JPH08217892A - Regenerated film - Google Patents

Abstract

PURPOSE: To obtain a regenerated film of a polyester slightly discoloring by using waste of a laminated film provided with a thin film. CONSTITUTION: In a regenerated film comprising a single-layer film or at least one layer of a multi-layer film made by using a polyester containing a regenerated material, this regenerated film comprises the regenerated material composed of a material obtained by recovering a laminated film made by providing at least one side of the polyester film with a thin film comprising a composition prepared by blending 100 pts.wt. at least one resin selected from the group consisting of a polyester resin, an acrylic resin, an acrylic modified polyester resin, a polyurethane resin, a polyether resin, an epoxy resin and an antistatic resin with 0.005-12 pts.wt. at least one antioxidant selected from the group consisting of a phenolic compound, a phosphorus-based compound and a thioether compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recycled film obtained by using a polyester containing a recycled material, and more specifically, a polyester film containing a recycled material is used to form a film with little coloring, and an electronic material or a graphic material. , A plate making film, an OHP film, a magnetic card (for example, a telephone card, a prepaid card), a magnetic tape (for example, an audio tape, a video tape), a magnetic disk (for example, a floppy disk), and the like.

[0002]

2. Description of the Related Art Polyester films, particularly polyester films such as polyethylene terephthalate film and polyethylene naphthalate film, are generally used for magnetic recording materials such as magnetic cards, magnetic tapes and magnetic disks, and also for packaging materials, photographic materials and graphic materials. Widely used for industrial materials.

Such a polyester film is poor in slipperiness, so that it is difficult to wind it into a roll, and since it is charged by friction or the like, dust or dust is easily attached to the surface of the film.
Since it has poor adhesiveness, it has drawbacks such that various laminated layers are easily peeled off.

In order to improve such drawbacks, a laminated film in which a thin film such as a slippery coating film, an antistatic coating film or an easily adhesive coating film is provided on the surface of a polyester film is usually used.

On the other hand, when a polyester film is produced, a waste film which does not become a product (for example, a film end cut and removed from the product) is produced. In order to produce the film economically, a method of recovering such waste film and reusing it as a recycled material is adopted. However, when this method is used for a film having a coating film laminated as described above, the coating film component contained in the recycled material is thermally deteriorated during melt film formation (recovery is poor), so that the recycled material is included. The film obtained using polyester is markedly colored and lacks in practicality.

Particularly, when a compound having a nitrogen element, a sulfur element, a halogen element or an ether bond in the molecule is contained in the coating film component, these compounds are easily deteriorated by heat, so that the coloring becomes remarkable. For this reason, it is difficult to obtain a laminated film which is limited in the components contained in the coating film and which is excellent in slipperiness, antistatic property or adhesiveness and is excellent in recoverability.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems of the prior art and to provide a recycled film with less coloring.

[0008]

In order to achieve such an object, the present invention has the following constitution. At least one layer of a single-layer film or a multi-layer film is formed by melt film formation using polyester containing a recycled material, and the recycled material has 100% by weight of the following resin (A) on at least one side of the polyester film. A regenerated film obtained by collecting a laminated film provided with a thin film containing a composition in which 0.005 to 12 parts by weight of the following antioxidant (B) is blended for each part. .

However, the resin (A) is at least one resin selected from the group consisting of polyester resin, acrylic resin, acrylic modified polyester resin, polyurethane resin, polyether resin, epoxy resin and antistatic resin, and is oxidized. The inhibitor (B) is a phenolic compound (B-1) having a phenol group in which at least one of hydrogen elements is substituted with a tertiary butyl group in the molecule, an alkyl group having 6 to 40 carbon atoms in the molecule, or At least one selected from the group consisting of a phosphorus compound (B-2) having a phenyl group in which at least one of hydrogen elements is substituted with a tertiary butyl group and a thioether compound (B-3) having an ester group in the molecule. It is one type of antioxidant.

Hereinafter, the present invention will be described in detail.

[Recycled Film] The recycled film of the present invention comprises, on at least one side of a polyester film, 100 parts by weight of the resin (A) and 0.0% of the antioxidant (B).
A single layer formed by melt film formation using polyester containing a material (hereinafter referred to as "recycled material") obtained by collecting a laminated film provided with a thin film containing a composition blended in an amount of 05 to 12 parts by weight. A film, or a multi-layered film having two or more layers, at least one layer of which is made of a polyester containing a recycled material by melt-casting (hereinafter, the single-layered film and the multi-layered film are collectively referred to as "recycled film"). Sometimes).

