JPS63288747A - Thermoplastic resin laminated film - Google Patents

Abstract

PURPOSE:To attempt to improve adhesive property of a thermoplastic resin film with hydrophilic polymers, hydrophobic polymers and inorganic substances, by laminating a phosphorus compound-modified copolymer on the surface of a thermoplastic resin film. CONSTITUTION:A copolymer is laminated on a thermoplastic resin film. The above described copolymer has a phosphorus compound represented by the following formula in its backbone. It is preferable that the content of the phosphorus compound is in the range of 100-5,000ppm of phosphorus atomic wt. in the copolymer. As the copolymer laminated on the thermoplastic resin, phosphorus compound-modified copolymer polyesters are preferable. The copolymer polyesters can be obtained by polycondensating a dicarboxylic acid and a glycol. Copolymer polyester-polyurethanes obtained by chain-extention of this phosphorus compound-modified copolymer polyester with a polyisocyanate can be also sued. In the formula, R1 is a monovalent ester-formable functional group, R2 and R3 are halogen atoms, 1-10C hydrocarbon groups or a monovalent ester- formable functional group, A is a di- or tri-valent organic residue, n1 is 1 or 2 and n2 and n3 are intergers of 0-4 respectively.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a thermoplastic resin laminated film with excellent adhesiveness,
In particular, the present invention relates to a thermoplastic resin laminate film that has good adhesion to hydrophilic polymers, hydrophobic polymers, and inorganic materials.

(Prior art) Thermoplastic resin films such as polyester, polyamide, and polypropylene (especially polyester films such as polyethylene terephthalate) have 1) excellent mechanical strength, heat resistance, chemical resistance, transparency, 2) dimensional stability, and magnetic properties. Base film for tape.

It is widely used in applications such as insulating tape, photographic film, tracing film, and food packaging film. However, these thermoplastic resin films usually lack adhesion to hydrophilic polymers, hydrophobic polymers, and inorganic materials.

Therefore, when a magnetic material, a photosensitive agent, a matting agent, etc. are to be laminated on this film, it is necessary to apply a corona discharge treatment to the film surface and then provide an anchor coat layer.

In addition, this film can be used as a food packaging film,
Even if a printed layer or a heat seal layer is provided, the adhesion between these layers and the thermoplastic resin film is weak.

Heat seal strength may decrease.

In order to improve the adhesion of thermoplastic resin films, in addition to corona discharge treatment, the film is subjected to ultraviolet irradiation treatment,
Methods of performing physical treatments such as plasma discharge treatment, flame treatment, and corona discharge treatment under a nitrogen atmosphere have been proposed. Chemical treatment methods such as alkali treatment and primer treatment, as well as the combination of these and physical treatment methods, are also used.

but.

No matter which method is used, the adhesion of the thermoplastic resin film is not sufficiently improved. In particular, the adhesion between the hydrophilic polymer or hydrophobic polymer and the film is insufficient.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and its object is to provide a wood-philic polymer.

The object of the present invention is to provide a thermoplastic resin laminate film that has good adhesion to both hydrophobic polymers and inorganic substances.

(Means for Solving the Problems) The present invention provides a hydrophilic polymer,
Adhesion between a hydrophobic polymer or an inorganic substance and a thermoplastic resin film can be significantly improved.

It was completed based on the inventor's knowledge.

The thermoplastic resin laminated film of the present invention is a thermoplastic resin laminated film in which a copolymer is laminated on a thermoplastic resin film, and the copolymer has a phosphorus compound represented by the 9th formula in its skeleton, This achieves the above objective.

+R1 is a monovalent ester-forming functional group here.

R2 and R3 are the same or different and are a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

or a monovalent ester-forming functional group, A is divalent or trivalent
The organic residue +nl is 1 or 2. and R2 and n
, are each integers from O to 4.

Examples of phosphorus compounds represented by the above formula include compounds having two, for example, primary structures (a) to (2), (α) and (β).

