JP2002363389A - Resin composition, resin film using the same and resin covered metallic plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which has good impact resistance, chemical resistance, moldability, heat resistance, gas barrier properties against corrosion factor substances, water resistance, and adhesion to metals and does not cause the deformation due to embrittlement and shrinkage and the like even when used in a severe environment such as in hot water, a resin film using the same, and a resin covered metallic plate which is covered with a resin film obtained by laminating the resin film. SOLUTION: The resin composition is obtained by adding 0.1-50 mass% inorganic particles having polarity to a mixture containing (A) a polyester resin having an intrinsic viscosity of >=0.3 dl/g and (B) a vinyl polymer having >=1 mass% unit having a polar group. The resin film uses this resin composition, and the resin covered metallic plate uses the resin film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition, a resin film and a resin-coated metal plate using the same.

[0002]

2. Description of the Related Art Polyester resins have excellent mechanical properties, electrical properties and heat resistance, and are widely used as molding materials for parts of automobiles and electric appliances, housings and the like. further,
Excellent lubrication during processing, abrasion resistance, gas barrier properties of metal corrosion factors such as water vapor and oxygen, and excellent adhesion to metals, improving corrosion resistance and workability and imparting design to the surface It is widely used as a metal coating material for the purpose of doing so.

[0003] When a polyester resin is used as a coating material for a metal plate, as a method for further improving these characteristics, as disclosed in JP-A-7-195617 and JP-A-7-290644, a polyester resin is used. A method of alloying with an ionomer resin is known. In this method, the mechanical properties and adhesion to metal are improved by the ionomer resin. Further, as disclosed in WO99 / 27026, a rubber elastic resin is further added to a resin composition of the above-described polyester resin and a vinyl polymer having a polar group such as an ionomer, and the polyester resin polar group is added. A technique for finely dispersing a rubber-like elastic body in which an elastic resin is encapsulated by a vinyl polymer having the same is disclosed, and it is known that impact resistance and thermal stability are further improved.

[0004]

However, the inventors of the present invention have further analyzed the characteristics of the resin composition of the above polyester resin and a vinyl polymer having a polar group such as an ionomer. When the coated metal plate is exposed to an environment of 100 ° C. or higher or hot water for a long period of time, the resin may be embrittled or deformed due to thermal shrinkage, resulting in blister-like irregularities and cracks. In particular, this tendency was sometimes more remarkable when immersed in hot and warm water. As a result, when a metal plate coated with the resin composition is applied to an application such as a unit bath that uses hot water for a long period of time, deformation of the printed pattern or change in color tone impairs the design, and furthermore, the resin coating In some cases, the base metal plate was deformed to cause corrosion. These causes, because water enters the polyester resin, and in a high temperature environment,
The plasticization of the polyester resin is promoted, and the interaction between the ionomer and the polyester resin is weakened by the intrusion of water, the interfacial bonding force between the polyester resin and the ionomer becomes insufficient, and the polyester in which the ionomer is sufficiently plasticized It is presumed that this is due to the inability to absorb the deformation stress of the resin.

[0005] The present invention suppresses the plasticization of the polyester resin in such an environment or increases the interfacial adhesion between the polyester resin and a vinyl resin having a polar group such as an ionomer. Shock resistance, chemical resistance, moldability, heat resistance,
It is an object of the present invention to provide a resin composition which has good gas barrier properties, water resistance and adhesion to metals of a corrosion-causing substance, and does not cause deformation due to embrittlement or shrinkage. Further, another object of the present invention is to provide a resin film using such a resin composition and a resin-coated metal plate covered with a resin film obtained by laminating the resin film.

[0006]

Means for Solving the Problems The present inventors diligently studied to solve the above problems and completed the present invention. That is, the present invention relates to a mixture comprising a polyester resin (A) having an intrinsic viscosity of 0.3 dl / g or more and a vinyl polymer (B) containing a unit having a polar group of 1 mass% or more, and having inorganic particles having a polarity of 0.1 to 0.1%. A resin composition characterized by adding 50 mass%.

The polarity of the inorganic particles is preferably such that the difference in the electronegativity of Pauling is 1.0 (eV) ^0.5 or more. Further, the number of the inorganic particles unevenly distributed at the interface between the polyester resin (A) and the vinyl polymer (B) is 20% or more of all the inorganic particles, and / or
Alternatively, the resin composition is characterized in that the inorganic particles unevenly distributed in 20% or more of the number of interface layers between the polyester resin (A) and the vinyl polymer (B) are present.

Further, the resin composition is characterized in that a part or all of the phase of the vinyl polymer (B) contains a rubber-like elastic resin (C) phase. In addition, the intrinsic viscosity of the polyester resin (A) is more preferably 0.7 to 1.5 dl / g. In addition, the resin composition is a resin film characterized by being formed alone, or laminated in combination with another resin or a resin composition and / or an adhesive, and the resin film is the resin It is a resin film composed of three layers: a composition film layer, a printing layer, and a top layer.

Further, the crystallization temperature (Tc) or the melting temperature (Tm) of the top layer is 100 ° C. or more, and the crystallization ratio of the top layer is 15% of the saturation crystallinity of the resin constituting the top layer. % Of the resin film. Further, the present invention is a resin-coated metal plate obtained by covering the surface with the resin film. Further, the present invention is a resin-coated metal plate having a surface coated with a molten film of the resin composition.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester resin (A) having an intrinsic viscosity of 0.3 dl / g or more and a unit having a polar group.
A resin composition characterized in that a polar inorganic component is added in an amount of 0.1 to 50 mass% to a mixture containing a vinyl polymer (B) containing at least mass%. Hereinafter, the present invention will be described in detail.

The polyester resin (A) used in the present invention
Is a hydroxycarboxylic acid compound residue only, or a dicarboxylic acid residue and a diol compound residue, or
It is a thermoplastic polyester having a hydroxycarboxylic acid compound residue, a dicarboxylic acid residue and a diol compound residue as constituent units. Further, a mixture thereof may be used.

Examples of the hydroxycarboxylic acid compound as a raw material of the hydroxycarboxylic acid compound residue include p-hydroxybenzoic acid, p-hydroxyethylbenzoic acid, 2- (4-
Hydroxyphenyl) -2- (4′-carboxyphenyl) propane, and the like, even when used alone,
You may mix and use two or more types. 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 in combination of two or more. You may use it.

Next, examples of diol compounds forming a diol residue include 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol A”),
(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,
Aromatic diols such as 4'-biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, and the aromatic ring portions of these aromatic diols are partially Hydrogenated, 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, aliphatic diols such as hydrogenated bisphenol A, and alicyclic diols such as cyclohexane dimethanol.These may be used alone, or two or more kinds may be mixed. Can also be used.

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.

Further, the polyester resin used in the present invention
(A) is a small amount of structural units derived from a polyfunctional compound such as trimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, and pentaerythritol, for example, containing an amount of 2 mol% or less. May be. From the viewpoint of heat resistance and processability, the most preferred combination of these dicarboxylic acid compounds and diol compounds is terephthalic acid 50 to 95 mol%, isophthalic acid and / or orthophthalic acid 50 to 5 mol% of dicarboxylic acid. It is a combination of a compound 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-terephthalate.
Among them, 2,6-naphthalate and the like can be mentioned, among which polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene-2,6-naphthalate, which have moderate mechanical properties, gas barrier properties, and metal adhesion, are the most preferable. preferable.

