JP3258172B2 - Multilayer film for metal lamination - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a film for metal lamination. More specifically, a metal that has excellent adhesion to a metal plate, and when laminated on a metal plate, has excellent can-making properties such as squeezing processing to form a metal can, ironing workability, and has good impact resistance. The present invention relates to a multilayer film for metal lamination that provides a laminate.

[0002]

2. Description of the Related Art Conventionally, a paint is generally applied to prevent corrosion of the inner and outer surfaces of a metal can, and a thermosetting resin is used for the paint.

However, thermosetting resin coatings are generally of the solvent type and require a long time to form a coating film.
High-temperature heating of 0 to 250 ° C. is required. At the time of this baking, a large amount of organic solvent is scattered or evaporated, which has an adverse effect on the environment and poses a problem in work safety.
In addition, cracks and pinholes are apt to occur during subsequent processing, and therefore, these improvements are required.

Recently, for the purpose of simplifying the process, improving hygiene, preventing pollution, etc., development of a method for obtaining rust prevention without using an organic solvent has been promoted. One of the methods is a thermoplastic resin film of a metal can. Has been attempted. That is, a method of laminating a thermoplastic resin film on a metal plate of tin, tin-free steel, aluminum, or the like, followed by drawing, etc., has been studied. Polyolefin films and polyamide films have been tried as this thermoplastic resin film, but moldability, heat resistance,
It does not satisfy all of fragrance retention and impact resistance.

[0005] JP-A-56-10451 and JP-A-1-192546 disclose that a biaxially oriented polyethylene terephthalate film is laminated on a metal plate via a low-melting-point polyester adhesive layer and used as a can-making material. Is disclosed. However, the biaxially oriented polyethylene terephthalate film is excellent in heat resistance and fragrance retention, but is insufficient in moldability, and causes whitening (generation of minute cracks) and breakage of the film in canning with large deformation. Sometimes.

[0006] JP-A-1-192545 and JP-A-2-57339 disclose that an amorphous or extremely low-crystalline copolymerized aromatic polyester film is laminated on a metal plate and used as a can-making material. It has been disclosed.

However, an amorphous or extremely low-crystalline aromatic polyester film has good moldability, but is inferior in fragrance retention, and is subjected to post-processing such as printing after can-making, retort sterilization, and the like. May easily be embrittled by long-term storage, and may be transformed into a film which is easily broken by an impact from the outside of the can.

JP-A-64-22530 discloses that a low-orientation, heat-set, biaxially stretched polyethylene terephthalate film is laminated on a metal plate and used as a can-making material.

However, this film has not yet reached a low orientation applicable to can processing, and even if it can be processed in a region having a small degree of deformation, subsequent printing, sterilization of the contents of the can, etc. By the retort treatment, the film may be easily embrittled, and may be changed into a film which is easily broken by an impact from the outside of the can.

According to the study of the present inventor, the copolymerized aromatic polyester film undergoes a structural change with time, and the impact resistance, especially at low temperatures, gradually decreases. Therefore, it was found that when an impact was given after a while after bonding this film to the metal, the film was easily cracked. Poor impact resistance at low temperatures is caused by juice,
This is a serious problem in the case where the product is handled in a cooled state such as a metal can for soft drinks.

Polycarbonate withstands the forming process of a laminated plate and has excellent heat resistance and impact resistance, but ordinary polycarbonate has a somewhat insufficient adhesiveness to metal and fragrance retention.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a film for metal lamination which has excellent adhesiveness to a metal plate and, when laminated to a metal plate, has excellent moldability, heat resistance and impact resistance. To provide.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a film layer made of a specific polyester resin and a polycarbonate resin alone or a 1% by weight of a polycarbonate resin. The present inventors have found that a multilayer film obtained by laminating a film layer composed of a resin composition comprising a polyester resin and a polycarbonate resin containing the above shows excellent adhesiveness, impact resistance and the like when laminated on a metal plate.

That is, according to the present invention, (A) the melting point is 200 ° C.
First layer (A1) composed of a polyester resin having a formula (1)

[0015]

Embedded image

Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 6 ring carbon atoms, or R ¹ and R ² May form together with the carbon atom to which they are attached a cycloalkyl group having 5 to 6 ring carbon atoms,
R ³ and R ⁴ are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom, and m and n are each independently 0, 1 or 2. A second layer (A2) consisting of a resin composition consisting of 1 to 100% by weight of a polycarbonate resin substantially consisting of a repeating unit represented by the following formula (1) and 0 to 99% by weight of a polyester resin having a melting point of more than 200 ° C; A) A multilayer film for metal lamination, characterized in that the overall film thickness is in the range of 5 to 100 µm.

The multilayer film for metal lamination of the present invention comprises a first layer (A1) and a second layer (A2) made of a polyester resin having a melting point exceeding 200 ° C. Second layer (A
2) can be composed of a polycarbonate resin substantially consisting of the repeating unit represented by the above formula (1), and a polyester resin having a melting point exceeding 200 ° C. and a repeating unit substantially consisting of the repeating unit represented by the above formula (1) And a polycarbonate resin composition.

Such a polyester resin has a melting point of 2
When the temperature is lower than 00 ° C., a sufficient multilayer film cannot be obtained from the viewpoint of heat resistance and impact resistance. Preferably, the melting point of the polyester resin is 210 ° C. or higher.

In such a polyester resin, at least 70 mol% of the dicarboxylic acid component is terephthalic acid residues and / or isophthalic acid residues, and at least 70 mol% of the diol component is ethylene glycol residues and / or tetracarboxylic acid residues. A polyester resin which is a methylene glycol residue and has a melting point of 210 ° C. or more is preferable.

In such a polyester resin, at least 80 mol% of the dicarboxylic acid component contains terephthalic acid residues and / or
Or more preferably an isophthalic acid residue;
More preferably, 0 mol% or more is terephthalic acid residues and / or isophthalic acid residues. As the ratio of terephthalic acid residues to isophthalic acid residues, (moles of terephthalic acid residues) / (moles of terephthalic acid residues + moles of isophthalic acid residues) is 0.5 or more. It is more preferably 0.6 or more, and particularly preferably 0.7 or more. The dicarboxylic acid component other than the terephthalic acid residue and the isophthalic acid residue is not particularly limited as long as it is a divalent carboxylic acid.
Preferable examples include residues such as 6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, sebacic acid and adipic acid.