(Left below) The phosphorus compound has a phosphorus atomic weight of 10 in the copolymer.
0 to 50,000 ppm, preferably 500 to 11,000
The content is preferably within the range of 0pp. If it is less than 1100 pp, the adhesiveness of the copolymer will not be developed, and therefore the adhesiveness of the obtained thermoplastic resin laminate film will be insufficient. If it exceeds 50,000 ppm, not only the physical properties of the obtained thermoplastic resin laminate film will deteriorate, but also the workability in producing the modified copolymer will deteriorate.

The copolymer to be laminated to the thermoplastic resin of the present invention includes:
A copolymerized polyester modified with the above-mentioned phosphorus compound is preferably used. The copolymerized polyester may also be a copolyester polyurethane obtained by chain-extending a phosphorus compound-modified copolyester obtained by polycondensing dicarboxylic acid and glycol with a polyisocyanate. In order to make these copolymerized polyesters and copolymerized polyester polyurethanes into radiation-curable resins, an acrylic double bond-containing compound may be introduced into the skeleton of the copolymer. The acrylic double bond-containing compound may be introduced either during the synthesis of the copolyester or during the urethanization of this polyester.

The dicarboxylic acid is an aromatic dicarboxylic acid.

Both aliphatic dicarboxylic acids and alicyclic dicarboxylic acids can be used. For aromatic dicarboxylic acids.

Examples include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid.

Aromatic dicarboxylic acid accounts for 40 mol% of the total carboxylic acid components.
If it is above, it is preferable. If it is less than 40 mol%, the mechanical strength and water resistance of the obtained copolyester will decrease. Examples of aliphatic dicarboxylic acids and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, 1.3-
Cyclopentanedicarboxylic acid, ■, 2-cyclohexanedicarboxylic acid, 1°3-cyclohexanedicarboxylic acid, 1.
Examples include 1,4-cyclohexanedicarboxylic acid.

Although these aliphatic dicarboxylic acids and alicyclic dicarboxylic acids may improve the adhesion of copolymerized polyester (polyurethane)1, they usually reduce mechanical strength and water resistance, so aromatic dicarboxylic acids are mainly used. is preferable.

For the glycol to be reacted with the above dicarboxylic acid.

Aliphatic glycol having 2 to 8 carbon atoms, carbon atoms @6 to
There are 12 alicyclic glycols. Glycols that can be used include 9, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1, 4
-butanediol, neopentyl glycol, 1.6-
Hexanediol, 1,2-cyclohexane dimetatool, 1,3-cyclohexane dimetatool, l,4-cyclohexane dimetatool, p-xylene glycol,
These include diethylene glycol and triethylene glycol.

Polyethers are also used as glycols. Polyethers include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

This copolyester can be obtained by a conventional melt polycondensation method. This polycondensation method includes an ester method and a transesterification method. In the ester method, a dicarboxylic acid component and a glycol component are directly reacted, and then water is distilled off to perform esterification.

Polycondensation takes place. In the transesterification method, a dimethyl ester component of a dicarboxylic acid and a glycol component are reacted, methyl alcohol is distilled off, transesterification is performed, and then double condensation is performed. Copolymerized polyesters are synthesized not only by the melt polycondensation method but also by the solution polycondensation method and the interfacial polycondensation method.

Furthermore, when this copolyester is used as an aqueous dispersion when coating a thermoplastic resin film, it can be copolymerized with an ester-forming sulfonic acid metal base-containing dicarboxylic acid during the production process of the copolyester. good.

This dicarboxylic acid is contained in the copolymer in a proportion of 0.5 to 15 mol%. This copolymerized polyester is produced in the coexistence of a water-soluble organic compound and water.

By stirring at 40 to 120°C, an aqueous dispersion is obtained. For dicarboxylic acids containing sulfonic acid metal bases.

Examples include metal salts of the following compounds: sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5
- (4-sulfophenoxy)isophthalic acid. In particular, 5
-Sodium sulfoisophthalic acid and sodium sulfoterephthalic acid are preferred.

