JP2897285B2 - Thermoplastic resin film laminate - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a thermoplastic resin film laminate having improved adhesion, and is particularly excellent for all hydrophilic polymers, hydrophobic polymers, inorganic substances and the like. While showing good adhesion,
The present invention relates to a thermoplastic resin film laminate having good antistatic properties.

[Prior art] As is well known, thermoplastic resin films such as polyester, polyamide, polypropylene, polycarbonate,
Polyetherimide, polyether sulfone, polyphenylene sulfide, polyetherester, etc., especially polyester film, especially polyethylene terephthalate film is excellent in mechanical strength, heat resistance, chemical resistance, transparency, dimensional stability, etc. It is widely used for magnetic tape base films, insulating tapes, photographic films, tracing films, food packaging films, and the like. However, these thermoplastic resin films usually have low adhesion to hydrophilic polymers and inorganic substances. Therefore, when laminating a magnetic material, a photosensitizer, a matting agent, etc. on these films, it is necessary to perform a treatment such as applying a corona discharge treatment to the film surface and further providing an anchor coat layer to enhance the adhesiveness. Become. Further, when used for packaging foods, the overall heat seal strength is low because of poor adhesion to the printing layer and the heat sheet layer.

By the way, as a method of improving the adhesiveness of the thermoplastic resin film surface, a corona discharge treatment method is most widely used, and in addition, an ultraviolet irradiation treatment method, a plasma discharge treatment method,
A flame treatment method, a physical treatment method such as a corona discharge treatment method under a nitrogen atmosphere, a chemical treatment method such as an alkali treatment method, a primer treatment method, and a treatment method in which the above methods are appropriately combined are known. . However, at the moment,
A thermoplastic resin film, particularly a polyester film, which exhibits excellent adhesion to all of hydrophilic and hydrophobic polymers and inorganic substances is not known. In addition, when the primer treatment is performed among the above-mentioned various treatments, there is a problem that the slipperiness of the film is reduced and workability such as winding property is deteriorated.

[Problems to be Solved by the Invention] The present invention has been made in view of the problems of the prior art as described above, and its object is to excel in all of hydrophilic polymers, hydrophobic polymers, and inorganic substances. An object of the present invention is to provide a thermoplastic resin film laminate that can exhibit adhesiveness and has good antistatic properties.

[Means for Solving the Problems] The configuration of the thermoplastic resin film laminate according to the present invention includes:
At least one surface of an unstretched or uniaxially stretched thermoplastic resin film is coated with a composition mainly composed of a polyamide having a tertiary amino group and / or a quaternary ammonium group, and further stretched. It has.

[Operation] The present invention is configured as described above. In short, the present invention mainly comprises a polyamide having a tertiary amino group and / or a quaternary ammonium group on at least one surface of an unstretched or uniaxially stretched thermoplastic resin film. By coating and further stretching the composition, it was found that the adhesion with hydrophilic polymers, hydrophobic polymers, inorganic substances, etc. was significantly improved, and that the film was excellent in slipperiness, and completed the present invention. .

The polyamide having a tertiary amino group according to the present invention can be obtained, for example, by using monomers represented by the following general formulas (I) to (V) as polymerization raw materials.

[In the above general formulas (I) to (V), R ₁ , R ₂ , and R ₃ are an alkylene group having 1 to 15 carbon atoms, and R ₄ and R ₅ are 1 carbon atom.
10 pieces of hydrocarbon residues, A, B are -NH _2, -COOH, -COOR ₉
(R ₉ represents the remaining amount of a hydrocarbon having 1 to 10 carbon atoms), and A and B may be the same or different;
R _6, R ₇ is a hydrocarbon residue having 1 to 10 carbon atoms, R ₆
And R ₇ may together form an aliphatic ring or a heterocyclic ring. R ₈ is a lower alkyl group having 1 to 3 carbon atoms or (R ₆ and R ₇ are the groups described above), and Y represents a γ-aminopropyl group. Specific examples of the monomer represented by the general formula (I) include N, N′-bis (aminomethyl ) Piperazine,
N, N'-bis (β-aminoethyl) piperazine, N, N'-
Bis (β-aminoethyl) piperazine, N, N′-bis (β-aminoethyl) methylpiperazine, N- (aminomethyl) -N ′-(β-aminoethyl) piperazine, N,
Diamines such as N'-bis (γ-aminopropyl) piperazine, N, N'-bis- (carboxymethyl) piperazine, N, N'-bis (carboxymethyl) methylpiperazine, N, N'-bis (carboxy Methyl) -2,6-dimethylpiperazine, N, N′-bis (β-carboxymethyl) piperazine, N, N′-bis (γ-carboxypropyl) piperazine, N, N ′-(β-carboxyethyl)- N'-
Dicarboxylic acids such as (carboxymethyl) piperazine or their lower alkyl esters, acid halides and N- (aminomethyl) -N '-(carboxymethyl)
Piperazine, N- (aminomethyl) -N '-(β-carboxymethyl) piperazine, N- (β-aminoethyl)
-N '-(β-carboxyethyl) piperazine, N-
(Aminomethyl) -N '-(carboxymethyl) -2-
Ω-amino acids such as methylpiperazine and the like.