The polyester resin (A) contained in the resin composition of the present invention sometimes contains a metal compound such as germanium, antimony, or titanium, which is a residue of a polyester production catalyst. The content of the metal compound in the polyester resin used in the resin composition of the present invention is not particularly limited, but generally, the content of the metal compound as a residue of the polymerization catalyst is preferably 100 ppm or less.

The polyester resin (A) used in the present invention
Must have an intrinsic viscosity of at least 0.3 dl / g, measured at a concentration of 0.5% in o-chlorophenol at 25 ° C. 0.3dl / g
If it is less than 3, the polymer effect cannot be exhibited. Although the upper limit of the intrinsic viscosity is not particularly specified, the intrinsic viscosity is 2.0 d
If it exceeds l / g, the moldability will be poor, and it is preferred that it be 2.0 dl / g or less. More preferably, the intrinsic viscosity is 0.7 to 1.5 dl / g
If it is less than 0.7 dl / g, the material strength of the polyester resin (A) itself is insufficient, and if it is used for a very long time in an environment using boiling water, cracking or swelling may occur. Also 1.5d
If it exceeds l / g, the dispersibility of the added inorganic particles may be deteriorated.

The polyester resin (A) used in the present invention
May be amorphous or crystalline, and when crystalline, the crystal melting temperature (Tm) is preferably 100 ° C. or higher. If it is lower than 100 ° C., it may be deformed when using boiling water. Further, Tm is 210-265 ° C, preferably 210-245 ° C, and the low temperature crystallization temperature (Tc) is 110-2.
The temperature is desirably 20 ° C, preferably 120 to 215 ° C. Tm
Is higher than 265 ° C. or Tc is higher than 220 ° C., the vinyl polymer (B) may decompose during kneading. If Tm is less than 210 ° C. or Tc is less than 110 ° C., the heat resistance may be insufficient and the film shape may not be maintained during processing. 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 preferably 50 to 120 ° C., more preferably 60 to 100 ° C. In the case of being amorphous, the above Tg is desirably 100 ° C. or higher. When the material is amorphous and has a Tg of less than 100 ° C., the heat resistance is insufficient, and cracks may occur when hot water is used.

The resin composition of the present invention has a polar group
Contains vinyl polymer (B) containing 1% by mass or more of units
Must be done. 1% by mass of a unit having a polar group
 The above-mentioned vinyl polymer (B) is defined as
0.45 (eV)^0.5The group where the above elements are bonded
Vinyl polymer containing 1% by mass or more of
You. If the unit containing polar groups is less than 1% by mass, impact resistance
Performance may be reduced. Poling electronegativity difference
Is 0.45 (eV)^0.5Specific examples of groups where the above elements are bonded
When shown, -C-O-, -C = O, -COO-, epoxy group, C_TwoO_Three, C_Two
O_TwoN-, -CN, -NH_Two, -NH-, -X (X: F, Cl, Br), -SO_Three-,etc
Is mentioned. It is also neutralized with metal ions as a polar group.
May have an acid salt ion. In this case,
An example of ON is Na⁺, K⁺, Li⁺, Zn²⁺, Mg²⁺, Ca²⁺, Co
²⁺, Ni²⁺, Pb²⁺, Cu²⁺, Mn²⁺, Ti ³⁺, Zr³⁺, Sc³⁺Etc. 1
Valent, divalent or trivalent metal cations.

As an example of a unit having a polar group, -C
Vinyl alcohol as an example having a -O- group, vinyl chloromethyl ketone as an example having a -C = O group, acrylic acid, methacrylic acid, vinyl acetate as an example having a -COO- group,
Glycidyl esters of α, β-unsaturated acids such as vinyl acid such as vinyl propionate and its metal salts or ester derivatives, and glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaacrylate as examples having an epoxy group; Maleic anhydride as an example having a C ₂ O ₃ group, imide derivative of maleic anhydride as an example having a C ₂ O ₂ N-group, acrylonitrile as an example having a —CN group, acrylamine as an example having a —NH ₂ group , -N
Vinyl chloride Examples with acrylamide, a -X group as an example having a H- group, -SO ₃ - styrene sulfonic acid, and the like are mentioned as examples having the group, also all or a portion of these acidic functional groups And compounds neutralized with the above-mentioned metal ions, and these may be contained alone or in plural in the 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. Examples thereof include a polymer of a single unit or two or more kinds of units, and a copolymer of the polar group-containing vinyl unit with a nonpolar vinyl monomer represented by the following general formula (i). -CHR ¹ = CR ² R ^3- (i) (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. Represents a phenyl group or hydrogen.) Specific examples of the nonpolar vinyl monomer of the general formula (i) include:
Ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1
-In addition to α-olefins such as dodecene, aliphatic vinyl monomers such as isobutene and isobutylene, and styrene monomers
Aromatic vinyls such as alkylated styrenes such as o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene and t-butylstyrene, and styrene-based monomer addition polymer units such as α-methylstyrene Monomers and the like.

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 non-polar vinyl monomer include ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, and copolymers of these. Ionomer resin, 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- All or some of the maleic anhydride copolymers and their acidic functional groups Ionomer resins neutralized with genus ions.

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, which is obtained by neutralizing a part or all of the carboxylic acid in the copolymer with a metal cation. Examples of the vinyl monomer include the above-mentioned α-olefin and styrene monomer, and examples of the α, β-unsaturated carboxylic acid include carbon atoms.
3-8 α, β-unsaturated carboxylic acids, more specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, monomethyl maleate, maleic anhydride, monoethyl maleate and the like.

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 ²⁺ , C
^Monovalent , divalent or trivalent metal cations such as u ²⁺ , Mn ²⁺ , Ti ³⁺ , Zr ³⁺ and Sc ³⁺ are mentioned. 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. And a resin in which some or all of the carboxyl groups in the copolymer are neutralized with metal ions such as sodium, potassium, lithium, zinc, magnesium, and calcium.

Of these, ethylene and acrylic acid are most preferable for the purpose of improving the impact resistance and improving the compatibility between the polyester resin (A) and the rubbery elastic resin body (C) described later. Or a copolymer of methacrylic acid (constituent units having a carboxyl group is 2 to 15 mol%), a resin in which 30 to 70% of the carboxyl groups in the polymer is neutralized with a metal cation such as Na or Zn. It is.

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

Particularly, in view of high impact resistance, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, and acidic functional groups in these copolymers are more preferable. Ionomer resin in which some or all of the groups are neutralized with metal ions, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer 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 Coalescence, ethylene-carbon monoxide-glycidyl acrylate copolymerization , Ethylene - anhydride Maren'i acid copolymer, butene - ethylene - glycidyl methacrylate copolymer, butene - ethylene - glycidyl acrylate copolymers.

From the viewpoint of ensuring the barrier properties, a copolymer of an α-olefin and a unit having a polar group is a preferable combination. The vinyl polymer used in the present invention
(B) may be a vinyl polymer containing 1% by mass or more of a unit having a polar group, and is not limited to the above specific examples. The molecular weight of the vinyl polymer (B) is not particularly limited, but the number average molecular weight is 2,000 or more and 5,000 or more.
00 or less is preferable. If it is less than 2000 or more than 500,000, the impact resistance may decrease.

The dispersion shape and state of the vinyl polymer (B) are not particularly limited, but are preferably dispersed in the form of particles having an average particle size of 5 μm or less, more preferably 1 μm or less. In the form of particles. 5μm
Above this, film processing may be difficult. By dispersing the particles into particles having an average particle size of 1 μm or less, the impact strength increases, and the effect of relaxing the deformation stress in a boiling water environment increases.