The diol component is more preferably 80 mol% or more of ethylene glycol residues and / or tetramethylene glycol residues, and 90 mol% or more of ethylene glycol residues and / or tetramethylene glycol residues. Is particularly preferred. Particularly preferred are ethylene glycol and tetramethylene glycol residues. The proportions of ethylene glycol and tetramethylene glycol used are not particularly limited, and it is also preferable to use each alone. The diol component other than the ethylene glycol residue and the tetramethylene glycol residue is not particularly limited, but preferably includes, for example, residues such as hexamethylene glycol, neopentylene glycol, diethylene glycol, and cyclohexanedimethanol.

These polyester resins can be produced by a conventionally known melt polymerization method. As the polyester resin, specifically, polyethylene terephthalate,
Polytetramethylene terephthalate, poly (ethylene /
(Tetramethylene) terephthalate copolymer, polyethylene (terephthalate / isophthalate) copolymer, and the like.

One or more of these polyester resins can be used.

The above polyester is phenol / 1,1,1,
2,2-tetrachloroethane mixed solvent (weight ratio 60/4)
In 0), the intrinsic viscosity measured at 35 ° C. is preferably from 0.3 to 1.2, and particularly preferably from 0.4 to 1.0.

As the polycarbonate resin used for the second layer, in the above formula (1), R ¹ and R ² are
Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, or R ¹ and R ² represent a ring together with a carbon atom to which they are bonded; A cycloalkyl group having 5 to 6 carbon atoms may be formed.

The alkyl group having 1 to 5 carbon atoms may be linear or branched, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, i
Examples thereof include so-butyl and pentyl.

Examples of the cycloalkyl group having 5 to 6 ring members include cyclopentyl and cyclohexyl.

R ³ and R ⁴ are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom. Examples of the alkyl group having 1 to 5 carbon atoms are the same as those described above. Examples of the halogen atom include fluorine, chlorine, and bromine.

M and n are each independently 0, 1 or 2.

Preferred examples of the repeating unit represented by the above formula (1) include bisphenol A type carbonate units in which R ¹ and R ² are methyl and m and n are 0.

The polycarbonate resin used in the present invention may be composed of the same type of repeating unit represented by the above formula (1), and may be composed of two or more types of different type of repeating units represented by the above formula (1). Can also.

The polycarbonate resin is usually prepared by reacting the corresponding dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or molecular weight regulator (interfacial polymerization method). Alternatively, it is produced by a transesterification reaction (melt polymerization method) between a corresponding dihydric phenol and a carbonate precursor such as diphenyl carbonate.

The method for producing the polycarbonate resin used in the present invention is not particularly limited, but it can be produced, for example, by the following method. That is, (a) a method in which a dihydric phenol is excessively reacted with a carbonate precursor when producing a resin by an interfacial polymerization method, (b) a method in which terminal blocking is carried out in producing a resin by an interfacial polymerization method, (C)
A method of adjusting the ratio between a dihydric phenol and a carbonate precursor when producing a resin by a melt polymerization method, and (d) adding a polyhydroxy compound at a later stage of the polymerization reaction when producing a resin by a melt polymerization method. Method (e): A polycarbonate resin having a terminal OH content of less than 20 mol / 10 ⁶ g and an appropriate amount of a dihydric phenol are melt-mixed, and if necessary, a catalyst is added to react the polycarbonate resin with the dihydric phenol. To increase the terminal OH content.

The polycarbonate resin and polyester resin in the present invention have a terminal OH and a terminal COOH. The present inventors have found that the greater the amount of these terminal groups, the better the adhesion to the metal plate.

The multilayer film of the present invention can be used so that any one of the first layer side and the second layer side is in contact with metal, but it is preferable to carry out as follows.

When the second layer is made of only a polycarbonate resin and is used after being laminated with a metal so that the second layer side is in contact with the metal, the polycarbonate resin is at least 2 parts.
Having a terminal OH of 0 eq / 10 ⁶ g and 10,000 to
Having a viscosity average molecular weight in the range of 40,000;
In particular, the adhesiveness to a metal plate is good and preferable. More preferably the terminal OH is at least 25eq / 10 ⁶ g, more preferably at least 30eq / 10 ⁶ g, and particularly preferably 40~200eq / 10 ⁶
g.

The second layer is made of polyester resin and polycarbonate.
And based on the total weight of these resins
And the polycarbonate resin accounts for 50 to 99% by weight
It is made of a resin composition, and the second layer side is in contact with metal
When used in a laminated form, the resin composition
Terminal O of polycarbonate resin and polyester resin
H, and the total amount of terminal COOH of the polyester resin is
At least 25 eq / 10 ⁶g
It is preferable from the viewpoint of adhesiveness. More preferably, terminal OH and terminal
The total amount of terminal COOH is at least 30 eq / 10⁶in g
Yes, more preferably 40 to 200 eq / 10⁶in g
is there.

Similarly, the second layer is composed of a polyester resin and a polycarbonate resin, and the resin composition is such that the polycarbonate resin accounts for 1 to 50% by weight based on the total polymerization of these resins. When used, the terminal OH and terminal CO of the resin composition
The total amount of OH is preferably at least 25 eq / 10 ⁶ g from the viewpoint of adhesiveness to a metal plate. More preferably, the total amount of terminal OH and terminal COOH is at least 30 e
q / 10 6 g, and more preferably 40 to 200 e.
q / 10 ⁶ g.

As described above, when the multilayer film of the present invention is laminated on a metal, the first polyester resin layer is preferably a surface layer (the side not in contact with the metal).

When the second layer is formed of a resin composition comprising a polyester resin and a polycarbonate resin, a polyester produced using a germanium compound and / or a titanium compound as a catalyst is preferably used. Such a polyester is excellent in film-forming stability when melt-mixed with a polycarbonate resin to form a film.

Further, a polyepoxy compound was added to the second layer (A
0.1 to 5 parts by weight, preferably 0.2 parts by weight, per 100 parts by weight of the polycarbonate resin or the resin composition forming 2).
To 4 parts by weight, more preferably 0.3 to 3 parts by weight.

In this case, the following compounds are preferably used as the polyepoxy compound.

(1) Glycidyl ether compounds such as 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4- (Hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxydiphenylsulfone, resorcinol, phenol novolak, cresol novolak, aromatic polyols such as naphthol novolak; phenol, Polyols obtained by a dehydration condensation reaction of an aromatic hydroxy compound such as naphthol with an aldehyde such as glyoxal, glutaraldehyde, benzaldehyde or p-hydroxybenzaldehyde, for example, under an acidic catalyst; Glycidyl ethers such as polyols such as polyhydric alcohols such as butanediol, neopentyl glycol, glycerol, polyethylene glycol and polypropylene glycol.