Specific monomers represented by the above general formula (II) include, for example, N- (β-aminoethyl) piperazine, N-
(Γ-aminopropyl) piperazine, N- (ω-aminohexyl) piperazine, N- (δ-aminocyclohexyl) piperazine, N- (β-aminoethyl) -3-methylpiperazine, N- (β-aminoethyl) -2,5-dimethylpiperazine, N- (β-aminopropyl) -3-methylpiperazine, N- (γ-aminopropyl) -2,5-
Diamines such as dimethylpiperazine, N-carboxymethylpiperazine, N- (β-carboxyethyl) piperazine, N- (γ-carboxypropyl) piperazine;
N- (ω-carboxyhexyl) piperazine, N- (δ
Ω-amino acids such as -carboxyhexyl) piperazine, N- (β-carboxyethyl) -3-methylpiperazine, N- (β-carboxyethyl) -2,5-dimethylpiperazine, or lower alkyl esters thereof. No.

Specific monomers represented by the general formula (III) include, for example, N, N-di (β-aminoethyl) ethylamine, N, N-di (γ-aminopropyl) methylamine, N, N
-Di (β-aminoethyl) methylamine, N, N′-di (γ-aminopropyl) ethylamine, N, N-di (γ-
Aminopropyl) isopropylamine, N, N-di (γ-
Aminopropyl) cyclohexylamine, N, N-di (δ
-Amino-n-butyl) phenylamine, N-methyl-
Diamines such as N- (β-aminoethyl) -1,3-propanediamine, N, N-di (carboxymethyl) methylamine, N, N-di (β-carboxyethyl) methylamine, N, N- Di (β-carboxyethyl) methylamine,
Dicarboxylic acids such as N, N-di (β-carboxyethyl) isopropylamine and N-carboxymethyl-N- (β-carboxyethyl) methylamine, or lower alkyl ethyl esters and acid halides thereof, and N- ( Aminomethyl) -N (carboxymethyl) methylamine, N
-(Β-aminoethyl) -N- (β-carboxyethyl) methylamine, N- (aminomethyl) -N- (β-
(Carboxyethyl) isopropylamine, N- (γ-aminopropyl) -N- (γ-carboxypropyl) isopropylamine, N- (γ-aminopropyl) -N-
And ω-amine acids such as (β-carboxyethyl) methylamine.

Specific monomers represented by the general formula (IV) include, for example, N, N′-dimethyl-N, N′-di- (γ-aminopropyl) ethylenediamine, N, N′-dimethyl-N, N ′
-Di- (γ-aminopropyl) tetramethylenediamine, N, N′-diisobutyl-N, N′-di- (γ-aminopropyl) hexamethylenediamine, N, N′-dicyclohexyl-N, N′-di -(Γ-aminopropyl) hexamethylenediamine, N, N′-di- (γ-aminopropyl)
Diamines such as -2,2,4-trimethylhexamethylenediamine, N, N'-dimethyl-N, N'-di (carboxymethyl) ethylenediamine, N, N'-dimethyl-N, N'-di-
(Γ-carboxyethyl) ethylenediamine, N, N′-
Dicarboxylic acids such as dimethyl-N, N'-di- (γ-carboxypropyl) hexamethylenediamine, or lower alkyl esters, acid halides, and N,
N′-dimethyl-N- (aminomethyl) -N ′-(carboxymethyl) -ethylenediamine, N, N′-dimethyl-N- (β-aminoethyl) -N ′-(β-carboxyethyl) ethylenediamine, N , N'-dimethyl-N-
Ω-amino acids such as (aminomethyl) -N '-(carboxyethyl) hexamethyleneamine.

Specific monomers represented by the general formula (V) include, for example, 6-methyl-6- (N, N-dimethylaminomethyl) -4,8-dioxaundecanediamine, 6-methyl-6- (N, N-diethylaminomethyl) -4,8-dioxaundecanediamine, 6-ethyl-6- (N, N-dimethylaminomethyl) -4,8-dioxaundecanediamine, 6,6-bis (N , N-dimethylaminomethyl) -4,8-
And diamines such as dioxaundecanediamine.