The amount of the vinyl polymer (B) is preferably not more than 20% by volume ratio. If the volume ratio exceeds 20%, the basic properties such as heat resistance of the resin composition may change. further,
Polar inorganic particles must be added to the resin composition of the present invention, but are generally added in an amount of 0.1 to 50 mass% based on the total mass of the polyester resin (A) and the vinyl polymer (B). The inorganic particles having polarity are inorganic particles having an element (I) -element (II) bond in the molecule in which the difference in electronegativity of Pauling is 0.45 (eV) ^0.5 or more, and the mass% of the same component is 8%.
If it is 0 mass% or more, an inorganic substance outside the range may be mixed. If the content of this component is less than 0.1 mass%, the effect of enhancing the adhesion at the interface between the polyester resin (A) phase and the vinyl polymer (B) phase, and the plasticity of the polyester resin (A) phase under hot and hot water The effect of inhibiting the formation of a gas decreases, and cracking is likely to occur when used in a high-temperature and high-humidity environment such as boiling water. If it exceeds 50 mass%, the resin composition becomes brittle. By controlling the polarity within the above range, electrostatic components such as hydrogen bonding, ionic interaction, and coordination interaction between the component and the polar group between the polyester resin (A) and the vinyl resin (B) can be prevented. An interaction or covalent bond occurs. As a result, the adhesion at the interface can be enhanced, and the plasticization of the polyester resin (A) phase under hot and hot water can be suppressed. In order to further enhance these interactions, it is preferable that the difference in Pauling's electronegativity is 1.0 (eV) ^0.5 or more.

The inorganic particles of the present invention have a Pauling electric shade.
0.45 (eV)^0.5If it has a certain polarity
Although not particularly limited in chemical structure, metal oxides
And metal carbonates, sulfates, nitrates, phosphates, silicic acids
Salts, chromates, hydroxides and the like. Specifically nothing
For example, oxidized particles originally used as pigments
Titanium (titanium white, rutile type, anatase type, etc.
_Two), Zinc oxide (zinc white, ZnO), antimony oxide (Sb_TwoO_Three),
Iron oxide (Fe_ThreeO_Four), Silica (silica powder, SiO_Two), White car
Bon (SiO_Two・ NH_TwoO), diatomaceous earth (SiO_Two・ NH_TwoO), talc (talc)
Powder, 3MgO ・ 4SiO_Two・ H_TwoO), barium sulfate (BaSO_Four), Sulfuric acid
Lucium (CaSO_Four), Barium carbonate (BaCO_Three), Calcium carbonate
(CaCO_Three), Plaster (CaSO_Four・ 2H_TwoO), clay (e.g. Al_TwoO_Three・
2SiO_Two・ 2H_TwoO), magnesium carbonate (e.g., 3MgCO_Three
・ Mg (OH)_Two・ 3H_TwoO to MgCO_Three・ 3Mg (OH) _Two・ 11H_TwoO etc.), Al
Mina (Al (OH)_Three), Lead chromate (PbCrO_Four), Zinc chromate (Zn
CrO _Four), Barium chromate (BaCrO_Four), Iron oxide yellow (FeO
(OH) ・ nH_TwoO), ocher (main component Fe_TwoO_Three, SiO_Two, Al_TwoO
_ThreeEtc.), calcium leadate (Ca_TwoPbO_Four), Red-bright graphite (PbCrO_Four・ Pb
O), navy blue (Fe_Four[Fe (CN)₆]_Three・ NH_TwoO, etc.), cobalt blue
(CoO ・ nAl_TwoO_Three), Viridian (Cr_TwoO (OH)_Four) And the like,
Furthermore, as inorganic particles originally used as a filler,
Dry silica, colloidal silica, lithium fluoride, etc.
These can be used alone or
In addition, two or more kinds can be mixed and used.

Above all, it has a high thermal stability, has a bond with a difference of 1.0 (eV) of ^0.5 or more in Pauling's electronegativity, has a strong interaction with the polar unit in the vinyl polymer (B), and has a close contact with the interface. Metal oxides are preferred from the viewpoint of strengthening the force and suppressing the plasticization of the polyester resin (A) phase under hot and hot water. Specific examples of the inorganic particles include titanium oxide (titanium white, rutile type, anatase type, etc., TiO ₂ :
2.0 (eV) ^0.5), zinc oxide (zinc ^{white, ZnO: 1.9 (eV) 0.5} ), antimony oxide _{(Sb 2 O 3: 1.6 (} eV) 0.5), iron oxide _{(Fe 3 O 4: 1.7 (} e
V) ^0.5 ) and silica (silica powder, SiO ₂ : 1.7 (eV) ^0.5 ). Of these, white is preferable from the viewpoint of imparting various designs such as printing in a later step, and titanium oxide having high hiding power and versatility is particularly preferable. The type of titanium oxide to be added is not particularly limited, and may be any of anatase type, rutile type, vulcarite type, and the like.

The dispersion shape and state of these inorganic particles are not particularly limited, but preferably these particles are dispersed in the composition in the form of particles having an average particle diameter of 5 μm or less, and more preferably, It is desirable that the particles are dispersed in the form of particles having an average particle diameter of 1 μm or less. From the viewpoint of enhancing the interface strength between the polyester resin (A) phase and the vinyl polymer (B) phase, these components are preferably localized at the interface.
Specifically, 20% or more of the number of inorganic particles (X1) is unevenly distributed at the interface between the polyester resin (A) phase and the vinyl polymer (B) phase, or the polyester resin (A) and the vinyl polymer (B) Number of interfacial layers (X2)
It is preferable that the inorganic particles are dispersed so that at least 20% of the inorganic particles are present. More preferably, it is in a dispersed state in which 50% or more of X1 is present at the interface or 50% or more of X2 has one or more of the particles. Further, from the viewpoint of suppressing the plasticization of the polyester resin (A) phase under hot water, it is preferable that the inorganic particles are also dispersed in the polyester resin (A) phase, and in particular, 10% or more of X1 is a polyester. It is preferably dispersed in the resin (A) phase.

[0035] The dispersion state of the polyester resin
It can be observed by identifying the (A) phase, the vinyl polymer (B) phase, and the inorganic particles by a known method. The following method can be exemplified as a specific method. Polyester resin as required
After making the (A) phase and the inorganic particle phase distinguishable by staining contrast, the vinyl polymer (B) phase is etched with a solvent that dissolves only the vinyl polymer (B), and observed with an electron microscope. The uneven distribution of the inorganic particles on the etched surface (the interface between the polyester resin (A) phase and the vinyl polymer (B) phase) can be quantified using an image processing method or the like. Specifically, the identified inorganic particles are randomly extracted at random, and the polyester resin
The number ratio of the inorganic particles present at the interface between the (A) phase and the vinyl polymer (B) phase, or the interface layer between the polyester resin (A) phase and the vinyl polymer (B) phase is similarly extracted, and the inorganic particles are extracted. The uneven distribution state can be quantitatively evaluated based on the number ratio of the interface layer in which is present. The number of inorganic particles or interface layers to be subjected to uneven distribution determination is not particularly limited, but is preferably 10 or more, more preferably 20 or more from the statistical significance.