As the above-mentioned multi-layer film, for example, a multi-layer film in which an intermediate layer of a three-layer film is a layer using polyester containing a recycled material and layers other than the intermediate layer are layers using polyester containing no recycled material are used. Can be mentioned.

Further, the recycled film has a thin film laminated on at least one surface thereof, which contains a composition in which 0.005 to 12 parts by weight of the antioxidant (B) is mixed with 100 parts by weight of the resin (A). May be

The recycled film of the present invention can be manufactured by a conventionally known method. For example, polyester containing the recycled material is melted by an extruder and cast from a single-layer die onto a cooling drum as a single-layer sheet, or at least one of a plurality of extruders is melted to form at least one of multilayer dies. It can be produced by casting a layer as a multilayer sheet on a cooling drum to obtain an unstretched film, and then stretching the unstretched film in the machine direction and subsequently in the cross direction.

It is also possible to re-stretch in the machine direction and / or the transverse direction. The stretching treatment is the second-order transition point (Tg) of the polyester constituting the single-layer sheet or the multi-layer sheet.
It is preferable to perform stretching at a temperature higher than −10 ° C. in each direction by 2 times or more, further preferably 3 times or more. At that time, the area stretching ratio is preferably 8 times or more, and more preferably 9 times or more. The upper limit of the area draw ratio depends on the use of the film, but is preferably up to 35 times, more preferably up to 30 times. The oriented crystallization can be completed by heat treatment after stretching.

[Recycled Material] The recycled material in the present invention is
Resin (A) 1 on at least one side of the polyester film
Antioxidant (B) is added in an amount of 0.005-1 with respect to 00 parts by weight.
It is a crushed product obtained by crushing a waste film produced from a film in which thin films containing a composition of 2 parts by weight are laminated, or a chip obtained by melt-extruding the crushed product. This recycled material can be used alone or mixed with other polyester chips for melt film formation. The proportion of the recycled material in the polyester used for producing the recycled film is preferably 30% by weight or more.

Further, when the mixing ratio (% by weight) of the antioxidant (B) in the coating film is in the range represented by the following formula (I), the hue of the regenerated film obtained is good. More preferable.

[0018]

[Formula 2] X ≧ 7 × 10 ⁻⁵ × Y + 0.003 (I) [In the formula (I), X is a blending ratio (wt%) of the antioxidant (B) in the coating film, and Y is a melt product). The ratio (% by weight) of the recycled material used in forming the film is shown. ]

[Other compounding agents] Single-layer recycled film,
Alternatively, in order to improve the slipperiness of the film, at least one of the outermost layers of the multi-layer reclaimed film uses organic or inorganic fine particles having an average particle diameter of about 0.01 to 20 μm as a lubricant, for example, 0 It can be contained at a blending ratio of 0.005 to 20% by weight. Specific examples of such fine particles include calcium carbonate, calcium oxide, amylnium oxide, titanium oxide, graphite, kaolin, silicon oxide, zinc oxide, carbon black, silicon carbide, tin oxide,
Preferable examples include acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles, silicone resin particles and the like.

In addition to the above-mentioned fine particles, the recycled film contains a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, a pigment,
Optical brightener, plasticizer, crosslinking agent, slip agent, ultraviolet absorber,
Other resins and the like can be added as needed.

[Polyester] In the present invention, the polyester used for making the recycled film or the polyester which is the main constituent of the polyester film is a linear polyester comprising a dicarboxylic acid component and a glycol component.

Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, 4,4'-diphenyldicarboxylic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid. Among them, terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferable.

Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol and 1,6-hexanediol. , Cyclohexanedimethanol, polyethylene glycol, polytetramethylene glycol and the like can be mentioned, and ethylene glycol is particularly preferable.

Of these polyesters, when polyethylene terephthalate or polyethylene-2,6-naphthalate is used, it has excellent mechanical properties such as a high Young's modulus and excellent thermal properties such as good heat resistance and dimensional stability. It is preferable because a film can be obtained.

The polyethylene terephthalate or polyethylene-2,6-naphthalate may be a polyester obtained by copolymerizing the above-mentioned dicarboxylic acid component or glycol component, and the polyester may be a trifunctional or higher polyvalent carboxylic acid component or polyol component. It may be a polyester copolymerized in a small amount in a substantially linear range (for example, 5 mol% or less).

The polyester can be produced by a conventional method, and it is preferable that the number average molecular weight is 10,000 or more because the recycled film has good mechanical properties.

[Resin (A)] In the present invention, the resin (A) as a component constituting the thin film is selected from polyester resin, acrylic resin, acrylic modified polyester resin, polyurethane resin, polyether resin, epoxy resin and antistatic resin. It is preferable to use at least one resin selected from the group consisting of polyester resin, acrylic resin, acrylic modified polyester resin, or antistatic resin as the resin (A) because a regenerated film having excellent mechanical properties can be obtained. . The number average molecular weight of the resin (A) is preferably within the range shown below. When the number average molecular weight is within this range, the adhesion between the thin film and the base film and the toughness of the thin film will be excellent.

[Polyester Resin] The polyester resin that can be used as the resin (A) is a linear polyester having a dicarboxylic acid component and a glycol component as constituent components, and has a number average molecular weight of 5,000 to 25,000. Those are preferable.

As the dicarboxylic acid component, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4 '
-Diphenyldicarboxylic acid, adipic acid, sebacic acid,
Preferable examples include dodecanedicarboxylic acid and hexahydroterephthalic acid.

As the glycol component, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diglycol Preferable examples include propylene glycol, triethylene glycol, bisphenol A-alkylene oxide adduct, hydrogenated bisphenol A-alkylene oxide adduct, 1,4-cyclohexanedimethanol, polyethylene glycol, and polytetramethylene glycol.

The polyester resin may be copolymerized with a component having a sulfonate group in order to impart hydrophilicity. It is preferable to impart hydrophilicity to the polyester resin because the dispersibility in the aqueous coating liquid becomes good when a thin film is laminated using the aqueous coating liquid. Such ingredients include
Examples thereof include 5-Na sulfoisophthalic acid and 5-K sulfoisophthalic acid.

The polyester resin may be obtained by copolymerizing a trifunctional or higher polyvalent carboxylic acid component and a polyol component in a small amount (for example, 5 mol% or less) within a range of forming a substantially linear polymer. Examples of the trifunctional or higher polyvalent carboxylic acid include trimellitic acid, pyromellitic acid, dimethylolpropionic acid, and the like, and examples of the polyol include glycerin, trimethylolpropane, and the like.

[Acrylic Resin] The acrylic resin is, for example, ethyl acrylate, methyl acrylate, acrylic acid, butyl acrylate, sodium acrylate, ammonium acrylate, ethyl methacrylate, methyl methacrylate, methacrylic acid, butyl methacrylate, Glycidyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, methacrylamide, N-methoxymethyl acrylamide, N-methylol acrylamide, etc., which are polymers or copolymers containing an acrylic monomer as a main component and have a number average. Those having a molecular weight of 5,000 to 250,000 are preferable.

The acrylic resin is a copolymer containing styrene, α-methylstyrene, sodium styrene sulfonate, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ether, sodium vinyl sulfonate, sodium methallylate, etc. as a copolymerization component. Good.

[Acrylic Modified Polyester Resin] The acrylic modified polyester resin is an acrylic acrylate, methyl acrylate, acrylic acid, butyl acrylate, sodium acrylate, ammonium acrylate, ethyl methacrylate, methacrylic acid in the presence of the polyester resin. Made by polymerizing acrylic monomers such as methyl acid, methacrylic acid, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, methacrylamide, N-methoxymethyl acrylamide, and N-methylol acrylamide. And a number average molecular weight of 5,000 to 250,000 is preferable.

Acrylic modified polyester resin is styrene, α-methylstyrene, sodium styrene sulfonate,
It may contain a monomer such as vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ether, sodium vinyl sulfonate, sodium methallylate as a copolymerization component.

[Polyurethane Resin] The polyurethane resin is a polymer or copolymer obtained from a polyfunctional isocyanate and a compound having a polyhydroxy group, and preferably has a number average molecular weight of 5,000 to 25,000. As the polyurethane resin, for example, diisocyanate, polyether, polyester, glycol, diamine, dimethylolpropionate or the like can be used, and an emulsion or an aqueous solution is preferable.

[Epoxy resin] The epoxy resin is a polymer or copolymer obtained from a compound having an epoxy group, and preferably has a number average molecular weight of 150 to 30,000. Examples of the above compounds include bisphenol glycidyl ether, glycerin polyglycidyl ether, aminoglycidyl ether and the like.

[Polyether Resin] Examples of the polyether resin include polyethylene oxide, polypropylene oxide, and phenoxy resin, and those having a number average molecular weight of 800 to 400,000 are preferable.

[Antistatic Resin] The antistatic resin is a polymer having a quaternary amine salt cation in the molecule, a polymer having a sulfonate in the molecule or a polymer having a phosphate in the molecule. Is a polymer having Examples of such a polymer include sodium polystyrene sulfonate, sodium polyisoprene sulfonate, polyacrylic acid ester-based polymer having a phosphoric acid alkyl ester Na base in the molecule, quaternary polyalkylamine / alkyl sulfate group-substituted acrylamide / ethylene copolymer. Etc., and the number average molecular weight is 2,000 to 70,
000 is preferable.

[Other resin] To the resin (A) in the present invention, other resin such as vinyl resin (for example, vinyl chloride resin, vinyl acetate resin, polystyrene resin), water-soluble resin (for example, cellulose resin), etc. should be added. You can

[Antioxidant (B)] In the present invention, the antioxidant (B) constituting the thin film is a phenol compound (B-1), a phosphorus compound (B-2) or a thioether compound. It is at least one antioxidant selected from the group consisting of (B-3).

The amount of the antioxidant (B) blended is the resin (A).
0.005 to 12 parts by weight with respect to 100 parts by weight,
Particularly, 0.05 to 6 parts by weight is preferable. This amount is 0.00
If it is less than 5 parts by weight, the effect of preventing coloration is insufficient, and if it exceeds 12 parts by weight, the mechanical properties such as the toughness of the thin film deteriorate.

In the present invention, the antioxidant (B) is
Phenolic compound (B-1), phosphorus compound (B-
2) and at least one selected from the group consisting of thioether compounds (B-3) may be used, but it is preferable to use two or more kinds in combination because the effect of preventing coloration during production of a recycled film is improved. .

Particularly when a polyester resin, an acrylic resin or an antistatic resin is used as the resin (A), a phenol compound (B-) is used as the antioxidant (B).
It is preferable to use 1) alone or in combination of two or more containing the phenolic compound (B-1) because a regenerated film with less coloring can be obtained.

[Phenolic Compound (B-1)] The phenolic compound (B-1) is a phenolic compound having in its molecule a phenol group in which at least one hydrogen element is substituted with a tertiary butyl group. Further, a compound having a skeleton shown below is preferable.

[0047]

Embedded image

[Wherein R is C (CH ₃ ) ₃ , R ¹ is an alkylene group, a substituted alkylene group or an ether group-containing alkylene group, R ² is an alkyl group having 1 to 40 carbon atoms, and n is 1 or 2 Indicates an integer. ]

[0049]

[Chemical 4]

[However, R is C (CH ₃ ) ₃ , R ¹ , R ³
Is an alkylene group, a substituted alkylene group or an ether group-containing alkylene group, and n is an integer of 1 or 2. ]

Among such compounds, particularly, a phenolic compound having at least one tertiary butyl group at a position adjacent to a hydroxyl group and having a substituent having an ester bond has a good hue in the recycled film. Therefore, it is preferable.

Specific preferred examples of the phenolic compound (B-1) include the following compounds.

[0053]

Embedded image

[Wherein R represents C (CH ₃ ) ₃ ] ]

[0055]

[Chemical 6]

[Wherein R represents C (CH ₃ ) ₃ ] ]

[0057]

[Chemical 7]

[In addition, R represents C (CH ₃ ) ₃ . ]

[Phosphorus Compound (B-2)] The phosphorus compound (B-2) is an alkyl group having 6 to 40 carbon atoms in the molecule, or at least one of hydrogen elements is substituted with a tertiary butyl group. A phosphorus-based compound having a phenyl group
Particularly, a phosphorus compound having the structural formula of the following (Chemical formula 1) or the following (Chemical formula 2) is preferable because the hue of the reproduced film becomes good.

[0060]

Embedded image

[In the above formula, R ₁ , R ₂ and R ₃ represent an alkyl group having 6 to 40 carbon atoms or a phenyl group in which at least one of hydrogen elements is substituted with a tertiary butyl group. ]

[0062]

[Chemical 9]

[In the above formula, R ₁ and R ₂ have 6 to 4 carbon atoms.
0 represents a phenyl group in which at least one of an alkyl group or a hydrogen element is substituted with a tertiary butyl group. ] Examples of such compounds include the following compounds.

[0064]

[Chemical 10]

[0065]

[Chemical 11]

[Wherein R represents C (CH ₃ ) ₃ ] ]

[0067]

[Chemical 12]

[0068]

[Chemical 13]

[Wherein R represents C (CH ₃ ) ₃ ] ]

[Thioether compound (B-3)] The thioether compound (B-3) is a thioether compound having an ester group in the molecule, and for example, a compound having a skeleton shown below is preferable.

[0071]

Embedded image

[Wherein R ⁴ represents an alkyl group having 1 to 40 carbon atoms, and R ⁵ represents an alkylene group having 1 to 6 carbon atoms. ]

[0073]

[Chemical 15]

[Wherein R ⁴ is an alkyl group having 1 to 40 carbon atoms, R ⁵ and R ⁶ are alkylene groups having 1 to 6 carbon atoms, m is an integer of 1 to 4 and p is 0 to 3 Is an integer and m + p =
It is 4. ]

[0075]

Embedded image

[Wherein R represents C (CH ₃ ) ₃ , R ⁴ is an alkyl group having 1 to 40 carbon atoms, R ⁵ is an alkylene group having 1 to 6 carbon atoms, and n is an integer of 1 or 2] . ]

[0077]

[Chemical 17]

[Wherein R ⁶ and R ⁷ are alkyl groups having 1 to 3 carbon atoms, R is C (CH ₃ ) ₃ and n and m are integers of 1 or 2]. ] Examples of such compounds include the following compounds.

[0079]

Embedded image

[Wherein R represents C (CH ₃ ) ₃ ] ]

[0081]

[Chemical 19]

[0082]

Embedded image

[0083]

[Chemical 21]

[Wherein R represents C (CH ₃ ) ₃ ] ]

[Thin Film] In the present invention, a method of providing a thin film comprising a resin (A) and an antioxidant (B) on the film surface on at least one side of a polyester film or a recycled film is such that both components in the thin film are uniform. The method is not particularly limited as long as it is such that, for example, a method of applying an aqueous coating solution obtained by mixing an aqueous solution of an antioxidant (B) with an aqueous solution of a resin (A), or preliminarily applying to the resin (A) Antioxidant (B)
A method of coating with an aqueous coating solution dissolved or dispersed in water, a method of melt-kneading the resin (A) and the antioxidant (B) and then extruding and laminating on the surface of the film. It can be illustrated. Among these, the method of applying a coating film using an aqueous coating liquid is particularly preferable. This method will be described below as an example.

[Aqueous Coating Liquid] In the present invention, when a coating film is applied using an aqueous coating liquid containing the resin (A) and the antioxidant (B), the aqueous coating liquid may slip on the surface of the coating film. 0.5 to 40 weight% in the coating film, using organic or inorganic fine particles having an average particle size of about 0.002 to 3 μm as a lubricant in order to improve the property and the blocking resistance of the film. It can be added so that the compounding ratio becomes%.

Examples of such lubricants include calcium carbonate, calcium oxide, amylnium oxide, titanium oxide,
Inorganic fine particles such as graphite, kaolin, silicon oxide, zinc oxide, carbon black, silicon carbide, tin oxide, etc., such as polystyrene resin, acrylic resin, melamine resin, silicone resin, fluororesin, urea resin, benzoguanamine resin, polyamide resin, polyester resin Examples thereof include organic fine particles. These organic fine particles may be thermoplastic resin fine particles or resin fine particles having a crosslinked structure as long as they are contained in the form of solid fine particles in the coating film.

The aqueous coating liquid may further contain other components such as surfactants, low molecular weight antistatic agents, colorants, pigments, optical brighteners, plasticizers, cross-linking agents, and slip agents (slipping agents such as waxes). ), An ultraviolet absorber, etc. can be mix | blended.

The solid content concentration of the aqueous coating solution is 1 to 30% by weight.
Is preferable, and 2 to 20% by weight is particularly preferable. When the solid content concentration is within this range, the viscosity of the aqueous coating liquid becomes suitable for coating. The aqueous coating solution used in the present invention can be used in any form such as an aqueous solution, an aqueous dispersion, and an emulsion. Also,
The aqueous coating liquid may contain a small amount of organic solvent.

[Coating of coating film] In the present invention, at least one surface of the polyester film or the recycled film is coated with
When a coating film is applied by applying the aqueous coating solution, heating and drying, and stretching, as the application method of the aqueous coating solution, any known coating method can be applied, for example, a gravure coating method and a reverse roll coating method. Method, die coating method, kiss coating method, reverse kiss coating method, offset gravure coating method, Meyer bar coating method, roll brush method, spray coating method, air knife coating method, impregnation method, curtain coating method, etc., alone or in combination. be able to. The WET coating amount of the aqueous coating liquid is preferably 1 to ²⁰ g, and particularly preferably ^{2 to} 12 g per 1 m ² of the running film. When the coating amount is within this range, drying is easy and coating spots are less likely to occur, which is preferable.

The polyester film or the regenerated film to which the aqueous coating liquid is applied is, for example, an unstretched film obtained by heat-melting polyester or a polyester containing a regenerated material to form a film as it is; the unstretched film in the longitudinal direction (longitudinal direction) or Uniaxially stretched film stretched in one of the transverse direction (width direction); biaxially stretched film in which longitudinal direction or transverse direction uniaxially stretched film is sequentially stretched in transverse direction or longitudinal direction, or unstretched film in longitudinal direction And a biaxially stretched film which is simultaneously stretched in two transverse directions; and a biaxially stretched heat-treated film in which the biaxially stretched film is heat-set and / or heat-relaxed.

The thickness of the polyester film or recycled film is 10 to 1000 μm for the unstretched film.
m, 2 to 500 μm for uniaxially stretched film, 1 to 300 μm for biaxially stretched film and biaxially stretched heat-treated film.
m is preferred.

The aqueous coating solution is applied to a stretchable film of the polyester film or the recycled film, for example, a uniaxially stretched film, particularly a uniaxially stretched film in the longitudinal direction, and dried and stretched to obtain a strong adhesiveness of the coating film. It is preferable because it is possible to efficiently produce an antistatic film. For example, polyester or polyester containing recycled material is heat-melted, extruded into a sheet and cooled to obtain an unstretched film, and the unstretched film is longitudinally stretched to form a uniaxially stretched film, and then an aqueous coating solution is applied. Then, the film is stretched in the transverse direction while being dried, and if necessary, re-stretched in the longitudinal and transverse directions and then heat-treated to form a film having a coating film applied thereon.

The thickness of the applied coating film is 0.005 to 3 μm.
m, particularly 0.015 to 1 μm is preferable. If the thickness of the coating film is less than 0.005 μm, the effect of preventing coloration may be insufficient, and if it exceeds 1 μm, the coating film may be easily scraped, which is not preferable.

[0095]

EXAMPLES The present invention will be described in more detail with reference to examples. Each characteristic value was measured by the following method. The average molecular weight is the number average molecular weight.

1. Coloring degree of recycled film Crush the film without a thin film and use an extruder to
Melted at ℃ and made into chips. Next, the obtained chip was used to perform melt film formation to prepare a blank film. The coloring degree of this film was set as a blank. On the other hand, the sample film provided with the thin film was crushed and melted at about 300 ° C. by an extruder to be made into chips. Next, the obtained chip was used to perform melt film formation to prepare a recycled film. The coloring degree of this film was evaluated according to the following criteria.

Rank A: Coloring degree is similar to blank film Rank B: Film is slightly colored Rank C: Film is highly colored and lacks practicality

[Example 1] Polyethylene terephthalate having an intrinsic viscosity of 0.64 was melted and cast on a cooling drum, and then stretched 3.5 times in the machine direction at 108 ° C to obtain a uniaxially stretched film. On both sides of this uniaxially stretched film,
Copolymerized polyester (A-1; average molecular weight 20,000) in which the acid component is terephthalic acid and isophthalic acid, and the glycol component is ethylene glycol, diethylene glycol, neopentyl glycol and polyethylene glycol.
0: Polyester resin) 3% by weight, copolymer obtained by polymerizing methyl methacrylate, ethyl acrylate and ammonium acrylate (A-2; average molecular weight 45.0)
00; acrylic resin) 2% by weight, ethylene, ethyl acrylate and [CH ₂ ═CHCOO (CH ₂ ) ₃ N ⁺ (C
_{H 3) 3] [OSO3CH 3} -] copolymer obtained by polymerizing (A-3; average molecular weight: 8,500; antistatic resin) 87 wt%, the phenol represented by formula (I-1) 0.3% by weight of compound, 0.4% by weight of phosphite compound represented by (formula II-3), 0.3% by weight of thioether compound represented by (formula III-1) and 7% by weight of polyoxyethylene nonylphenyl ether 9% of the composition consisting of
A wt% aqueous coating solution was applied with a gravure coater. Then, the coated film was dried at 98 ° C, stretched at 105 ° C in the transverse direction by 3.6 times, and heat-treated at 230 ° C to form a laminated film having a thickness of 153 µm and a light transmittance of 88%. It was The coating thickness of this film was 0.44 μm. This laminated film is crushed and then crushed by an extruder to about 300
Melted at ℃ and made into chips. Next, the obtained chip was used for melt film formation to prepare a recycled film having a thickness of 155 μm. Table 1 shows the evaluation results of the coloring degree of this film.

[Examples 2 to 6] Laminated films were obtained in the same manner as in Example 1 except that the composition of the coating liquid and the coating thickness were changed as shown in Table 1. Table 1 shows the evaluation results of the coloring degree of the recycled film prepared from this laminated film in the same manner as in Example 1.

[Comparative Examples 1 to 11] Laminated films were obtained in the same manner as in Example 1 except that the composition of the coating liquid and the coating thickness were changed as shown in Table 2. Table 2 shows the evaluation results of the coloring degree of the recycled film produced from this laminated film in the same manner as in Example 1.