Polycondensation is performed by using one or more of these monomers having a basic nitrogen to form a polyamide. That is, a monomer capable of forming a polyamide by homopolymerization, such as an ω-amino acid or an alkyl ester thereof, can be used alone.

On the other hand, if the monomer is a dicarboxylic acid or an alkyl ester thereof, an acid halide or the like, a diamine is used, and if the monomer is a diamine, a polyamide is formed by condensation polymerization with a dicarboxylic acid or a derivative thereof. .

Further, as a raw material for polymerization of polyamide used in the present invention,
In addition to the monomers represented by the above general formulas (I) to (V), aliphatic and / or aromatic dicarboxylic acids, diamines, ω-amino acids, lactams and the like used in the polymerization of ordinary polyamides are used in combination. You may.

Examples of dicarboxylic acids that can be used in combination include succinic acid,
Adipic acid, glutaric acid, azelaic acid, sebacic acid,
Examples thereof include aliphatic and / or aromatic dicarboxylic acids such as decanedicarboxylic acid, terephthalic acid, isophthalic acid, and cyclohexanedicarboxylic acid, lower alkyl esters thereof, and acid halides. Examples of the diamine include straight-chain saturated aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, meta-xylylenediamine, para-xylylenediamine and the like. And alicyclic diamines such as cyclohexanebismethylamine. Examples of ω-amino acids include aminocaproic acid, aminoheptanoic acid, aminocaprylic acid, aminocapric acid, aminolauric acid and the like. Lactams include, for example, ε-caprolactam, α-methyl-ε
-Caprolactam, ε-methyl-ε-caprolactam,
Cycloheptanone isoxime, cyclooctanone isoxime and the like can be used.

The polymerization of polyamide using these monomers can be carried out according to a conventionally known method for producing polyamide.
The basic nitrogen-containing monomer component accounts for 10 to 100 mol%, preferably 20 to 50 mol%, of all polyamide components.

The polyamide used in the present invention may be a polyamide containing nitrogen obtained by quaternizing basic nitrogen and ammonium chloride, and may be used together with or instead of a polyamide having a tertiary amino group.

As a method for obtaining a polyamide having a quaternary ammonium group, for example, a method in which a polyamide having a basic nitrogen atom and a quaternizing agent are dissolved and mixed in an appropriate solvent and reacted, or both are melted at an appropriate temperature. There is a method of mixing and reacting, or a method of reacting by adding a polyamide having a basic nitrogen atom to the gaseous phase of the quaternizing agent. A polyamide having a basic nitrogen atom and a quaternizing agent may be mixed and reacted simultaneously with a photopolymerizable monomer having an unsaturated bond, a photosensitizer, a thermal polymerization inhibitor and the like.

As the quaternizing agent, known compounds such as a protonic acid, a metal salt, and an alkyl halogen compound can be used. Protic acids include inorganic acids such as hydrochloric acid and sulfuric acid, formic acid, acetic acid,
There are organic acids such as chloroacetic acid, maleic acid, fumaric acid, adipic acid and acrylic acid. In particular, those having a polymerizable unsaturated bond such as acrylic acid, maleic acid and cinnamic acid in the molecule.
The grading agent acts as a cross-linking agent by photopolymerization and exhibits a sufficient insolubilizing effect. The addition amount of the quaternizing agent is appropriately selected in consideration of the amount of the basic nitrogen present in the polyamide, the solubility in water, and the like.

The polyamide polymer is, for example, dissolved in a solvent and applied to a thermoplastic resin film. As the solvent used at this time, for example, water, methanol, ethanol, carbon tetrachloride,
Toluene, xylene and the like are used, but are not limited thereto. It is also recommended to include another solvent, for example, a fluorine-based or silicon-based compound, for the purpose of improving coating properties or improving drying after coating.

Examples of the thermoplastic resin film (base film) on which the above composition is laminated include a polyester film, a polyamide film, a polycarbonate film, a polyphenylene sulfide film, a polyetherimide film, a polyethersulfone film, a cellulose film, a PVA film, and an acrylic film. -Based films, vinyl chloride-based films, etc., and the most suitable one is selected and used in each case according to the application and required characteristics of the film laminate, but the most common are polyester films, polyamide films, polycarbonate films, and cellulose-based films. Film.

The base film is usually obtained by melting and extruding a thermoplastic resin as a raw material, or by dissolving the resin in a solvent and casting. Such an unstretched film is uniaxially stretched if necessary, and then the above composition is applied (coated) to the surface thereof by a method described later. In consideration of imparting moisture and the durability of the obtained film, a method of applying the composition to an unstretched or uniaxially stretched base film and further stretching the composition was adopted. That is, the base film that has been biaxially stretched has a wide film width, and it is somewhat difficult to apply the composition uniformly because it is necessary to increase the running speed of the film in order to apply the composition thinly on the base film. Become.