Further, a rubber-like elastic body (C) is included in a part of the vinyl polymer (B), preferably in all phases, so that the impact resistance and boiling water environment of the resin composition can be improved. It is desirable from the viewpoint of increasing the effect of relaxing the deformation stress below. Known rubber-like elastic resins can be widely used for the rubber-like elastic body (C). Among them, the glass transition temperature of the developing part (Tg, sample amount of about 10 mg, measured by a differential thermal analyzer (DSC) at a heating rate of 10 ° C./min) is 50 ° C. or less, the Young's modulus at room temperature is 1000 MPa or less, and A rubber-like elastic resin having a breaking elongation of 50% or more is preferable. Tg of the rubber elasticity development part exceeds 50 ° C, Young's modulus at room temperature
If it exceeds 1000 MPa and the elongation at break is less than 50%, the impact resistance and the effect of relaxing the deformation stress in a boiling water environment cannot be sufficiently exhibited. Furthermore, from the viewpoint of further increasing these effects, Tg
Is preferably 10 ° C. or lower, more preferably -30 ° C. or lower. Further, the Young's modulus at room temperature is 100 MPa or less, more preferably 10 MPa or less, the elongation at break is 100%
As described above, more preferably, it is 300% or more.

Specific examples of the rubber-like elastic body (C) include:
Examples include solid rubber, latex, thermoplastic elastomer, liquid rubber, powdered rubber, and the like described in the Industrial Research Committee (1985) published by Shinzo Yamashita, "Handbook of Rubber Elastomer Utilization". Among these, solid rubber and thermoplastic elastomer are most preferred from the viewpoint of film processability, and polyolefin rubber-like elastic bodies are most preferred from the viewpoint of barrier properties against metal corrosion factors. Specific examples of preferred polyolefin rubbery elastomers include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, and ethylene-3-
Ethyl pentene copolymer, copolymer of ethylene and α-olefin having 3 or more carbon atoms, such as ethylene-1-octene copolymer, or butadiene, isoprene, 5-methylidene-2- Norbornene, 5-ethylidene-2-
It is a terpolymer comprising ethylene copolymerized with norbornene, cyclopentadiene, 1,4-hexadiene, etc., an α-olefin having 3 or more carbon atoms, and a non-conjugated diene. Among them, binary copolymers of ethylene-propylene copolymer and ethylene-1-butene copolymer, or ethylene-propylene copolymer and ethylene-1-butene copolymer, 5-non-conjugated diene Using methylidene-2-norbornene, 5-ethylidene-2-norbornene, cyclopentadiene and 1,4-hexadiene, a resin obtained by copolymerizing an α-olefin content of 20 to 60 mol% and a non-conjugated diene of 0.5 to 10 mol% Is most preferred from the viewpoint of film workability.

A specific example of a method of encapsulating the rubber-like elastic body (C) in the vinyl polymer (B) phase is as follows. According to the chemical structure of the rubber-like elastic body (C), Polar unit m
The ass% is controlled in the range of 1 mass% or more, and the interfacial tension between the three so that the vinyl polymer (B) phase is wetted at the interface between the rubbery elastic body (C) phase and the polyester resin (A) phase, that is, , By controlling the wettability.

The dispersion state in which the rubber-like elastic body (C) is included in the vinyl polymer (B) phase of the present invention is defined as 80% or more, preferably 95% or more, of the interface of the rubber-like elastic resin (C) phase. The vinyl polymer
(B) is coated, polyester resin (A) and rubber-like elastic resin
The structure is such that the direct contact area with (C) is less than 20%. With such a structure, the fine dispersion of the rubber-like elastic body (C) encapsulated with the vinyl polymer (B) is facilitated, the impact resistance and the film-forming property are improved, and the rubber-like elasticity is improved. The body 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, even if finely dispersed particles contact the metal plate, This has the effect of ensuring the adhesion between the composition and the metal plate. The state of inclusion can be determined by identifying the rubber-like elastic body (C) and the vinyl polymer (B) by a known staining method or the like, and observing them with an electron microscope or the like.

The addition amount of the rubber-like elastic body (C) is not particularly limited, but the preferable addition amount is 50 mass% or less of the vinyl polymer (B) + the rubber-like elastic body (C) with respect to the polyester resin (A). is there. If it exceeds 50 mass%, the hardness may decrease. Also,
The resin composition of the present invention has other purposes, that is, rigidity, linear expansion characteristics, lubricity, surface hardness, heat stability, light stability, oxidation stability, mold release, imparting of dyeing, antistatic, antibacterial and antifungal, etc. For the purpose, an appropriate amount of these known property modifiers may be added. Among them, among the antioxidants, a radical inhibitor is particularly preferable, and one or more selected from a phenolic radical inhibitor, a sulfide radical inhibitor, and a nitrogen radical inhibitor are preferably added.

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

In the case of kneading by melt mixing, if necessary, a masterbatch prepared by previously mixing inorganic particles in one or a plurality of resins is prepared, and these masterbatches are used for part or all of the resin. It may be melt-mixed. On the contrary, after melt-mixing only the resin component in advance,
Inorganic particles may be added and melt-mixed. The film of the present invention is a resin film obtained by molding the resin composition of the present invention alone or by laminating it in combination with another resin or a resin composition and / or an adhesive. In the case of single molding, a known production method can be widely applied. Specific examples include a solvent casting method, a heat compression method, a calendar method, a T-die casting method, a T-die uniaxial or biaxial stretching method, an inflation method, and the like, but are not particularly limited thereto. A known laminating method can also be used when laminating another resin or a resin composition film on a single molded film. Specific examples include a method of laminating at the time of molding by a multilayer T-die method, and a method of laminating a single molded film via thermocompression bonding or an adhesive.
In the case of laminating a single-molded film via a thermocompression bonding or an adhesive, in order to increase the surface tension of the single-molded film and enhance adhesion, a known film treatment such as a corona discharge treatment or a plasma treatment, Surface tension of 500μN
It is preferable to control the pressure to not less than / cm. In particular, when performing corona discharge treatment, it is preferable to adjust the discharge amount (watt density) according to the apparatus and to perform treatment at a low discharge amount, specifically 10 to 40 W / m ² / min. When the treatment discharge amount is high, the surface is locally heated, and the surface is deformed to generate defects such as wrinkles, which may deteriorate the design. Further, when an adhesive is used, the adhesive can be further applied by a known gravure method or roll coater method. The coating method can be selected depending on the application, but when a very high-definition design is required, the roll coater method is more preferable because the adhesive has less unevenness. Further, the adhesive, polyester resin-based aqueous dispersant disclosed in JP-B-60-12233, JP-B-63-13829
Patent Application Publication No. 61-14934
Known adhesives such as polymers having various functional groups disclosed in JP-A-1 can be widely used. It is preferable to select an effective adhesive for the main component resin according to the layer to be bonded and the main component of the resin composition layer of the present invention. Further, a known organic layer or inorganic layer may be laminated on the upper and lower layers of the film of the present invention for the purpose of imparting surface hardness or conductivity.

In particular, when the film of the present invention is applied to a field requiring a high degree of design, such as a building material or a housing of a home electric appliance, a printed layer and a top layer are laminated on the film of the present resin composition. The used film can be suitably used. By using the resin composition film as an underlayer, deformation can be prevented even when used under heat, impact resistance or hot and hot water, and adhesion to a metal plate and corrosion resistance can be ensured. Further, by providing the printing layer, various designs can be easily provided without impairing productivity. The printing method of the printing layer is not particularly limited, such as gravure printing, offset printing, and silk printing, but silk printing is preferable when clearer printing is required. When a print layer is provided on a film of the present resin composition, a known film treatment such as the corona discharge treatment or plasma treatment may be performed as necessary for the purpose of increasing the surface tension of the film and improving printability. It does not matter. In this case, the surface tension is set to 500 μN / c under appropriate processing conditions.
It is preferable to control it to m or more. Further, by providing the top layer, the design can be maintained even after long-term use. The position where the printing layer is provided may be the upper surface of the resin composition film of the present invention or the lower surface of the upper film layer. When an adhesive layer is required between the top layer and the resin composition film layer of the present invention, and a very high-definition design is required, the lower surface of the top layer is used to avoid a decrease in sharpness due to refraction of the adhesive layer. It is preferable to print on the paper.