[Examples 7 to 8] Polyethylene terephthalate containing 9% by weight of titanium oxide and having an intrinsic viscosity of 0.65 was used for the base film, and the composition of the coating liquid and the coating thickness were changed as shown in Table 1. A laminated film having a light transmittance of 1% was obtained in the same manner as in Example 1 except for the above. Table 1 shows the evaluation results of the coloring degree of the recycled film prepared from this laminated film in the same manner as in Example 1.

[Examples 9 to 17] Laminated films were obtained in the same manner as in Example 1 except that the composition of the coating liquid and the coating thickness were changed as shown in Table 1. Table 1 shows the evaluation results of the coloring degree of the recycled film prepared from this laminated film in the same manner as in Example 1.

[Embodiment 18] Thickness 153 obtained in Embodiment 1
50% by weight of chips obtained by pulverizing a laminated film having a thickness of .mu.m and melt-extruding at 300.degree.
62 polyethylene terephthalate chip 50
A laminated film (recycled film) coated with a coating film was obtained in the same manner as in Example 1 except that the mixture was mixed with 1% by weight and dried and then fed to the extruder. The degree of coloring of this recycled film was A.

[Comparative Example 12] A chip 91 made of polyethylene terephthalate having an intrinsic viscosity of 0.61 and 9% by weight of a chip obtained by crushing the laminated film obtained in Comparative Example 1 and melt-extruding it at 300 ° C in an extruder. A laminated film (recycled film) coated with a coating film was obtained in the same manner as in Example 18 except that the mixture was mixed with 10% by weight and dried and then fed to the extruder. The coloring degree of this recycled film was C.

[Comparative Example 13] 69% by weight of a chip obtained by crushing the laminated film obtained in Comparative Example 2 and melt-extruding it at 300 ° C. with an extruder, and a chip 31 made of polyethylene terephthalate having an intrinsic viscosity of 0.64. A laminated film having a coating film applied thereon (recycled film) was obtained in the same manner as in Example 18 except that 100% by weight of the mixture was mixed and dried and then supplied to the extruder. The coloring degree of this recycled film was C.

Example 19 Thickness 153 obtained in Example 1
Chips (P1) made of polyester (E1) obtained by crushing a laminated film of μm and melt-extruding at 300 ° C. in an extruder, and chips (P2) made of polyethylene terephthalate (E2) having an intrinsic viscosity of 0.66. And after drying,
It is fed into separate extruders and the molten polymer is made up of three layers
The film was introduced into a 3-layer film forming die so as to have a ratio of 2 / E1 / E2 and extruded and cast on a cooling drum to obtain a 3-layer unstretched film. Then, this unstretched film is heated to 108 ° C.
Longitudinally stretched 3.5 times in the machine direction, further stretched at 105 ° C in the transverse direction 3.6 times, and heat treated at 230 ° C to obtain E2 / E1 / E.
A 3-layer biaxially stretched film having a thickness of 2 layers of 25 μm / 127 μm / 25 μm was prepared. The degree of coloring of the obtained three-layer biaxially stretched film (recycled film) was A.

[0107]

[Table 1]

[0108]

[Table 2]

The components constituting the coating liquid composition shown in Tables 1 and 2
The symbol indicates the following compound or polymer. [A-1]: the acid component is terephthalic acid and isophthalic acid,
The glycol component is ethylene glycol, diethylene glycol
Cole, neopentyl glycol and polyethylene glycol
Copolyester made of coal (polyester resin
Fat) [A-2]: methyl methacrylate, ethyl acrylate and
And a copolymer obtained by polymerizing ammonium acrylate
(Acrylic resin) [A-3]: ethylene, ethyl acrylate and [CH₂
= CHCOO (CH₂) ₃N⁺(CH₃)₃] [OSO
3CH₃ ^-] The copolymer obtained by polymerizing
Resin) [I-1]: Phenolic compound represented by the above (formula I-1)
Product [I-2]: Phenolic compound represented by the above (formula I-2)
Product [I-3]: Phenolic compound represented by the above (formula I-3)
Product [I-4]: compound represented by the following (formula I-4) [I-5]: compound represented by the following (formula I-5) [I-6]: represented by the following (formula I-6) Compound [II-2]: phosphite formation shown in the above (formula II-2)
Compound [II-3]: phosphite formation shown in the above (formula II-3)
Compound [II-5]: compound represented by the following (formula II-5) [II-6]: compound represented by the following (formula II-6) [II-7]: represented by the following (formula II-7) Compound shown [III-1]: Thioetherification shown in the above (formula III-1)
Compound [III-2]: Thioetherification shown in the above (formula III-2)
Compound [III-5]: compound represented by the following (formula III-5) [III-6]: compound represented by the following (formula III-6) [III-7]: represented by the following (formula III-7) Shown compound [C-1]: polyoxyethylene nonylphenyl ether
Le