The coating solution is usually applied to the surface of the base film in an amount of 0.003 to 5
g / m ^2, and preferably coated at a rate of 0.01 to 3 g / m ^2. When the coating amount is less than 0.003 g / m ² , the adhesiveness to the resin is poor, and when it exceeds 5 g / m ² , the obtained film is poor in slipperiness and blocking resistance.

In addition, as a method for forming the polyamide-based composition on the base film, a method of preparing the above-mentioned coating solution and coating the same on the base film can be adopted.

Before laminating the composition by a method such as coating,
Alternatively, after lamination, it is also effective to subject the surface of the base film to a corona discharge treatment, an ultraviolet irradiation treatment, a plasma treatment, or an electron beam treatment in an air or nitrogen atmosphere. By performing these treatments, the adhesion between the base film and the resin composition layer and the adhesion between the obtained film and another resin can be further improved.

Since the thermoplastic resin laminated film of the present invention is constituted by laminating a composition containing a polyamide resin containing a tertiary amino group and / or a quaternary ammonium group on a thermoplastic resin film, a hydrophilic polymer, a hydrophobic polymer It exhibits good adhesion to both the conductive polymer and the inorganic substance, and has extremely good antistatic properties. For this reason, this thermoplastic resin laminated film is used for magnetic tapes such as audio, video and computers, recording media for microfilms, magnetic cards, leader tapes, floppy disks, foods, chemicals, fertilizers, vapor-deposited packaging, packing materials, etc. Packaging applications, as well as plate making, tracing, membrane switches,
General industrial applications such as stamping, adhesive tape, labels, namers, OHP sheets, laminated cards, nameplates, mirrors, printing materials, printer ribbons, solar controls, pasting bases, light-shielding films, photographic paper, PPC films, white boards, stickers, etc. Furthermore, it is suitably used for agricultural uses such as agricultural houses and decorative uses such as gold and silver threads.

If like the above applications, if necessary in the composition to be laminated, a coloring agent, an antistatic agent, a crosslinking agent, a blocking agent, a lubricant such as inorganic or organic particles, a conductive agent, other polymers, An ultraviolet absorber, a deterioration inhibitor, and other additives may be added to such an extent that the effects of the present invention are not impaired. The additives include water-soluble, organic solvent-soluble or oil-soluble dyes and pigments, and insoluble dyes and pigments.

As a crosslinking agent, an alkoxy group, an isocyanate group,
Compounds containing two or more functional groups capable of reacting with active hydrogen, such as an epoxy group, an azinyl group (meth) acryloyl group, and an alkoxyalkyl group, are included.

Examples of the antiblocking agent include higher fatty acids and their salts, esters, amides, amines, mineral oils, silicones, fluorine compounds and the like.

Examples of lubricants such as inorganic or organic particles include silica, calcium carbonate, kaolin, barium sulfate, titanium, talc, benzoguanamine, polyolefin, melamine, polyacrylate, polyamide, and polyester. , Polycarbonate, etc., which may be surface-treated. The particle size may be arbitrarily selected according to the application.

Examples of the ultraviolet absorber include benzophenone-based, salicylate-based, and triazole-based.

Examples of the deterioration inhibitor include various compounds such as phenol-based, epoxy-based, sulfur-containing, phosphorus-containing, nitrogen-containing, metal-containing, and conjugated double bond-containing compounds.

Additives other than the above include anti-fogging agents, flame retardants and the like.

The film laminate according to the present invention comprises a hydrophilic polymer, a hydrophobic polymer, and an inorganic material obtained by laminating a composition containing a polyamide having a tertiary amino group and / or a quaternary ammonium group as a main component on a base film as described above. It exhibits excellent adhesiveness to any of these, and can be widely used in various fields by utilizing its characteristics.

[Examples] Next, the present invention will be specifically described with reference to examples. In the examples, "parts" indicates parts by weight.

Example 1 A polymer obtained from 40 parts of N, N'-bis (γ-aminopropyl) piperazine adipate and 60 parts of ε-caprolactam was dissolved in methanol to a concentration of 10% by weight to prepare a coating liquid.