(2) Glycidyl ester compounds, for example, glycidyl esters of polycarboxylic acids such as phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid and the like.

(3) N-glycidyl compounds; for example, compounds in which active hydrogen bonded to the nitrogen atom of a nitrogen-containing compound such as aniline, isocyanuric acid, 4,4'-diaminodiphenylmethane is substituted by a glycidyl group.

(4) Glycidyl ether ester compounds, for example, glycidyl ether esters of hydroxycarboxylic acids such as p-hydroxybenzoic acid and hydroxynaphthoic acid.

(5) Epoxy resins obtained from unsaturated alicyclic compounds such as cyclopentadiene, dicyclopentadiene, etc., triglycidyl compounds of p-aminophenol, vinylcyclohexene dioxide and the like.

One or more of these polyepoxy compounds can be used. Among these, a polyepoxy compound such as diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) can be preferably used.

If the amount of the polyepoxy compound is less than 0.1 part by weight per 100 parts by weight of the polycarbonate resin or the resin composition forming the second layer, the effect of improving the adhesiveness by the addition of the polyepoxy compound becomes insufficient. Also 5
When the amount is more than the weight part, the heat resistance and mechanical properties inherent to the polycarbonate resin or the resin composition are easily lost, which is not preferable.

The film for forming the second layer can be produced by a conventionally known film forming method in which the polycarbonate resin or the resin composition is melt-extruded from a slit-shaped discharge such as a T-die and pulled by a casting roller. When the above-mentioned polyepoxy compound is contained, a polycarbonate resin or a resin composition and a polyepoxy compound may be melt-blended in advance and then formed into a film. A method of directly forming a film by blending is preferable in terms of productivity.

The polyester resin for forming the first layer and / or the polycarbonate resin or the resin composition for forming the second layer of the present invention may contain, if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, or the like. Agents, inorganic particles, organic particles, and additives such as an antistatic agent can be dispersed and compounded.

Further, the multilayer film of the present invention has a fine particle having an average particle diameter of 2.5 μm or less, a polyester resin for forming the first layer and a polyester resin for improving the handleability (winding property) in the film production process as described above. It is particularly recommended to contain 0.01 to 1 part by weight based on 100 parts by weight of the polycarbonate resin or the resin composition forming the second layer.

The lubricant may be inorganic or organic, but inorganic is preferred. Examples of the inorganic lubricant include silica, alumina, titanium dioxide, calcium carbonate, barium sulfate and the like, and examples of the organic lubricant include cross-linked polystyrene particles,
Examples include silicone particles. In any case, the average particle diameter is desirably 2.5 μm or less. When the average particle diameter of the lubricant exceeds 2.5 μm, coarse lubricant particles (for example, particles having a diameter of 10 μm or more) of a portion deformed by molding work have a starting point. And a pinhole may be formed or, in some cases, broken.

Particularly preferred lubricants in terms of pinhole resistance are monodispersed lubricants 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. It is a lubricant. Examples of such a lubricant include spherical silica, spherical titanium oxide, spherical zirconium, and spherical silicone particles.

The multilayer film for metal lamination of the present invention is preferably laminated with a steel plate, subjected to an impact, and then subjected to electric conduction (impact resistance test) so that the multilayer film has a current value of 0.1 mA or less. Shows excellent impact resistance over time. Such a film is suitably used for a metal container manufactured by deep drawing.

The multilayer film for metal lamination of the present invention should have a decrease in elongation of 30% or less after immersion in water at 50 ° C. for 24 hours. Preferred for small. Such a multilayer film has good impact resistance over time when laminated with metal and immersed in, for example, water. A more preferable elongation reduction rate is 25.
%, More preferably the elongation reduction rate is 20% or less.

The multilayer film of the present invention may be composed of three layers. In this case, the first layer (A1) and the second layer (A2)
And a third layer (A3). The third layer (A3)
It is preferable that the first layer, the second layer, and the third layer are stacked in this order with the second layer (A2) as an intermediate layer. The third layer is preferably made of the polyester resin forming the first and second layers and having a melting point of more than 200 ° C., specifically, polyethylene terephthalate, copolymerized polyethylene terephthalate having a melting point of more than 200 ° C., and polytetrafluoroethylene. It is preferred to be composed of methylene terephthalate or a blend of these polyesters.

The multilayer film of the present invention has a total thickness in the range of 5 to 100 μm. When the film thickness is less than 5 μm, defects such as pinholes and cracks are likely to occur when laminated on a metal plate, and when the film thickness is more than 100 μm, the moldability and the like deteriorate, and the cost is disadvantageously disadvantageous. The film thickness of the multilayer film for metal lamination of the present invention is preferably from 5 to 80 μm, more preferably from 6 to 75 μm, still more preferably from 10 to 60 μm, and
Particularly preferred is 5 to 40 μm.

The multilayer film comprises a first layer (A1) and a second layer (A1).
When the first layer (A1) is composed of the layer (A2), the thickness of the first layer (A1) is preferably 0.03 to 0.97, more preferably 0.05 to 0.95, when the thickness of the multilayer film is 1. Is 0.1 to 0.9.

When the multilayer film is composed of three layers,
First layer (A1), second layer (A2) and third layer (A3)
Is preferably in the range of 1 to 40 μm.

The multilayer film for metal lamination of the present invention may be prepared by separately melting the resins forming the respective layers, co-extruding, laminating and bonding before solidification, and, if necessary, biaxially stretching and heat-setting. Can be produced by a method of separately melting, extruding, and, if necessary, stretching the resins for forming the respective layers. In addition, in order to produce a multilayer film composed of the third layer, a two-layer laminated film may be produced in advance by co-extrusion and then laminated with another film of the third layer.

By the way, the second layer is made of only the polycarbonate resin, or
In the case of a layer comprising a resin composition comprising 99% by weight and 1 to 40% by weight of a polyester resin, a polycarbonate resin or a coating composition obtained by dissolving the resin composition in an organic solvent is used as a polyester for the first layer. Forming by applying to a film made of resin, or applying such a coating composition to a substrate such as a metal plate, and laminating a polyester resin layer on the obtained polycarbonate resin or resin composition applied layer. Can be.

The organic solvent used in this case preferably has a boiling point at normal pressure of 30 to 150 ° C. and does not react with polycarbonate. The organic solvent used here may be any solvent that satisfies the above conditions.Specifically, methylene chloride, chloroform, 1,2-dichloroethane, tricrene, tetrahydrofuran, dioxane, dioxolan, methyl ethyl ketone, methyl isobutyl ketone,
Acetonitrile, ethyl acetate, dimethylformamide and the like can be mentioned. These solvents can be used alone or in combination of two or more.

The ratio of the solvent to the polycarbonate resin or the resin composition is such that the polycarbonate resin or the resin composition is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the solvent.
Particularly preferably, it is 3 to 10 parts by weight.

In the coating composition, a component other than the polycarbonate resin or the resin composition may be blended as a subcomponent. As the components,
It is preferable to use a polyepoxy compound containing two or more epoxy groups in the molecule. As the polyepoxy compound, the same compounds as described above can be used.

As a method of applying the coating composition to a film or substrate made of the first layer polyester resin, a conventionally known coating method can be applied. For example, a roll coating method, a gravure coating method, a roll brushing method, a spray coating method, an air knife coating method, a curtain coating method, or the like can be applied alone or in combination. After the application, the solvent is removed by heating according to a conventional method. The coating composition may be applied to a polyester film after biaxial stretching, or may be further applied to an unstretched film or a film after longitudinal uniaxial stretching, and then further stretched.

The thickness of the applied polycarbonate layer or resin composition layer is preferably 0.1 to 5 μm. If the film thickness is less than 0.1 μm, the adhesion to metal becomes insufficient,
Polycarbonate may not be able to exhibit impact resistance, and if it is thicker than 5 μm, coating may be difficult and economical efficiency may be poor. The thickness of the polycarbonate film is more preferably 0.2 to 4 μm, and particularly preferably 0.3 to 3 μm.

In the multilayer film of the present invention, the first polyester resin layer is preferably biaxially oriented by stretching. It is also preferable that the layer of the second layer made of the resin composition is biaxially oriented.

As a metal plate to which the multilayer film of the present invention is bonded, particularly a plate made of tinplate, tin-free steel, aluminum or the like is suitable. The lamination of the film to the metal plate can be performed, for example, by the following methods (A) and (A).

(A) The metal plate is heated to a temperature higher than the softening temperature of the film, the film is bonded, and then cooled and adhered.

(A) An adhesive layer is primer-coated on a film in advance, and this surface is bonded to a metal plate. As the adhesive layer, a known resin adhesive, for example, an epoxy adhesive, an epoxy-ester adhesive, an alkyd adhesive, or the like can be used.

[0072]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the examples, "parts" means "parts by weight".

(I). The viscosity average molecular weight (Mv) of the polycarbonate was calculated from the intrinsic viscosity ([η]) measured in a methylene chloride solution using the following Schnell equation.

[0074]

(Equation 1)

(Ii). The amount of terminal OH groups of the polycarbonate was determined by color measurement (described in Die Makromol. Chem. 88 (1965) 215) by the interaction between TiCl ₄ and terminal OH groups.

(Iii) The terminal amount of the polycarbonate and polyester composition was measured as follows.

The aromatic terminal OH content is hexafluoro-2-
Measured by H-NMR in propanol-d, solvent.

The aliphatic terminal OH content was measured by ¹ H-NMR in a mixed solvent of phenol-d ₆ : chloroform-d ₁ = 3: 2.

The terminal COOH content was determined by titration with a benzyl alcohol solution of NaOH using tetrabromophenol blue as an indicator in a phenol: tetrachloroethane = 2: 3 mixed solvent.

(Iv) Peeling Strength The same two multilayer films are superposed and laminated with a steel plate so that the resin layer whose peeling strength is to be evaluated is on the outer side (the side in contact with the metal plate) and evaluated. The method of laminating is as follows.
It was laminated between two steel plates of 10 μm and laminated by holding them at a pressure of 20 kg / cm ² for 30 seconds by a hot press machine at 285 ° C. for 30 seconds. The laminate was cut into a size of 10 mm in width and 50 mm in length to prepare a test piece. The test piece was preliminarily coated with a release agent up to 20 mm at one end, so that the laminate plate was easily peeled off.

The test piece 20 on the side where the release agent was adhered was
The two steel plates are peeled in opposite directions at the
Fix both ends of the stripped part with a tensile tester,
Peel strength was measured at a pulling speed of 20 mm / min. (J
According to ISK 6854).

(V). Melting point (Tm) and glass transition temperature (T
g) was measured by DSC.

(Vi) Impact resistance over time A laminated plate is manufactured from one multilayer film and one steel plate in the same manner as described in (iv). 50 after production
Hold in water at ℃ for 24 hours. Thereafter, an impact deformation test is performed on the laminate according to the method described in JIS K5400. That is, a shooting die having a radius of curvature of 5 mm is set on the upper surface of the laminate plate on which the film is not laminated, and a weight having a mass of 200 g is dropped by gravity from a position of 20 cm on the shooting die. At this time, a rubber plate having a thickness of 5 mm is provided below the laminate plate.

After being subjected to the impact deformation test, one electrode was applied to a metal surface of the laminate plate on which the film was not laminated, and one electrode was placed at the position (convex portion) where the weight fell on the film surface of the other laminate plate. % Cotton solution and the other electrode. A voltage of 6 V is applied, and the current value at that time is measured. Current value (mA)
The smaller the value, the better the impact resistance with time.

(Vii) The elongation reduction rate of the film was calculated by the following formula by immersing the film in water at 50 ° C. for 24 hours, and measuring the elongation before and after the immersion.

[0086]

(Equation 2)

[Examples 1 to 4 and Comparative Example 1] (Production of copolymerized polyester film) Polyethylene terephtalate obtained by copolymerizing the components shown in Table 1 (intrinsic viscosity 0.64, particle size ratio 1.1, average) After drying titanium dioxide having a particle size of 0.3 μm (0.3% by weight) in a conventional manner, the extruder is melt-extruded from a slit die at a polymer temperature of about 280 ° C. using an extruder. Obtained. Next, after stretching this unstretched film longitudinally 3.1 times at 110 ° C.,
Biaxially oriented films F1 to F4 which were horizontally stretched twice and heat-set at 190 ° C. were obtained. The thickness of the obtained film was 6 μm.