The resin of the top layer is not particularly limited, but it is desirable that the printing layer can be protected even after long-term use. In order to make the printed layer clear, the total light transmittance should be 60
% Is desirable. The thickness of the top layer is preferably from 5 to 200 μm, and more preferably from about 13 to 150 μm, from the viewpoint of formability, cost, and the like. Examples of the resin of the top layer include a transparent resin film and a transparent paint such as varnish. Above all, a transparent polyester resin is most preferable from the viewpoint that physical properties with the underlying resin composition film of the present invention are very close. Specifically, polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6
-Naphthalate, polybutylene-2,6-naphthalate, polyarylate, etc., which can be used alone or as a mixture of two or more. Furthermore, when the top layer is a transparent resin,
The crystallization temperature (Tc) or melting temperature (Tm) is 100 ° C in order to keep the design of the constituent film unchanged even under hot water.
It is preferable that it is above. More preferably Tc or
Tm is 110 ° C or higher. When Tc or Tm of the polyester resin is 100 ° C. or lower, the design may change at 100 ° C. or recrystallize to change the design. Tc or Tm measured under normal conditions due to the plasticizing effect of water in hot water
In some cases, and may be sufficiently plasticized even at around 100 ° C. Therefore, Tc or Tm is 100 ° C or higher and the total light transmittance is 60% or higher. It is preferable to maintain the total design of the constituent films. If necessary, these resin films are preferably subjected to a known film treatment such as the corona discharge treatment or the plasma treatment and the surface tension is controlled to 500 μN / cm or more in order to enhance the adhesion.

In the step of laminating a printing layer and a top layer on a film of the present resin composition, it is necessary to avoid a design loss due to heat in a step of laminating the present resin composition film on a metal plate, which will be described later. In this case, it may be performed after the step of laminating the present resin composition film on a metal plate. The printing method in this case is preferably silk printing. When a design is further provided to the constituent film by embossing or the like, the top layer is preferably the above-mentioned polyester film which has not been stretched. The stretched film shrinks during embossing, and the dimensions are not stable. The thickness of the film layer is not particularly limited, but it is desirable that the total thickness of the constituent films is at least twice the embossed groove. If it is less than twice, the embossed groove may change when laminated on a metal plate. In addition, embossing may be performed at the stage of a film, or after lamination on a metal plate described later,
It may be performed by a known method using an embossing roll or the like. Further, an internal emboss having an embossed appearance may be applied to the laminated film by wiping printing.

The metal plate of the present invention is a metal plate whose surface is coated with the resin composition film of the present invention. 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, etc., hot-dip galvanized steel sheet, hot-dip zinc-iron alloy-plated steel sheet, hot-dip zinc sheet -Aluminum-magnesium alloy coated steel sheet, hot-dip zinc-aluminum-magnesium-silicon alloy coated steel sheet, hot-dip aluminum-silicon alloy coated steel sheet, hot-dip-tin alloy coated steel sheet, hot-dip coated steel sheet, electro-galvanized steel sheet, electric zinc- Surface-treated steel sheets such as electroplated steel sheets such as nickel-plated steel sheets, electro-zinc-iron alloy-plated steel sheets, electro-zinc-chromium alloy-plated steel sheets, cold-rolled steel sheets, and metal sheets such as aluminum, copper, nickel, zinc, and magnesium. Can be Further, the coating on the metal plate may be either one side or both sides. Further, the thickness of the coating film when the resin composition of the present invention is coated on a metal plate is not particularly limited, but is 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.

A known method can be used for coating the metal plate. Specifically, (1) a method in which the present 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 the film coming out of the T-die. Another method of directly thermocompression bonding a film is (3) T
Instead of this resin composition in the hopper of the extruder with a die,
Inject resin and inorganic particles as raw materials of the present resin composition,
A method in which the present resin composition is kneaded in an extruder and directly thermocompression-bonded thereto is exemplified. 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 dipping a metal plate in the molten resin composition, and (6) a method of dissolving the resin composition in a solvent and spin coating. (7) It is also possible to coat the metal plate with an adhesive or the like, and the coating method is not particularly limited.

The methods (1), (2) and (3) described above are the most preferable in terms of work efficiency as a method for coating a metal plate.
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, the surface roughness of the film is the result of arbitrarily measured 1mm length of film surface roughness is preferably 500nm or less in R _max. If R _max is more than 500 nm, bubbles may be involved when coating by thermocompression bonding. In addition, because of 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 being stretched, and the number of steps can be reduced. Further, in the case of using as a metal coating material without stretching, it is not necessary to control the crystallinity in the thin film by controlling the temperature, the sheet passing speed, and the like, so that the process window can be enlarged and high-speed production can be performed. Further, since it is easy to control the molding temperature for controlling the crystallinity at the time of film formation and coating, it is possible to manufacture a product with stable performance.

When the resin film of the present invention is coated on a metal plate, it is coated on at least one surface and / or both surfaces of the metal plate by using at least the above resin film to form a single layer or a multilayer. be able to. At this time, one or two
Single or multiple layers may be laminated on one and / or both sides of a metal plate using more than one type of resin film,
Also, if necessary, polyethylene terephthalate film, polyester film such as polycarbonate film, polyolefin film such as polyethylene film, polyamide film such as 6-nylon film, other known resin film such as ionomer film, or Known resin composition films such as a crystalline / amorphous polyester composition film, a polyester / ionomer composition film, and a polyester / polycarbonate composition film may be laminated and coated on the lower layer and / or the upper layer. As a specific lamination method, when using the method of the above (1), (2) and (3), using a multilayer T die, the resin film of the present invention and other resin films and resin compositions There is a method of manufacturing a multilayer film with a film and thermocompression bonding the film. Further, when using the above methods (4) to (6), after coating the resin composition of the present invention after coating another resin composition, or after coating the resin composition of the present invention conversely By coating with another resin composition, it is possible to laminate in multiple layers.

The resin-coated metal plate of the present invention is a metal plate coated with the resin film of the present invention, and may be coated on one side or both sides. The thickness of the metal plate is not particularly limited, but is preferably 0.01 to 5 mm. 0.0
If it is less than 1 mm, it is difficult to develop strength, and if it exceeds 5 mm, processing is difficult. The resin composition of the present invention is a polyester resin having an intrinsic viscosity of 0.3 dl / g or more (A), a unit having a polar group of 1 mass%.
It is characterized in that 0.1 to 50 mass% of inorganic particles having polarity are added to the mixture comprising the vinyl polymer (B) contained above. Since the inorganic particles to be added have a polarity difference of Pauling's electronegativity of 0.45 (eV) ^0.5 or more, the polar unit such as the carbonyl group or the terminal functional group of the component and the polyester resin (A) or a vinyl polymer ( B) A covalent bond or electrostatic interaction can be exerted between the polar units. As a result, the adhesive force at the interface between the polyester resin (A) phase and the vinyl copolymer (B) phase can be enhanced, and the plasticization of the polyester resin (A) under hot and hot water can be suppressed. Further, this effect can be remarkably exhibited by specifying the polarity and dispersion state of the inorganic particles, the intrinsic viscosity of the polyester resin (A), and adding the rubber-like elastic body in a specific dispersion state.

As a result, even under severe use conditions such as use under boiling water for a long period of time, cracking deformation and design are not impaired. Furthermore, the impact resistance, chemical resistance, moldability, heat resistance, gas barrier properties of corrosion-causing substances, and water resistance inherent to the polyester resin (A) and the vinyl polymer (B) containing a unit having a polar group of 1 mass% or more. Since it has both properties and adhesion to metals, it can be suitably used as a resin molded product. Concretely, interior and exterior parts such as bumpers, bonnets, door materials, wheel covers, oil tanks and instrument panels, bathrooms, boilers, water heaters, elevators and other wall materials, tiles, tile carpets and other floor materials, door materials Interior building materials such as ceilings, partitions, pipes, sashes, etc.
It can be used for housings of toys, home appliances and light appliances (refrigerators, washing machines, air conditioners, freezer showcases, computers, mobile phones), film / sheet molded products, pipe molded products, etc.
In particular, the film composition of the present resin composition can be suitably used as a film material for coating a metal plate because of the above-mentioned properties. Further, the metal plate coated on the surface with the resin composition of the present invention can have characteristics such as high design, good workability and corrosion resistance, and can be suitably used for interior and exterior materials for buildings, housings of home electric appliances and the like. .

[0052]

Next, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples unless departing from the gist thereof.
In the following Examples and Comparative Examples, polyester resin
(A) as polyethylene terephthalate (PET) [Unitika
SA-1346P, SA-1235P, MA-1344, MA-1340 manufactured by Co., Ltd.), polybutylene terephthalate (PBT) [Polyplastics Co., Ltd.
Manufactured by Duranex 2001], one unit with a polar group
Ethylene-glycidyl methacrylate copolymer [Sumitomo Chemical Co., Ltd. Bond Fast 2C], ethylene-alkyl acrylate-glycidyl methacrylate copolymer [Sumitomo Chemical Co., Ltd.] ) Bond Fast 7L], ethylene ionomer [Himilan 1706, manufactured by DuPont Mitsui Co., Ltd.], ethylene-propylene rubber (EPR) as rubber-like elastic resin (C) [EP07P, manufactured by JSR Corporation], ethylene-butene rubber ( EBM) [EBM2041P manufactured by JSR Corporation] was used. In addition, when melt kneading, a phenolic antioxidant
[ADK STAB AO-60 manufactured by Asahi Denka Co., Ltd.] was used.

(Examples 1 to 20) Each resin and various inorganic particles 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. The phenolic antioxidant AO-60 was added in each case in an amount of 0.1 part by mass with respect to 100 parts by mass of the resin composition. This mixture was melt-kneaded at 260 ° C. with a twin-screw extruder to obtain resin composition pellets containing various inorganic particles. The difference in electronegativity of each inorganic particle poling is titanium dioxide: 2.0 (eV)
^0.5 , zinc oxide: 1.9 (eV) ^0.5 , barium sulfate: 2.6 (eV)
V) ^0.5 , silica: 1.7 (eV) ^0.5 , lithium fluoride: 3.0 (eV)
^0.5 , alumina: 2.0 (eV) ^0.5 , and the average particle size of each of the added inorganic particles is titanium dioxide: 0.5 μm, zinc oxide:
0.6 μm, barium sulfate: 0.8 μm, silica: 1.0 μm, lithium fluoride: 0.5 μm, and alumina: 1.2 μm.

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.
Was analyzed with a transmission electron microscope. As a result,
In each case, the rubber-like elastic resin (C) is almost a vinyl polymer (B).
The rubber-like elastic resin (C) had an equivalent sphere-equivalent diameter of 1 μm or less and was finely dispersed in the polyester resin (A). In addition, at least 20% of the number of the various inorganic particles added were unevenly distributed at the interface between the polyester resin (A) and the vinyl polymer (B).

[0055]

[Table 1]

Using these pellets, extrude 5 D
A film having a thickness of 0 μm was obtained (extrusion temperature: 280 ° C.). This film was bonded to one surface of a galvanized steel sheet having a thickness of 450 μm heated to 250 ° C., and rapidly cooled to 100 ° C. or less within 10 seconds by water cooling. The room temperature resin-coated metal sheet thus obtained was evaluated for adhesion, heat resistance, boiling water resistance, workability, stain resistance, solvent resistance, room temperature impact resistance and low temperature resistance according to the following evaluation methods. Each item of the impact property was evaluated.

<Adhesion> A cross cut was placed in the above resin-coated metal plate, immersed in distilled water at 50 ° C. for 10 days, and then the peel width (mm) (average of 10 samples) of the film at the cross cut portion was evaluated. did. Evaluation: ◎: 0.0 mm, ○: 0.0 to 0.5 mm, Δ: 0.5
2.02.0 mm and ×: more than 2.0 mm. Table 2 shows the results of the adhesion test.
Shown in

<Heat resistance> The above resin-coated metal plate was heated at 200 ° C.
After heating for 30 minutes at, changes in appearance (irregularity, shrinkage, peeling, etc.) were visually confirmed. The evaluation was ◎: no abnormality, :: slight change, Δ: surface considerably changed, and ×: base exposed. Table 2 shows the results of the heat resistance test. <Boiling water resistance> The above resin-coated metal plate is
The film was immersed for a period of time, and the peeling state of the film and changes in appearance (irregularities, shrinkage, peeling, etc.) were visually confirmed. Evaluation: ◎: No abnormality,
:: slight change, Δ: surface significantly changed, and x: underlayer exposed. Table 2 shows the results of the boiling water test.

<Workability> The above-mentioned resin-coated metal plate was heated at 25 ° C.
It was subjected to 0T bending, and the quality of workability such as cracking and whitening was visually checked. The evaluation was ◎: no abnormality, :: slight change, Δ: surface considerably changed, and ×: base exposed. Table 2 shows the results of the workability test. <Stain resistance> On the film surface of the above resin-coated metal plate, draw with black oil-based magic ink and leave for 24 hours, then wipe with a cloth impregnated with ethanol, and the extent of the magic ink remaining on the film surface Was visually checked. Evaluation is ◎:
No magic ink is recognized at all, ○: very small amount of magic ink remaining to the extent that there is no practical problem is recognized, Δ: slight magic ink remaining to a practically problematic level is observed, and ×: It was determined that a considerable amount of magic ink remained. Table 2 shows the results of the stain resistance test.

<Solvent Resistance> A sponge impregnated with methyl ethyl ketone was placed on the film surface of the above resin-coated metal plate and allowed to stand for 24 hours, and the degree of discoloration and swelling of the film surface was visually observed. The evaluation was :: no discoloration and swelling were observed at all, :: very slight discoloration and swelling were observed to the extent that there was no practical problem, Δ: slight discoloration and a practically problematic discoloration were observed. The occurrence of swelling was observed, and ×: the occurrence of discoloration and swelling was observed to a considerable extent. Table 2 shows the results of the solvent resistance test.

<Normal-Temperature Impact Resistance and Low-Temperature Impact Resistance> The impact resistance of the resin-coated metal sheet was evaluated by a DuPont drop impact test. The above resin-coated metal plate was cut into a size of 60 mm × 60 mm, and a 1 kg iron ball was dropped on the metal plate from a height of 50 cm at room temperature (about 25 ° C.) to apply an impact. The state of the film surface after applying the impact was visually evaluated. Further, after placing the resin-coated metal plate in a thermostat at 0 ° C. for 24 hours, the same impact resistance was evaluated, and the impact resistance at a low temperature was evaluated. Evaluation: ◎: no crack is observed in the film, ○: fine crack is recognized in a part of the film, Δ: fine crack is recognized in the entire film, ×: large crack is recognized in the entire film, The standard was used. Table 2 shows the results.