Isocyanates used for chain extension of copolymerized polyesters include 9, for example, 2,4-tolylene diisocyanate,
2.6-) lylene diisocyanate.

p-phenylene diisocyanate, biphenylmethane diisocyanate, m-phenylene diisocyanate, hexamethylene diisocyanate tetramethylene diisocyanate 3.3'-dimethoxy-4,4''-biphenylene diisocyanate, 2.4-naphthalene diisocyanate 3.3'-dimethyl-4, 4″-biphenylene diisocyanate, 4.4′-diphenylene diisocyanate, 4.4′-diisocyanate-diphenyl ether, 1.5″-naphthalene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 1.3-diisocyanate methyl Cyclohexane, 1,4-diisocyanatemethylcyclohexane, 4
．． 4'-diisocyanate dicyclohexane, 4.4
'-Diisocyanate There are diisocyanate compounds such as cyclohexylmethane and isophorone diisocyanate. These polyisocyanates include triisocyanate compounds such as trimer of 2,4-tolylene diisocyanate and trimer of hexamethylene diisocyanate.
It may be contained in a proportion of 7 mol% or less of all isocyanate groups.

The acrylic double bond-containing compounds introduced into the skeleton of these copolymerized polyesters and copolymerized polyester polyurethanes include carboxyl group-containing acrylic compounds, hydroxyl group-containing acrylic compounds, glycidyl group-containing acrylic compounds, and amino group-containing acrylic compounds. It is divided into compounds, isocyanate group-containing acrylic compounds, etc. Examples of carboxyl group-containing acrylic compounds include (meth)acrylic acid. Hydroxyl group-containing acrylic compounds include mono(meth)acrylates of glycols such as ethylene glycol, diethylene glycol, and hexamethylene glycol; mono(meth)acrylates and di(meth)acrylates of triol compounds such as trimethylolpropane, glycerin, and trimethylolethane. )
Acrylate: Mono (meth) of polyols with a valence of 4 or more such as pentaerythritol and dipentaerythritol
Acrylates, di(meth)acrylates and tri(
meth)acrylate; glycerin monoallyl ether;
Examples include glycerin diallyl ether. Glycidyl (meth) is an acrylic compound containing a glycidyl group.
There are acrylates, etc. Acrylic compounds containing amino groups include (meth)acrylamide, monomethylol (
There are meth)acrylic oxides, etc. Examples of isocyanate group-containing acrylic compounds include 2, for example, cyanethyl (
Examples include meth)acrylates. These acrylic double bond-containing compounds are contained so that each molecule of the copolymerized polyester or copolymerized polyester polyurethane has at least one or more acrylic double bond.

When the number of acrylic double bonds is less than one per molecule, sufficient crosslinking density cannot be obtained, and the copolymerized polyester (
The mechanical strength of polyurethane (polyurethane) is not improved.

Methods for producing the thermoplastic resin laminated film of the present invention by laminating a copolymer on the above-mentioned thermoplastic resin film include, for example, coextrusion coating method, extrusion lamination method, coating method, dry lamination method, hot melt adhesion. There is a law. The copolymer may be subjected to stretching or heat treatment before or after lamination of the copolymer. The thickness of the copolymer to be laminated is not particularly limited, but is made as thin as possible in order to improve adhesiveness. However, if it is desired to impart flame resistance to the thermoplastic resin film by laminating the copolymer, it is not preferable if the thickness of the copolymer is too thin. Flame resistance is determined by the content of phosphorus atoms in the copolymer being 1100
If it is 0 pp or more, it will be significantly applied. Furthermore, prior to or after lamination of this copolymer, conventional corona discharge treatment (in air or under a nitrogen atmosphere) or ultraviolet irradiation treatment may be applied to further improve the adhesiveness of the thermoplastic resin film. good.