[0088]

[Table 1]

(Production of polycarbonate) A reaction vessel equipped with a vacuum distilling system having a stirrer and a nitrogen gas inlet was charged with 216 parts of diphenyl carbonate, 228 parts of bisphenol A and 0.05 part of diNa salt of bisphenol A. , And the operation of introducing nitrogen gas after vacuum degassing at room temperature was repeated three times to replace the reaction system with nitrogen. Next, after heating and reacting at 190 ° C. under normal pressure for 30 minutes, the pressure was gradually reduced at the same temperature to 50 mmHg after 60 minutes. Further, the reaction temperature was raised from 190 ° C. to 290 ° C. over about 60 minutes, and at the same time, the degree of vacuum was changed from 50 mmHg to 1 mmHg or less. As the reaction proceeded, phenol generated by the reaction was distilled off. The reaction was carried out for 40 minutes under the same conditions to obtain a polycarbonate resin having a viscosity average molecular weight (Mv) of 26000 and a terminal OH content of 73 eq / 10 ⁶ g.

The obtained polycarbonate resin was melt-extruded at a polymer temperature of about 290 ° C. in the same manner as in the production of the copolymerized polyester film to form a film. However, in that case,
The copolymerized polyester film of F1 to F4 is supplied between the polycarbonate film and the casting roller to laminate and cool the two kinds of films, and a laminated film of the polyester layer (A1) and the polycarbonate layer (A2) Example 1 ( F1-A2) and Example 2 (F2-
A2), Example 3 (F3-A2) and Example 4 (F4-
A2) was prepared. The thickness of these laminated films is about 2
It was 5 μm.

With respect to this laminated film, the above (iv), (v
The laminate was laminated with a steel sheet according to the method of i), and the peel strength and the impact resistance with time of the laminate were measured. The lamination was performed such that the polycarbonate layer (A2) of the laminated film was in contact with the metal.

[0092]

[Table 2]

Comparative Example 1 is a case where the A1 layer composed of the polyester (F2) used in Example 2 is used alone.

Examples 5 to 8 and Comparative Example 2 (1) 216 parts of diphenyl carbonate, 228 parts of bisphenol A, and the diNa salt of bisphenol A 0.0
Five parts were charged into a reaction vessel equipped with a stirrer and a vacuum distillation system having a nitrogen gas inlet, and the operation of introducing nitrogen gas after vacuum degassing at room temperature was repeated three times to replace the reaction system with nitrogen. . Next, after heating and reacting at 190 ° C. under normal pressure for 30 minutes, the pressure was gradually reduced at the same temperature and 50 mm after 60 minutes.
Hg. Further, the reaction temperature was raised from 190 ° C. to 290 ° C. over about 60 minutes, and at the same time, the degree of vacuum was changed from 50 mmHg to 1 mmHg or less. As the reaction proceeded, phenol generated by the reaction was distilled off. 4 under the same conditions
0 minute reaction, viscosity average molecular weight (Mv) 26000,
A polycarbonate resin having a terminal OH content of 73 eq / 10 ⁶ g was obtained.

(2) Polyethylene terephthalate (intrinsic viscosity: 0.64, melting point: 256 ° C., containing 0.2% by weight of titanium dioxide having an average particle size of 0.3 μm) and the polycarbonate produced in the above (1) were prepared by a conventional method. And dry them with 2
The co-extruded layers were supplied to two extruders for forming a laminated film, and the polyethylene terephthalate film was melted and extruded through a co-extrusion slit at a polymer temperature of 280 ° C and a polycarbonate at a polymer temperature of 300 ° C. The co-extruded film was taken up by a casting drum with the polyethylene terephthalate side inside, to produce a laminated film. At this time, several kinds of laminated films having different film thicknesses as shown in Table 3 were obtained by changing the feed amount of the polymer and the film take-up speed.

For comparison, the viscosity average molecular weight (M
v) A polyester / polycarbonate laminated film (Comparative Example 2) using 25000, polycarbonate having a terminal OH content of 13 eq / 10 ⁶ g was produced.

[0097]

[Table 3]

Further, regarding this laminated film, the above (i)
The laminate was laminated with a steel sheet according to the methods of v) and (vi), and the peel strength and the impact resistance with time of the laminated plate were measured. As shown in Table 4, both were found to be excellent. The lamination was performed such that the polycarbonate layer of the laminated film was in contact with the metal.

[Example 9] In Example 5, the polyepoxy compound ("Epicoat" 82
8, manufactured by Yuka Shell Epoxy Co., Ltd.), except that 0.5 wt% was blended to form a film. The results are shown in Table 4.

[0100]

[Table 4]

Examples 10 to 15: Isophthalic acid (12 mol% or 8 mol%) copolymerized polyethylene terephthalate, sebacic acid (5 mol%) copolymerized polyethylene terephthalate, polyethylene terephthalate and polytetramethylene terephthalate shown in Table 5 50 of the two
/ 50 (weight ratio) blends (all with an average particle size of 0.3
μm titanium dioxide (containing 0.3% by weight) was used as the polyester film layer (A1) and had a viscosity average molecular weight of 25.0
00, polycarbonate having a terminal OH content of 10 eq / 10 ⁶ g was separately dried and melted by a conventional method so as to become a polycarbonate film layer (A2), and co-extruded from dies adjacent to each other to form a laminate. After being attached, it was rapidly cooled and solidified to produce six kinds of laminated films shown in Table 5.

IA in Table 5 is isophthalic acid, SA
Is sebacic acid, PET is polyethylene terephthalate,
PBT is an abbreviation for polytetramethylene terephthalate.

[0103]

[Table 5]

With respect to this laminated film, the above (iv), (v
The laminate was laminated with a steel sheet according to the method of i), and the peel strength and the impact resistance over time of this laminated plate were measured. As shown in Table 6, all were found to be excellent. The lamination was performed such that the polyester layer of the laminated film was in contact with the metal.

[0105]

[Table 6]

[Examples 16 to 19] (Production of copolymerized polyester film) Polyethylene terephthalate prepared by copolymerizing isophthalic acid or sebacic acid at the ratio shown in Table 7 (intrinsic viscosity 0.64, average particle size 0.3 μm)
m of titanium dioxide (containing 0.3% by weight) was dried by a conventional method, and then dried at about 280 ° C. using an extruder.
The polymer was melt-extruded from a slit die at a polymer temperature of, and was taken up by a casting roller to obtain an unstretched film.
Next, the unstretched film was longitudinally stretched 3.1 times at 110 ° C., horizontally stretched at 125 ° C. three times, and heat-set at 190 ° C. to obtain a biaxially oriented film. The thickness of the obtained film was 6 μm.