After the polyethylene terephthalate is melt-extruded at 280 to 300 ° C., it is cooled with a cooling roll at 15 ° C. to obtain an unstretched film having a thickness of 1000 μm, and the unstretched film is passed through a pair of rolls at 85 ° C. having different peripheral speeds. It was stretched 3.3 times in the direction. The coating liquid was applied to the surface of the film by an air knife method, and dried with hot air at 70 ° C. to form a resin composition layer. This film is tentered at 98 ° C in a transverse direction with a tenter.
Stretch twice and heat-set at 200-210 ° C, thickness 100μm
(Resin composition layer 0.15 μm) to obtain a biaxially stretched coated polyester film.

A 10% aqueous solution of polyvinyl alcohol and a 10% solution of polyvinyl chloride in DMF were prepared, each solution was colored with a red dye, and both were coated on the resin composition layer side of the two thermoplastic resin laminated films described above. Printed separately to give a layer of 2 g / m ² .

A cut was made in the obtained printed layer at a 1 mm interval with a cutter knife in the form of a base mesh to form 100 squares. After uniformly applying a cellophane tape (L-pack, manufactured by Nichiban) to each printed surface of the thermoplastic resin laminated film, the tape was quickly peeled off so that the peeling angle became 180 degrees, and the squares remained. The number was counted and the adhesiveness was evaluated. At this time, the applied voltage was 500 V with a Takeda Riken Co.
The electrical resistance of the film surface was measured under the conditions of a room temperature of 20 ° C. and a humidity of 65%, and the antistatic property was evaluated.

Example 2 Except that the composition of the coating liquid was changed to a polyamide resin obtained from 6-methyl-6 (N, N'-diethylaminomethyl) -4,8-dioxaundecanediamine and adipic acid,
A coated polyester film was obtained in the same manner as in Example 1. The adhesiveness and antistatic property of the obtained polyester film were evaluated in the same manner as in Example 1.

Comparative Example 1 An uncoated polyester film was used as it was, and the adhesiveness and antistatic property of this film were evaluated in the same manner as in Example 1.

Comparative Example 2 A coating polyester was obtained in the same manner as in Example 1, except that the composition of the coating solution was changed to N-methoxymethylated polyhexamethylene adipamide (methoxy group, 6.5% by weight). The obtained polyester film was evaluated for adhesiveness and antistatic property in the same manner as in Example 1.

Comparative Example 3 Polyethylene terephthalate was melt-extruded at 280 to 300 ° C., and then cooled with a cooling roll at 15 ° C. to obtain an unstretched film having a thickness of 1000 μm. The film was stretched 3.3 times in the longitudinal direction through the gap. This film is tentered at 98 ° C in a transverse direction with a tenter.
The film was stretched twice and heat-set at 200 to 210 ° C. to obtain a biaxially stretched polyester film having a thickness of 100 μm.

The coating liquid shown in Example 1 was applied to the surface of this film by an air knife method, and dried with hot air at 70 ° C. to form a resin composition layer (resin composition layer 0.50 μm). The adhesiveness and antistatic property of the obtained polyester film were evaluated in the same manner as in Example 1.

These results are shown in Table 1 collectively.
It can be clearly seen that the sample of No. 2 has excellent adhesiveness and antistatic properties as compared with Comparative Examples 1 to 3.

Example 3 Poly-ε-caprolactam containing 3% by weight of polymethaxylylene adipamide was melt-extruded at 260 ° C and cooled with a cooling roll at 20 ° C to obtain an unstretched film having a thickness of 250 µm. The unstretched film was passed through a pair of rolls at 60 ° C. having different peripheral speeds and stretched 3.3 times in the machine direction.

The coating solution shown in Example 1 was applied to the surface of this film by an air knife method, dried at 50 ° C. to form a resin composition layer, and then stretched 3.3 times in the transverse direction to 120 ° C. with a tenter.
It was heat-set at 0 ° C. to obtain a biaxially stretched coated polyamide film having a thickness of 25 μm (resin composition layer 0.10 μm).

The antistatic property of the film was 1.0 × 10 ¹⁰ (Ω · cm), and the number of remaining cells in the adhesion with a printing ink mainly composed of a nitrocellulose binder was 100 in a cross-cut method.

[Effects of the Invention] The present invention is configured as described above, and has excellent adhesion to all of hydrophilic polymers, hydrophobic polymers, metals and inorganic substances, and also has excellent antistatic properties. It has become possible to provide a laminate.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-78239 (JP, A) JP-A-57-126817 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B32B 1/00-35/00 C08J 7/04 B29C 55/00-55/30

Claims (1)

(57) [Claims] An unstretched or uniaxially stretched thermoplastic resin film coated on at least one surface with a composition mainly composed of a polyamide having a tertiary amino group and / or a quaternary ammonium group, and further stretched. A thermoplastic resin film laminate, characterized in that: