, Futtsu City, Chiba Prefecture Nippon Steel Corporation Technology Development Division F-term (reference) 4F071 AA12 AA15 AA15X AA22 AA27 AA28 AA28X AA29 AA30 AA32X AA33 AA34 AA36 AA42 AA45 AC11 AC11 AC11 AH05 BB05 BB06 BC01 BC02 4F100 AB01B AK01A AK01C AK18A AK18C AK21A AK21C AK25A AK25C AK41A AK41C AK64H AK65H AL05A AL05C AN01A AN01C BA02 BA03 BA06 BA07 BA10A E12E01 J01E02 E01E02E L08A JL08C JL11 YY00A YY00C 4F201 AA17 AA24 AB19 AB24 AD03 AD08 AH55 BA01 BA02 BC03 BC12 BC19 BD05 BK02 BK13 BK40 BL29 4J002 AC034 BB034 BB062 BB072 BB082 BB092 BB04 BG04 BB174 BB02 BB174 CF031 CF051 CF061 CF071 CF081 EJ016 EJ026 EJ036 EN066 EU046 EW066 EW126 FD036 GG01

Claims (9)

[Claims] 1. A polyester resin (A) and a vinyl polymer (B) containing at least 1% by mass of a unit having a polar group.
A resin composition characterized in that it contains 0.001 to 7 parts by mass of a radical inhibitor and 0.001 to 7 parts by mass of a polytetrafluoroethylene-containing powder with respect to 100 parts by mass of the resin composition (I). 2. The method according to claim 1, wherein the polytetrafluoroethylene-containing powder comprises polytetrafluoroethylene particles (a) having a particle diameter of 10 μm or less and organic polymer particles (b). Resin composition. 3. The organic polymer particles (b) may contain one or more (meth) acrylate monomers having an epoxy group.
The resin composition according to claim 2, wherein the resin composition is a polymer or a polyester resin containing not less than mass%. 4. The resin composition according to claim 1, wherein the resin composition (I) further contains a rubber-like elastic resin (C). 5. A rubber-like elastic resin (C) is finely dispersed in a polyester resin (A), and at least a part of the rubber-like elastic resin (C) is encapsulated in a vinyl polymer (B). The resin composition according to claim 4 having a structure. 6. A resin composition containing the radical inhibitor according to any one of claims 1 to 5 and a polytetrafluoroethylene-containing powder, which is molded alone, or is formed of another resin composition and / or A resin film obtained by laminating or applying in combination with an adhesive. 7. A metal plate which is laminated on one side and / or both sides in a single layer using at least the resin film according to claim 6 or in a multilayer in combination with another resin composition and / or an adhesive. A resin-coated metal plate formed by coating. 8. A resin-coated metal container formed by molding the resin-coated metal plate according to claim 7. 9. A polyester resin (A) and a vinyl polymer (B) containing at least 1% by mass of a unit having a polar group.
Mixing the resin composition (I), and wherein the polyester resin (A) contains a metal compound, and the radical inhibitor 0.001 to 7 with respect to 100 parts by mass of the resin composition (I). In order to prevent decomposition of the resin composition (I) in the mixing step, 0.001 to 7 parts by weight of a polytetrafluoroethylene-containing powder was added to the resin composition to prevent the resin from adhering in the kneader in the mixing step. A method for producing a resin composition, characterized by suppressing stagnation.