Table 7 shows the melting point (by DSC) and glass transition temperature of each of the copolymerized polyesters (Polymer Nos. 1 to 4).

[0108]

[Table 7]

(Production of Laminated Film) Viscosity Average Molecular Weight 2
5000 bisphenol A-based polycarbonate resin (terminal OH content 15 eq / 10 ⁶ g) (abbreviated as PC) 16
0 parts by weight and 40 parts by weight of a polyethylene terephthalate resin (abbreviated as PET) having an intrinsic viscosity of 0.6 were dried by a conventional method, and then melt-extruded from a slit die at a polymer temperature of about 290 ° C. using an extruder to form a film. . At that time, each of the copolymerized polyester films obtained as described above from Polymer Nos. 1 to 4 was supplied between casting rollers when the above-mentioned blended polymer film (PC + PET) was formed, and two kinds of films were laminated and integrated. After cooling, a laminated film composed of the polyester layer (A1) and the blended polymer layer (A2) was produced.
The thickness of this laminated film was about 30 μm.

With respect to these films, the terminal OH content and COOH content were measured according to the above-mentioned method (Table 8).

Further, with respect to this laminated film, the above (i)
The laminate was laminated with a steel sheet according to the methods of v) and (vi), and the peel strength and the impact resistance with time of the laminate were measured. As shown in Table 8, both were found to be excellent. The above laminated films were laminated so that the blend polymer layer was in contact with the metal.

[0112]

[Table 8]

[Embodiments 20 to 23] The above embodiments 16 to 1
The production and evaluation of a laminated film were performed in the same manner as in these examples except that a polytetramethylene terephthalate resin (tetrabutyl titanate catalyst, intrinsic viscosity 0.9) (PBT) was used instead of the polyethylene terephthalate resin (PET) of No. 9. went.

The results are as shown in Table 9.

[0115]

[Table 9]

Examples 24 to 28 (Production of polycarbonate) 216 parts of diphenyl carbonate, 228 parts of bisphenol A and 0.05 part of a diNa salt of bisphenol A were placed in a vacuum distillation apparatus equipped with a stirrer and a nitrogen gas inlet. The reaction system was charged into a reaction vessel equipped with an outlet system, and the operation of introducing a nitrogen gas after vacuum degassing at room temperature was repeated three times to replace the reaction system with nitrogen. Then, under normal pressure
After heating and reacting at 90 ° C. for 30 minutes, the pressure was gradually reduced at the same temperature to 50 mmHg after 60 minutes.

Further, the reaction temperature was raised from 190 ° C. to 290 ° C. over about 60 minutes, and at the same time, the degree of vacuum was changed from 50 mmHg to 1 mmHg or less. As the reaction proceeded, phenol generated by the reaction was distilled off. 7 under the same conditions
0 minute reaction, viscosity average molecular weight (Mv) 28000,
A polycarbonate resin having a terminal OH content of 48 eq / 10 ⁶ g was obtained.

A polymer obtained by dry blending polyethylene terephthalate (germanium dioxide catalyst, containing 0.2% by weight of titanium dioxide having an intrinsic viscosity of 0.64 and an average particle size of 0.3 μm) and a predetermined amount of the polycarbonate and polyester produced above was used. These are dried by a conventional method, and these are supplied to two extruders for forming a two-layer co-extruded laminate film, respectively. The polyethylene terephthalate has a polymer temperature of 280 ° C, and the blended polymer has a polymer temperature of 270 to 290 ° C. It was melt extruded from the slit. The co-extruded film was taken up by a casting drum with the polyethylene terephthalate side inside, to produce a laminated film.
At this time, several kinds of laminated films having different film thicknesses as shown in Table 10 were obtained by changing the feed amount of the polymer and the film take-up speed.

[0119]

[Table 10]

Table 11 shows the properties of these laminated films.

The above laminated film was laminated such that the blend polymer side was in contact with the metal.

[0122]

[Table 11]

[Examples 29 to 30] (Production of polyester film) As a polyester film, a polyester film of polymer No. 2 in Table 7 was used.

(Production of Laminated Film) Viscosity Average Molecular Weight 2
A polymer prepared by dry blending a predetermined amount of a 5000, bisphenol A-based polycarbonate having a terminal OH content of 15 eq / 10 ⁶ g and a polyester having an intrinsic viscosity of 0.6 shown in Table 12 was dried by a conventional method, and then dried at about 290 ° C. using an extruder. The polymer was melt-extruded from a slit die at a polymer temperature of 5 to form a film. At that time, the polyester film is supplied between the casting rollers at the time of forming the above-mentioned blended polymer film, and the two kinds of films are laminated and integrated. After cooling, the film is composed of the polyester layer (A1) and the blended polymer layer (A2). A laminated film was manufactured. The thickness of this laminated film was about 30 μm.

[0125]

[Table 12]

Table 13 shows the performance of these laminated films.

[0127]

[Table 13]

Further, Example 29 of each of the above laminated films was used.
And 30 were laminated so that the polyester layer (A1) was in contact with the metal.

Examples 31 to 33 (Production of polycarbonate) 216 parts of diphenyl carbonate, 228 parts of bisphenol A and 0.05 part of a diNa salt of bisphenol A were placed in a vacuum distillation apparatus equipped with a stirrer and a nitrogen gas inlet. The reaction system was charged into a reaction vessel equipped with an outlet system, and the operation of introducing a nitrogen gas after vacuum degassing at room temperature was repeated three times to replace the reaction system with nitrogen. Then, under normal pressure
After heating and reacting at 90 ° C. for 30 minutes, the pressure was gradually reduced at the same temperature to 50 mmHg after 60 minutes.

Further, the reaction temperature was raised from 190 ° C. to 290 ° C. over about 60 minutes, and at the same time, the degree of vacuum was changed from 50 mmHg to 1 mmHg or less. As the reaction proceeded, phenol generated by the reaction was distilled off. 7 under the same conditions
0 minute reaction, viscosity average molecular weight (Mv) 28000,
A polycarbonate resin having a terminal OH content of 48 eq / 10 ⁶ g was obtained.