The thermoplastic resin laminated film of the present invention may contain a coloring agent, an antistatic agent, a conductive agent, a lubricant, and a heat protectant in the copolymer layer within a range that does not impair the effects of the present invention.

Crosslinking agents, anti-blocking agents, lubricants such as inorganic or organic particles, other polymers, ultraviolet absorbers, deterioration inhibitors, and the like may be added.

(Example) The present invention will be described below with reference to examples.

On the viewing plate (1) Preparation of thermoplastic resin laminated film 388 parts by weight of dimethyl phthalate, 248 parts by weight of ethylene glycol,
9.4 parts by weight of the phosphorus compound represented by formula (b) were polycondensed to obtain a phosphorus compound-modified copolymerized polyester. The intrinsic viscosity of this copolyester is 0.59. And the melting point was 256°C. This phosphorus compound-modified copolyester and polyethylene terephthalate (thermoplastic resin film, melting point 285°C) were charged into an extruder.
While melting and compounding into two layers in a gooey, it was extruded onto a cooling roll in the form of a sheet. Next, this sheet was
After stretching 3.5 times in the longitudinal direction at 130°C, the film was stretched 3.5 times in the transverse direction at 130°C, and heat-set at 200°C. As a result, a thermoplastic resin laminate film having a 50 μm polyethylene terephthalate layer and a 2 μm phosphorus compound-modified copolyester layer was produced.

(2) Evaluation of thermoplastic resin laminated film 10% aqueous solution of polyvinyl alcohol (PVA, hydrophilic polymer),
and polyvinyl chloride (PVC, hydrophobic polymer) 1
A 0% DMF (dimethylformamide) solution was prepared. Color each solution with red dye.

The phosphorus compound-modified copolyester layer side of the two thermoplastic resin laminated films obtained in (1)
They were printed separately at a concentration of 2 g/%.

on each printed side of this thermoplastic resin laminated film.

After uniformly applying cellophane tape (L-Pack, manufactured by Nichiban Co., Ltd.), the tape was quickly peeled off in 180° and 360° directions. On the printed surface after peeling off,
The ratio of the area of the ink remaining area to the total area was visually determined, and the adhesion was evaluated according to the following criteria. If the ratio of the area of the residual ink area to the total area is 95% or more, it is grade A, 50 to 95% is grade B, 10 to 50% is grade 0, and 1.
0% or less was classified as D grade. As a result, the adhesion of PV
Regarding A, it is B grade.

And in terms of PvC, it was grade A.

A thermoplastic resin laminated film was obtained in the same manner as in Example 1. on the phosphorus compound-modified copolyester layer side of this thermoplastic resin laminated film.

Cellulose acetate butyrate colored with red dye (
A 10% methyl cellosolve solution (usually used as an anti-inflammatory agent) was printed at a coating rate of 12 g/rJ.

Cellophane tape was attached to the printed surface of this thermoplastic resin laminated film in the same manner as in Example 1, and a peeling test was conducted. As a result, the adhesiveness was grade B.

Next Item 1 A thermoplastic resin laminate film was obtained in the same manner as in Example 1. After corona discharge treatment was applied to the phosphorus compound-modified copolyester side of this thermoplastic resin laminated film, 5ift and aluminum were applied in this order to approximately 700%
It was deposited to a human thickness and then immersed in boiling water for 30 minutes.

The thermoplastic resin laminated film that has been treated in this way is
Thereafter, PVA and PvC were printed in the same manner as in Example 1, and a peel test was conducted. the result.

The adhesion in all cases was grade A.

Pointed rattan mottled raw material (1) Preparation of thermoplastic resin laminate film Dicarboxylic acid units were 50 mol% of terephthalic acid.

Isophthalic acid 30 mol%, compound 1 represented by formula (t)
5 mol% (as acid residues) and 5 mol% of sodium 5-sulfoisophthalate, and the glycol unit is composed of 80 mol% of ethylene glycol and 20% of neopentyl glycol. was synthesized. A 10% aqueous dispersion of this copolymerized polyester.