[0062]

[Table 2]

In Examples 1 to 20, there was no change in appearance of the film surface (irregularity, shrinkage, peeling, etc.) due to heat resistance and boiling water resistance, and even if there was, there was no problem. After cutting out an ultrathin section with a microtome from the resin composition of the example after this treatment, dyed with ruthenic acid, a polyester resin
When the dispersion state of the vinyl polymer (B) and the rubber-like elastic resin (C) in (A) was analyzed by a transmission electron microscope, the interface between the polyester resin (A) and the vinyl polymer (B) was found. It was confirmed that the added inorganic particles were unevenly distributed, and that there was no change in the dispersed state as compared to before the treatment, or that there was very little.

(Comparative Examples 1 to 4) In the same manner as in the above Examples, resin compositions containing no inorganic particles were dry-blended at the respective composition ratios shown in Table 3 using a V-type blender. The composition of each resin is as shown in Table 3, and the phenolic antioxidant AO-60 was added in each case in an amount of 0.1 part by mass with respect to 100 parts by mass of the resin composition. This mixture is extruded with a twin-screw extruder
The mixture was melt-kneaded at 260 ° C. to obtain resin composition pellets not containing various inorganic particles.

An ultra-thin 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.
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 10
The rubber-like elastic resin (C) had an equivalent sphere-equivalent diameter of 1 μm or less and was finely dispersed in the polyester resin (A).

[0066]

[Table 3]

In the same manner as in Examples 1 to 20, the pellets were extruded using a T-die to obtain a film having a thickness of 50 μm (extrusion temperature: 280 ° C.). This film was bonded to one surface of a galvanized steel sheet having a thickness of 450 μm heated to 250 ° C., and rapidly cooled to 100 ° C. or less within 10 seconds by water cooling. With respect to the thus-obtained normal-temperature resin-coated metal sheet, adhesion, heat resistance, boiling water resistance, workability, stain resistance, solvent resistance, and normal temperature resistance were evaluated in the same manner as in Examples 1 to 20. Each item of impact resistance and low-temperature impact resistance was evaluated. Table 4 shows the results.

[0068]

[Table 4]

In Comparative Examples 1 and 2, although the physical properties were satisfied, changes in the appearance of the film surface (irregularity, shrinkage, peeling, etc.) were slightly observed due to boiling water resistance. Comparative Examples 3 and 4
The change in the heat resistance and boiling water resistance was remarkable. After cutting out ultrathin sections from the resin compositions of Comparative Examples 3 and 4 after this treatment with a microtome, staining with ruthenic acid, the vinyl polymer (B) in the polyester resin (A) and the rubber-like elastic resin ( When the dispersion state of C) was analyzed with a transmission electron microscope, it was confirmed that the interface between the polyester resin (A) and the vinyl polymer (B) was peeled off and the dispersion state was changed.

(Examples 21 and 22) As the polyester resin (A), polyethylene terephthalate (PET) [SA manufactured by Unitika Ltd.]
-1346P, MA-1344] and a masterbatch polyethylene terephthalate containing 50 mass% of titanium dioxide (average particle size: 0.2 to 0.3 µm) in each case. Table 5
As shown in each of the polyethylene terephthalate
(PET) 40% by mass, corresponding titanium dioxide 50ma
40% by mass of a master batch containing ss%, 10% by mass of Himilan 1706 as a vinyl polymer (B) having at least 1% by mass of a unit having a polar group, ethylene-butene rubber (EBM) as a rubbery elastic resin (C) ) And 0.1% by mass of ADK STAB AO-60 as a phenolic antioxidant, and dry-blended using a V-type blender. This mixture was melt-kneaded at 260 ° C. using a twin-screw extruder to obtain two types of resin composition pellets containing titanium dioxide particles (final concentration: 20%).

[0071]

[Table 5]

Ultra-thin sections were cut out from these two types of resin compositions with a microtome, and then stained with ruthenic acid to form the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A). The dispersion state was analyzed with a transmission electron microscope.
As a result, similarly to Examples 1 to 20, the rubber-like elastic resin (C) is almost 100% encapsulated by the vinyl polymer (B), and is equivalent to the rubber-like elastic resin (C). The equivalent sphere diameter was 1 μm or less, and the particles were finely dispersed in the polyester resin (A). Also, the titanium dioxide particles added in the master batch,
It was dispersed around the interface between the polyester resin (A) and the vinyl polymer (B).

In the same manner as in Examples 1 to 20, the pellets were extruded using a T-die to obtain a film having a thickness of 50 μm (extrusion temperature: 280 ° C.). This film was bonded to one surface of a galvanized steel sheet having a thickness of 450 μm heated to 250 ° C., and rapidly cooled to 100 ° C. or less within 10 seconds by water cooling. With respect to the thus-obtained normal-temperature resin-coated metal sheet, adhesion, heat resistance, boiling water resistance, workability, stain resistance, solvent resistance, and normal temperature resistance were evaluated in the same manner as in Examples 1 to 20. Each item of impact resistance and low-temperature impact resistance was evaluated. Table 6 shows the results. Example 21 obtained the same results as Example 5, and Example 22 obtained the same results as Example 7.

As is clear from the above Examples 1 to 22 and Comparative Examples 1 to 4, predetermined amounts of various inorganic particles were added to the polyester resin (A), the vinyl polymer (B), and the rubbery elastic body (C). By using these resin compositions without impairing the excellent physical properties such as impact resistance of the resin composition comprising the polyester resin (A) and the vinyl polymer (B), adhesion to metal, etc. Even if the coated metal plate is exposed to heat or hot water for a long time, the coated resin does not deform or crack, that is, it is possible to maintain or improve the design properties such as the appearance of the printed surface. Do you get it.

Example 23 The composition shown in Example 21 of Table 5, that is, polyethylene terephthalate (PET, SA-1346P)
40% by mass, 40% by mass of a master batch containing the corresponding 50% titanium dioxide, and 1% by mass of a unit having a polar group.
Himilan 1706 as a vinyl polymer (B) having 10 or more
% By mass, 10% by mass of ethylene-butene rubber (EBM) as the rubber-like elastic resin (C), and 0.1% by mass of ADK STAB AO-60 as a phenolic antioxidant, and were dry-blended using a V-type blender. . Using this mixture directly,
A 50 μm thick film was obtained with an extrusion T die (extrusion temperature:
280 ° C). After cutting out ultrathin sections from this resin composition film with a microtome, dyed with ruthenic acid, the dispersion state of the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A) is transmitted through. Analysis was performed with an electron microscope. As a result, as in Examples 1 to 22, the rubber-like elastic resin (C) is
Almost 100% was encapsulated with the vinyl polymer (B), and the equivalent spherical equivalent diameter of the rubber-like elastic resin (C) was 1 μm or less, and was finely dispersed in the polyester resin (A). Also, titanium dioxide particles added in the master batch (final concentration 20%)
Was dispersed around the interface between the polyester resin (A) and the vinyl polymer (B). When the hiding properties were evaluated with a color difference meter, a commercially available white biaxially stretched PET film containing 20% TiO ₂ (white,
(Film thickness 50 μm).

The obtained white resin composition film had a surface tension of 380 μN / cm, and a corona discharge treatment was performed on one surface under the condition of a discharge amount (watt density) of 20 W / m ² / min, to give a surface tension of 540 μN. / cm. Using an acrylic ink on the corona discharge treated surface of this film, the ink film thickness after drying 2-3
solid printing by the gravure printing method so as to be μm,
Geometric pattern printing was performed.