A polymer prepared by dry blending polyethylene terephthalate (containing 0.64% by weight of titanium dioxide having an intrinsic viscosity of 0.64 and an average particle diameter of 0.3 μm) and the above-prepared polycarbonates and polyesters was dried by a conventional method. These were supplied to two extruders for forming a two-layer co-extruded laminated film, respectively, and polyethylene terephthalate was heated at a polymer temperature of 280.
℃, the polymer temperature of the blended polymer is 270-290 ° C
The melt extrusion was performed through a co-extrusion slit. The co-extruded film was taken up by a casting drum with the polyethylene terephthalate side inside, to produce a laminated film. At this time, several kinds of laminated films having different film thicknesses as shown in Table 14 were obtained by changing the feed amount of the polymer and the film take-up speed.

[0132]

[Table 14]

Table 15 shows the properties of the laminated film. In this case, evaluation was performed by laminating the polyester layer (A1) so as to be in contact with the metal.

[0134]

[Table 15]

Examples 34 to 39 Polyethylene terephthalate and copolymerized polyethylene terephthalate shown in Table 16 (both containing 0.3% by weight of titanium dioxide having an average particle diameter of 0.3 μm) were coated with a polyester film layer (A
1) Similarly, the polyester or polyester blend shown in Table 16 was used as a polyester film layer (A3), and further, the viscosity average molecular weight was 25,000 and the terminal OH content was 15
eq / 10 ⁶ g of polycarbonate was separately dried and melted by a conventional method so as to form a polycarbonate film layer (A2).
Coextrusion was carried out from dies adjacent to each other so that 2) became an intermediate layer, and after lamination and fusion, they were quenched and solidified to produce six types of laminated films shown in Table 16.

The IA in Table 16 is isophthalic acid, P
ET is an abbreviation for polyethylene terephthalate, and PBT is an abbreviation for polytetramethylene terephthalate.

The thickness of each layer of each film was as shown in Table 16.

[0138]

[Table 16]

The laminated multilayer film was laminated with a steel sheet according to the above methods (iv) and (vi).
When the peel strength and the impact resistance with time of this laminated plate were measured, it was found that all were excellent as shown in Table 17. The lamination is A3 of the laminated film.
The procedure was such that the layer was in contact with the metal.

[0140]

[Table 17]

[Examples 40 to 45 and Comparative Examples 3 to 4] (Production of polycarbonate) 216 parts of diphenyl carbonate, 228 parts of bisphenol A and 0.05 part of a diNa salt of bisphenol A were mixed with a stirrer and nitrogen gas. A reaction vessel equipped with a vacuum distillation system having an inlet was charged, and the operation of introducing nitrogen gas after vacuum degassing at room temperature was repeated three times to replace the reaction system with nitrogen. Then, under normal pressure
After heating and reacting at 90 ° C. for 30 minutes, the pressure was gradually reduced at the same temperature to 50 mmHg after 60 minutes. Further, the reaction temperature was raised from 190 ° C. to 290 ° C. over about 60 minutes, and at the same time, the degree of vacuum was reduced from 50 mmHg to 1 mmHg or less. As the reaction proceeded, phenol generated by the reaction was distilled off. Reaction was carried out under the same conditions for 40 minutes, viscosity average molecular weight (Mv)
26000, a polycarbonate resin having a terminal OH content of 73 eq / 10 ⁶ g was obtained.

(Production of polyester film) Polyethylene terephtalate obtained by copolymerizing the components shown in Table 18 (intrinsic viscosity: 0.64, particle size ratio: 1.1, average particle size: 0.3 μm, 0.3 wt. Of titanium dioxide) %) Was extruded from a die, quenched and solidified to form an unstretched film. Then, the unstretched film is heated at 110 ° C.
Then, the film was stretched 3.1 times in the longitudinal direction, then stretched 3 times in the transverse direction at 125 ° C., and a biaxially oriented film heat-set at 190 ° C. was obtained. The thickness of the obtained film was 25 μm.

A predetermined amount (shown in Table 18) of the polycarbonate and polyepoxy compound ("Epicoat" 828, manufactured by Yuka Shell Epoxy Co., Ltd.) prepared above was dissolved in 100 parts of methylene chloride to prepare a coating composition. Manufactured. This was applied on a polyester film using a bar coater, and heat-treated at 50 ° C. for 3 minutes and then at 100 ° C. for 5 minutes to form a polycarbonate layer having a thickness of 2 μm, thereby producing six types of multilayer films. Table 18 also shows only the polyester film as a comparative example.

[0144]

[Table 18]

When the elongation reduction rate of these films was determined according to the method (vii), the reduction rate was low (Table 19).

Further, this film was laminated with a steel plate according to the above methods (iv) and (vi), and the peel strength and the impact resistance with time of this laminated plate were measured.
As shown in FIG. 9, all were found to be excellent. The lamination was performed such that the polycarbonate layer (A2) of the laminated film was in contact with the metal.

[0147]

[Table 19]

Example 46 10 parts of the polycarbonate produced in Example 40 was dissolved in 100 parts of 1,3-dioxolane to prepare a coating composition, which was coated on a tin-free steel sheet having a thickness of 0.25 mm. Apply using a bar coater, 1 minute at 70 ° C, then 5 minutes at 110 ° C
After a heat treatment for about 3 minutes, a polycarbonate layer having a thickness of about 3 μm was formed. The same treatment was applied to the opposite side of the tin-free steel plate to obtain a tin-free steel plate having a polycarbonate layer on both sides. Next, this was heated to 250 ° C., and the polyester film used in Example 40 was bonded to both sides. When the obtained laminate was evaluated in the same manner as in Examples 40 to 45, the peel strength,
The impact resistance with time was good.

[Examples 47 to 53 and Comparative Examples 5 to 6] (Production of polycarbonate) 216 parts of diphenyl carbonate, 228 parts of bisphenol A and 0.05 part of a diNa salt of bisphenol A were added to a stirrer and a nitrogen gas. A reaction vessel equipped with a vacuum distillation system having an inlet was charged, and the operation of introducing nitrogen gas after vacuum degassing at room temperature was repeated three times to replace the reaction system with nitrogen. Then, under normal pressure
After heating and reacting at 90 ° C. for 30 minutes, the pressure was gradually reduced at the same temperature to 50 mmHg after 60 minutes. Further, the reaction temperature was raised from 190 ° C. to 290 ° C. over about 60 minutes, and at the same time, the degree of vacuum was reduced from 50 mmHg to 1 mmHg or less. As the reaction proceeded, phenol generated by the reaction was distilled off. Reaction was carried out under the same conditions for 70 minutes, and the viscosity average molecular weight (Mv)
A polycarbonate resin having 28000 and a terminal OH content of 48 eq / 10 ⁶ g was obtained.