It was applied to a polyester biaxially stretched film and dried.

As a result, a thermoplastic resin laminate film having a 125 μm polyethylene terephthalate layer and a 0.5 μm phosphorus compound-modified copolyester layer was produced.

(2) Evaluation of thermoplastic resin laminated film γ-Fe20.
250 parts by weight of fine powder particles, 2 parts by weight of dioctyl sulfonate, copolymerized polyester (with dicarboxylic acid units of 45 mol% of terephthalic acid, 20 mol% of isophthalic acid, 32.5 mol% of sebacic acid, and 2.5 mol% of 5-sodium sulfoisophthalic acid). 48 parts by weight of Cellosolve acetate and 600 parts by weight of cellosolve acetate were placed in a ball mill and mixed for about 24 hours. To 400 parts by weight of this mixture, 100 parts by weight of the copolymerized polyester, 30 parts by weight of nitrocellulose, 70 parts by weight of vinyl chloride-vinyl acetate copolymer, 30 parts by weight of polyisocyanate and 400 parts by weight of methyl ethyl ketone were added, and the mixture was heated using a ball mill. Approximately 70
Mixed for an hour. After filtering and defoaming the resulting mixture, (
It was applied onto the thermoplastic resin laminated film obtained in section 1) using a gravure coater. When the coated surface was smoothed and dried at 80°C, a film with a coating thickness of 2 μm was obtained.

Cellophane tape was attached to the coated surface of this thermoplastic resin laminated film in the same manner as in Example 1, and a peeling test was conducted. As a result, the adhesiveness was grade A.

Example 1 UV was applied to the phosphorus compound-modified copolyester layer of the thermoplastic resin laminated film obtained by the same method as Example 4.
Curing ink red type (Daikure SSP Red, manufactured by Dainippon Ink Co., Ltd.) was applied to a thickness of 3 μm, and ultraviolet light (1
000mj/cj) for complete curing.

Cellophane tape was attached to the coated surface of this thermoplastic resin laminated film in the same manner as in Example 1, and a peeling test was conducted. As a result, the adhesiveness was grade B.

A copolyester synthesized in the same manner as in Example 4 was applied to a 100 μm thick polyethylene naphthalate film in a thickness of 0.3 μm while maintaining its solid content.

PVA and PvC were printed on the coated surface of this thermoplastic resin laminated film in the same manner as in Example 1.

Cellophane tape was attached and a peel test was conducted.

As a result, the adhesion was grade B for PVA.

And in terms of PvC, it was grade A.

Fruit fat ■1 A lθ% aqueous dispersion of a copolymerized polyester synthesized by the same method as in Example 4 was added to a 25 μm thick polyphenylene sulfide film (UL standard,
VTM-0) at a thickness of 0.5 μm.

This thermoplastic resin laminated film had self-extinguishing properties, and the coating layer itself also had flame resistance.

Inugami ± 1 By using the same method as in Example 4 and shortening the reaction time, 1 of 9 molecules of 14,000 phosphorus compound-modified copolyester was prepared.
A 0% aqueous dispersion was synthesized. This copolymerized polyester 10
After dissolving 0 parts by weight in 72 parts by weight of methyl ethyl ketone and 72 parts by weight of toluene.

To this solution were added 21 parts by weight of 4,4°-diphenylmethane diisocyanate and 0.05 parts by weight of diptyltin dilaurate, and the mixture was reacted at 70 to 80°C for 3 hours.

After the reaction, the solvent was evaporated to obtain an aqueous dispersion of copolymerized polyester polyurethane. Using this copolymerized polyester polyurethane, a thermoplastic resin laminate film was produced in the same manner as in Example 4.

After printing cellulose acetate butyrate on this thermoplastic resin laminated film in the same manner as in Example 2, a cellophane tape was attached to the printed surface in the same manner as in Example 1, and a peeling test was conducted. As a result, the adhesiveness was grade A.

To the copolymerized polyester polyurethane obtained in the same manner as in Example 8, 15 parts by weight of pentaerythritol was further added and reacted at 70 to 80°C for 2 hours. Dilute with solvent 1
A 0% aqueous dispersion was prepared, and this was applied to a 1 μm thick polyester film in a thickness of 125 μm.

A red type UV curable ink was applied to this thermoplastic resin laminated film in the same manner as in Example 5, and after curing by irradiation with ultraviolet rays, cellophane tape was pasted on the coated surface in the same manner as in Example 1. Then, a peel test was conducted. As a result, the adhesiveness was grade A.

This 1 pull 1 No phosphorus compound-modified copolyester is used.

A single-layer film of polyethylene terephthalate having the same thickness was produced in the same manner as in Example 1, except that only polyethylene terephthalate was charged into the extruder.

PVA and PvC were printed on the coated surface of this thermoplastic resin film in the same manner as in Example 1, and a peel test was conducted. As a result, the adhesion was grade D for PVA and grade 0 for PvC.

le comparison coal 1 No phosphorus compound-modified copolyester is used.

A single-layer film of polyethylene terephthalate having the same thickness was produced in the same manner as in Example 1, except that only polyethylene terephthalate was charged into the extruder.

Cellulose acetate butyrate was printed on this thermoplastic resin film in the same manner as in Example 2, and a peel test was conducted. As a result, the adhesiveness was grade D.

master of comparison No phosphorus compound-modified copolyester is used.

A monolayer film of a borister biaxially stretched film having the same thickness as the thermoplastic resin laminate film of Example 4 was produced.

A red type UV curable ink was applied to this thermoplastic resin film in the same manner as in Example 4.

It was completely cured by irradiating it with ultraviolet light.

on the ink-coated surface of this thermoplastic resin film.

Cellophane tape was attached in the same manner as in Example 1.

A pulling test was conducted. As a result, the adhesiveness was grade D.

As is clear from the Examples and Comparative Examples, the thermoplastic resin laminate film of the present invention has a phosphorus compound-modified copolyester layer, so it has good adhesion to hydrophilic polymers, hydrophobic polymers, and inorganic materials. In good condition. After printing or applying a copolymerized polyester containing a wood-philic polymer containing an ink, a hydrophobic polymer, or a magnetic paint to the copolymerized polyester layer of the thermoplastic resin laminated film, a peeling test using cellophane tape was performed. Even if you do this, the ink and magnetic paint will not transfer to the cellophane tape side. Conventional single-layer thermoplastic resin films made of polyethylene terephthalate or polyester biaxially oriented films lack adhesion to polymers and inorganic materials, so when a peel test similar to the above is performed, most of the ink and magnetic coatings are removed. transfers to the cellophane tape side.

(Effects of the Invention) Since the thermoplastic resin laminated film of the present invention is constituted by laminating the phosphorus compound-modified copolymer on the thermoplastic resin film, it can contain any of hydrophilic polymers, hydrophobic polymers, and inorganic materials. Both have good adhesion. As a result, this thermoplastic resin laminated film is a base film for magnetic tape.

Suitable for use in applications such as insulating tape, photographic film, tracing film, and food packaging film.

that's all

Claims (1)

[Scope of Claims] 1. A thermoplastic resin laminated film in which a copolymer is laminated on a thermoplastic resin film, wherein the copolymer has a phosphorus compound represented by the following formula in its skeleton. Film: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R_1 is a monovalent ester-forming functional group, R_2
and R_3 are the same or different, a halogen atom,
A hydrocarbon group having 1 to 10 carbon atoms or a monovalent ester-forming functional group, A is a divalent or trivalent organic residue, n
_1 is 1 or 2, and n_2 and n_3 are each an integer of 0 to 4. 2. The copolymer is at least one of a copolymerized polyester, a copolymerized polyester polyurethane, and a copolymerized polyester (polyurethane) into which an acrylic double bond-containing compound is introduced. The thermoplastic resin laminate film described above.