The printed film of the white resin composition and a commercially available transparent biaxially stretched PET (transparent easy-adhesion type,
Film thickness of 50 μm, Tm: 240 ° C., crystallinity of about 45%), using a two-part urethane adhesive (adhesive coating thickness after drying 6)
μm) and dry-laminated by a conventional method to obtain a film composed of a resin composition film layer, a printing layer, and a top layer.

The resin composition film layer side of the three-layer film was heated to 200 ° C. or more using a two-pack type polyester-based adhesive (for vinyl chloride resin, adhesive thickness after drying: 4 μm) to a thickness of 450 μm. Laminated on one side of a galvanized steel sheet using a rubber roll, and water cooled to 100 ° C within 5 seconds
It was quenched to the following. For the resin-coated metal plate thus obtained, by the same evaluation method as in Examples 1 to 22,
Each item of adhesion, heat resistance, boiling water resistance, workability, stain resistance, solvent resistance, room temperature impact resistance and low temperature impact resistance was evaluated. Table 6 shows the results.

[0079]

[Table 6]

As is clear from the results of Example 23, the polyester resin (A), the vinyl polymer (B), and the rubber-like elastic material (C)
In addition, by adding a predetermined amount of titanium oxide as various inorganic particles, excellent physical properties such as impact resistance of a resin composition comprising a polyester resin (A) and a vinyl polymer (B), adhesion to a metal, etc. Without damage, even if the coated metal plate of a film in which these resin compositions are used as a base layer and a printed layer and a top layer are laminated, even if exposed to heat or hot water for a long time, the coated resin may be deformed or cracked. Without, that is, it is possible to maintain or improve the design, such as the aesthetics of the printed surface, in particular, the resin composition film can be suitably used as a film material for coating a metal plate due to the above characteristics,
Further, the metal plate coated on the surface with the resin composition of the present invention can have characteristics such as high design, good workability, and corrosion resistance,
It was found that it can be suitably used for interior and exterior materials for buildings, housings of home electric appliances, and the like.

[0081]

The resin composition of the present invention has an intrinsic viscosity of 0.3 dl / g.
The above polyester resin (A), a mixture of a vinyl polymer (B) containing a unit having a polar group of 1 mass% or more, the difference of the electronegativity of Pauling 0.45 (eV) inorganic particles having a polarity of ^0.5 or more Is added in an amount of 0.1 to 50 mass%. Since the polarity of the inorganic particles to be added, that is, the difference in the electronegativity of Pauling is 0.45 (eV) ^0.5 or more, the polar unit such as the carbonyl group or the terminal functional group of the component and the polyester resin (A) or a vinyl polymer. A covalent bond or an electrostatic interaction can be exerted between the polar units of (B). As a result, the adhesive force at the interface between the polyester resin (A) phase and the vinyl copolymer (B) phase can be enhanced, and the plasticization of the polyester resin (A) under hot and hot water can be suppressed. In addition, this effect is the polarity of inorganic particles, surface tension, dispersion state,
It can be remarkably exhibited by specifying the intrinsic viscosity of the polyester resin (A) or adding the rubber-like elastic body in a specific dispersion state.

As a result, even under severe use conditions such as use under boiling water for a long period of time, cracking deformation and design are not impaired. In addition, the polyester resin (A), the vinyl polymer (B) containing at least 1 mass% of a unit having a polar group, has the inherent impact resistance, chemical resistance, moldability, heat resistance, and gas barrier properties of corrosion-causing substances. Since it also has water resistance and adhesion to metals, it can be suitably used as a resin molded product.
Specifically, bumper, bonnet, door materials, wheel covers, oil tanks, interior and exterior parts such as instrument panels, bathrooms, boilers, water heaters, elevators and other wall materials, tiles, tile carpets and other floor materials,
Interior materials such as door materials, ceilings, partitions, pipes, sashes, etc., toys, housings for home appliances and weak electricity (refrigerators, washing machines, air conditioners, freezer showcases, computers, mobile phones), film and sheet moldings, piping It can be used for molded products. In particular, the present resin composition film can be suitably used as a film material for coating a metal plate because of the above-mentioned properties.
Furthermore, the metal plate coated on the surface with the resin composition of the present invention,
It can have characteristics such as high design, good workability, and corrosion resistance, and can be suitably used for interior and exterior materials for buildings, housings of home electric appliances, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) (C08L 67/00 101: 02 21:00) (72) Inventor Hiroshi Ueshiro 20-1 Shintomi, Futtsu City, Chiba Prefecture Nippon Steel Corporation Technology Development Division (72) Inventor Yasuhiro Kikuchi 20-1 Shintomi, Futtsu City, Chiba Prefecture Nippon Steel Corporation Technology Development Division (72) Inventor Kazunari Niki 20-Shintomi, Futtsu City, Chiba Prefecture 1 Nippon Steel Corporation Technology Development Headquarters (72) Inventor Yoshihiro Nami 20-1 Shintomi, Futtsu-shi, Chiba F-term (reference) in Nippon Steel Corporation Technology Development Headquarters 4F100 AA00A AA00H AB01C AK01B AK41A AK70A AL05A AT00B BA02 BA03 BA07 BA10A BA10B BA10C BA41A DE01A DE01H GB07 GB32 GB48 HB31A JA04B JA06A JA11B JB02 JL01 YY00A YY00B YY00H 4J002 BB053 BB153 BE012 BF012 BF022 BG012 BG072 BG102 BH022BK CF071 CF081 DE136 DE146 DE236 DF036 DG046 DH046 DJ016 DJ036 FD206 GF00

Claims (10)

[Claims] 1. A mixture comprising a polyester resin (A) having an intrinsic viscosity of 0.3 dl / g or more and a vinyl polymer (B) containing at least 1 mass% of a unit having a polar group, is provided with inorganic particles having a polarity of 0.1 to 50 mass%. %. A resin composition characterized by being added thereto. 2. The resin composition according to claim 1, wherein the difference in poling electronegativity for expressing the polarity of the inorganic particles is 1.0 (eV) ^0.5 or more. 3. A polyester resin (A) and a vinyl polymer (B)
The number of the inorganic particles unevenly distributed at the interface of 20% or more of the total inorganic particles, and / or polyester resin (A) and vinyl polymer
3. The resin composition according to claim 1, wherein the inorganic particles are unevenly distributed in 20% or more of the number of interface layers with (B). 4. The resin composition according to claim 1, wherein a part or all of the vinyl polymer (B) contains a rubber-like elastic resin (C) phase. object. 5. The polyester resin (A) has an intrinsic viscosity of 0.7 to 0.7.
2. The resin composition according to claim 1, wherein the content is 1.5 dl / g. 6. A resin composition according to any one of claims 1 to 5, which is molded alone or laminated with another resin or a resin composition and / or an adhesive. Resin film. 7. The resin film according to claim 5, wherein the resin film comprises three layers of the resin composition film layer according to any one of claims 1 to 5, a printing layer, and a top layer. 8. The crystallization temperature (Tc) or the melting temperature (Tm) of the top layer is 100 ° C. or more, and the crystallization ratio of the top layer is 15% of the saturation crystallinity of the resin constituting the top layer.
8. The resin film according to claim 7, which is not less than 10%. 9. A resin-coated metal plate having a surface coated with the resin film according to claim 6. 10. A resin-coated metal plate obtained by coating and cooling the surface with a molten film of the resin composition according to claim 1.