A predetermined amount of each of the polycarbonate and polyester was dried by a conventional method, and then drive-blended.
The mixture was melt-kneaded using a 30 mmφ co-rotating biaxial extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) to produce three types of blended polymers (a), (b) and (c). Table 20 shows the type, amount and blending conditions of each component.

[0151]

[Table 20]

10 parts of each of the resulting three types of blended polymers were dissolved in 100 parts of 1,3-dioxolane to prepare three types of coating compositions.

(Production of polyester film) Polyethylene terephtalate (having an intrinsic viscosity of 0.64 and containing 0.3% by weight of titanium dioxide having an average particle size of 0.3 μm) containing the components shown in Table 21 as copolymer components was always used. After being dried and melted by the method, it was extruded from a die and quenched and solidified to prepare an unstretched film. Next, this unstretched film is put into a
After stretching longitudinally 3.1 times at a temperature of 130 ° C., it was stretched transversely three times at a temperature of 120 to 130 ° C. to obtain a biaxially oriented film heat-set at 190 ° C. The thickness of the obtained film was 25 μm.

The film produced above was used for (a), (b),
The coating composition (c) was applied using a bar coater, and was subjected to heat drying treatment with hot air at 100 ° C. for 1 minute and at 120 ° C. for 5 minutes to form a blend polymer layer having a thickness of about 2 μm. Table 21 also shows only the polyester film as a comparative example.

[0155]

[Table 21]

When the elongation reduction rate of these films was determined according to the method (vii), the reduction rate was low (Table 22).

Further, this film was laminated with a steel plate according to the above methods (iv) and (vi), and the peel strength and the impact resistance with time of this laminated plate were measured.
As shown in FIG. 2, all were found to be excellent. The lamination was performed such that the polycarbonate layer (A2) of the laminated film was in contact with the metal.

[0158]

[Table 22]

Example 54 The coating composition of (a) prepared in Example 47 was applied on tin-free steel having a thickness of 0.25 mm using a bar coater.
Hot air heating treatment was performed at 100 ° C. for 1 minute and then at 120 ° C. for 3 minutes to form a blend polymer layer having a thickness of about 2 μm. The same treatment was applied to the opposite side of the tin-free steel plate to obtain a tin-free steel plate having a blend polymer layer on both surfaces. Next, this was heated to 250 ° C., and the polyester film used in Example 47 was bonded to both sides. When the obtained laminates were evaluated in the same manner as in Examples 47 to 53, both the peel strength and the impact resistance with time were good.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 5-228867 (32) Priority date September 14, 1993 (September 14, 1993) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-248551 (32) Priority date September 21, 1993 (September 21, 1993) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-244515 (32) Priority date September 30, 1993 (September 30, 1993) (33) Countries claiming priority Japan (JP) (31) Priority claim number Japanese Patent Application Hei 5-266358 ( 32) Priority date October 25, 1993 (Oct. 25, 1993) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-268960 (32) Priority date 1993 October 27 (1993.10.27) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-289284 (32) Priority date November 18, 1993 (1993. 11.18) (33) Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-327274 (32) Priority date December 24, 1993 (December 24, 1993) (33) Priority claim country Japan (JP) (72) Inventor Hiroo Inada 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Prefecture Teijin Limited Iwakuni Research Center (56) References JP-A-6-226915 (JP, A) JP-A-7-9616 (JP) JP-A-63-144048 (JP, A) JP-A-7-186328 (JP, A) JP-A-7-186330 (JP, A) JP-A-7-80992 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (10)

(57) [Claims] (A) a first layer (A1) made of a polyester resin having a melting point exceeding 200 ° C. and the following formula (1): [Wherein R ¹ and R ² are each independently a hydrogen atom,
It is an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 6 ring carbon atoms, or R ¹ and R ² are taken together with the carbon atom to which they are bonded to form a cycloalkyl having 5 to 6 ring carbon atoms. R ³ and R ⁴ may be independently an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom, and m and n are independently 0 and 1, Or 2. Substantially Ri Na repeating unit represented by, the end of at least 20 eq / 10 ⁶ g
1-100% by weight of polycarbonate resin having terminal OH
And a second layer (A2) composed of a resin composition comprising 0 to 99% by weight of a polyester resin having a melting point exceeding 200 ° C., and (B) the overall film thickness is in the range of 5 to 100 μm.
And laminating the metal so that the second layer (A2) is in contact with the metal.
A multilayer film for metal lamination characterized by being used as a laminate. 2. The multilayer film for metal lamination according to claim 1, which shows a current value of not more than 0.1 mA when laminated with a steel plate, subjected to an impact and then energized (impact resistance test). 3. A port polycarbonate resins is 10,000
3. The multilayer film for metal lamination according to claim 1, which has a viscosity average molecular weight in a range of 40,000. Wherein Ri second layer Do a resin composition comprising 50 to 99 wt% polyester resin 1-50% by weight of a polycarbonate resin, terminal OH and the terminal C of the resin composition
3. The multilayer film for metal lamination according to claim 1, wherein the total amount of OOH is at least 25 eq / 10 ⁶ g. Wherein Ri second layer Do a resin composition comprising 1 to 50 wt% polyester resin 50 to 99 wt% of a polycarbonate resin, terminal OH and the terminal CO of the resin composition
3. The multilayer film for metal lamination according to claim 1, wherein the total amount of OH is at least 25 eq / 10 ⁶ g. 6. A polyester resin having a melting point of more than 200 ° C. for forming the first layer, comprising at least 7 of dicarboxylic acid components.
6. A metal laminate according to claim 1, wherein 0 mol% is a polyester resin in which terephthalic acid and / or isophthalic acid are present and at least 70 mol% of the diol component is ethylene glycol and / or tetramethylene glycol. For multilayer film. 7. The polyepoxy compound is contained in the second layer (A2) in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the polycarbonate resin or the resin composition forming the same.
7. The multilayer film for metal lamination according to any one of items 6 to 6. 8. Fine particles having an average particle diameter of 2.5 μm or less are used as first particles.
Polyester resin 100 forming it in layer (A1)
The amount is 0.01 to 1 part by weight per part by weight.
The multilayer film for metal lamination according to any one of the above. 9. The polyester resin according to claim 1, wherein the polyester resin in the resin composition forming the second layer (A2) is produced using a germanium compound and / or a titanium compound as a catalyst. 2. The multilayer film for metal lamination according to item 1. 10. The multilayer film for metal lamination according to claim 1, wherein the polyester resin forming the first layer (A1) is biaxially oriented.