[0110]

[Chemical formula 22]

[0111]

[Chemical formula 23]

[0112]

[Chemical formula 24]

[0113]

[Chemical 25]

[0114]

[Chemical formula 26]

[0115]

[Chemical 27]

[0116]

[Chemical 28]

[0117]

[Chemical 29]

[0118]

Embedded image

[0119]

In the present invention, since the specific resin and the antioxidant having the specific structure are used as the coating film components, the coloring is suppressed even if the laminated film coated with the coating film is recovered and used as the material for the recycled film. To be done. In particular, even if the polymer is melted at a temperature of 250 ° C. or more to form a film, the coloring is suppressed, and a practical recycled film can be obtained.

The recycled film of the present invention has a small coloring degree,
It is useful for magnetic recording media, magnetic cards, packaging materials, photographic materials, graphic materials, film for plate making, OHP film and the like.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/36 KKA C08K 5/36 KKA 5/49 KKC 5/49 KKC C08L 33/00 LHT C08L 33/00 LHT 63/00 NJX 63/00 NJX 67/00 LNZ 67/00 LNZ 71/02 LQE 71/02 LQE 75/04 NFZ 75/04 NFZ 101/00 LSY 101/00 LSY C09K 15/08 C09K 15/08 15 / 12 15/12 15/32 15/32 C // B29K 33:00 63:00 67:00 71:00 75:00 101: 00 105: 26 B29L 9:00

Claims (6)

[Claims] 1. A regenerated film produced by melt-casting at least one layer of a single-layer film or a multi-layer film by using a polyester containing a regenerated material, wherein the regenerated material is at least one surface of the polyester film having the following resin. (A) A material obtained by recovering a laminated film provided with a thin film containing a composition in which 0.005 to 12 parts by weight of the following antioxidant (B) is mixed with 100 parts by weight. Characterized recycled film. However, the resin (A) is at least one resin selected from the group consisting of polyester resin, acrylic resin, acrylic modified polyester resin, polyurethane resin, polyether resin, epoxy resin, and antistatic resin, and the antioxidant ( B) is a phenolic compound (B-) having in its molecule a phenol group in which at least one hydrogen element is substituted with a tertiary butyl group.
1), a phosphorus compound (B-2) having an alkyl group having 6 to 40 carbon atoms in the molecule or a phenyl group in which at least one of hydrogen elements is substituted with a tertiary butyl group, and an ester group in the molecule It is at least one antioxidant selected from the group consisting of thioether compounds (B-3). 2. A recycled film produced by melt-casting at least one layer of a single-layer film or a multilayer film using polyester containing recycled material,
The recycled film according to claim 1, wherein a thin film containing a composition in which 0.005 to 12 parts by weight of the antioxidant (B) is mixed with 100 parts by weight of the resin (A) is provided. 3. The phenolic compound (B-1) is a phenolic compound having at least one tertiary butyl group at a position adjacent to a hydroxyl group and having a substituent having an ester bond. Or the recycled film described in 2. 4. The phosphorus compound (B-2) is represented by the following (Chemical formula 1).
Alternatively, the regenerated film according to claim 1 or 2, which is a phosphorus-based compound having the following structural formula (Formula 2). Embedded image [In the above formula, R ₁ , R ₂ and R ₃ represent an alkyl group having 6 to 40 carbon atoms or a phenyl group in which at least one of hydrogen elements is substituted with a tertiary butyl group. ] [Chemical 2] [In the above formula, R ₁ and R ₂ represent an alkyl group having 6 to 40 carbon atoms or a phenyl group in which at least one of hydrogen elements is substituted with a tertiary butyl group. ] 5. The regenerated film according to claim 1, wherein at least one layer of the single-layer film or the multi-layer film is formed by melt film formation using polyester containing 30% by weight or more of the regenerated material. 6. The recycled film according to claim 1, wherein the mixing ratio (% by weight) of the antioxidant (B) in the thin film is in the range represented by the following formula (I). [Formula 1] X ≧ 7 × 10 ⁻⁵ × Y + 0.003 (I) [In the formula (I), X is the compounding ratio (wt%) of the antioxidant (B) in the thin film, and Y is the melt film-forming. The ratio (% by weight) of the recycled material used in the above is shown. ]