JP3139527B2 - Laminated film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film. Excellent in smoothness, lubricity, adhesiveness, blocking resistance, etc., suitable as a base film used for magnetic recording materials, various photographic materials, thermal transfer materials, packaging materials, electrical insulating materials, general industrial materials, etc. The present invention relates to a laminated film. In particular, the present invention relates to a laminated film suitable as a base film used for a magnetic recording material.

[0002]

2. Description of the Related Art Polyesters, especially polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate or poly-1,4-cyclohexane dimethylene terephthalate and polyesters based on these are excellent. It has physical and chemical properties and is widely used as fibers, films or sheets, and also as molded products thereof. In particular, polyester films have excellent properties in heat resistance, chemical resistance, and mechanical properties, and are used in many applications such as magnetic recording materials, various photographic materials, packaging materials, electrical insulating materials, and general industrial materials. I have.

[0003] In these applications, the polyester film is not used alone, and various coatings such as a magnetic paint, a chemical mat paint, a diazo photosensitive paint, a gelatin composition, and a heat seal are applied to the film surface. It is used by applying or printing a composition, ink, or the like. In particular, films used for magnetic tapes and floppy disks are required to have flatness and smoothness for high reliability and high density of magnetic recording. There is a strong demand for improved adhesion to films. However, when an adhesive force to the magnetic paint is applied to the film, blocking occurs between the films, and various workability is deteriorated and magnetic recording performance is deteriorated. For this reason, in order to impart the adhesiveness of the film, it is necessary to simultaneously satisfy the properties of the film such as slipperiness and blocking prevention.

However, since the polyester itself is generally inert and has poor adhesiveness, various coatings such as a magnetic paint, a chemical mat paint, a diazo photosensitive paint, a gelatin composition, and a heat-sealing composition are provided on the film surface. object,
When applying or printing ink, etc., in order to improve the adhesiveness with the coating, the film surface is subjected to physical treatment such as corona discharge or plasma, or chemical treatment using alkali or amine chemicals. There are known methods for performing various treatments, and methods for coating easily adhesive substances. However, the physical or chemical surface treatment method complicates the process, not only increases the cost, but also does not provide sufficient adhesiveness.

On the other hand, a method of coating an easily adhesive substance can be carried out in the process of producing a polyester film, is advantageous in cost, and it is necessary to select an adhesive substance which can cope with various coatings. It is possible. Further, from the viewpoints of handleability of the polyester film and workability at the time of producing the film, various water-dispersed or water-soluble copolymerized polyesters and lamination or coating of the copolymerized polyester on a polyester film have been proposed. For example, Japanese Patent Application Laid-Open Nos. 50-83497 and 53-2
No. 536 and JP-A-54-3848 disclose a polyester obtained by copolymerizing an ester-forming sulfonic acid metal salt compound and an aliphatic dicarboxylic acid component, and diethylene glycol. JP-A-59-215318 discloses an ester. Examples include a film undercoated with a polyester obtained by copolymerizing a metal sulfonic acid compound and an aliphatic dicarboxylic acid component.

On the other hand, as a biaxially oriented thermoplastic resin film in which the surface characteristics of the base film are improved, substantially spherical silica particles originating from colloidal silica are contained in polyester which is a thermoplastic resin. A film is known (for example, JP-A-59-171623).

In such a biaxially oriented thermoplastic resin film, the silica particles contained can form projections on the surface of the film, reduce the frictional resistance of the surface, and improve the handling and running properties. is there.

[0008]

However, the above-mentioned prior art has the following problems. That is, JP-A-50-83497 and JP-A-53-253.
No. 6, JP-A-54-3848 and JP-A-5-3848.
As described in JP-A-9-215318, when an ester-forming sulfonic acid metal salt compound and an aliphatic dicarboxylic acid component, and further diethylene glycol are copolymerized, adhesion is exhibited, but blocking resistance and slipperiness are improved. There are disadvantages such as inferiority.

In the biaxially oriented thermoplastic resin film disclosed in JP-A-59-171623, the contained particles are randomly distributed over the entire region in the thickness direction of the film. There is a limit to the density increase, and the height of the projections also varies at random. Therefore, there is a limit to the improvement of the film running property and the like by reducing the frictional resistance, the performance of preventing the film surface from being damaged (hereinafter referred to as scratch resistance) and the abrasion resistance.

[0010]

SUMMARY OF THE INVENTION The present invention solves these drawbacks and is a biaxially oriented thermoplastic resin film having a laminated structure of a thermoplastic resin A and a thermoplastic resin B. By adopting a biaxially oriented thermoplastic resin film that improves the film surface characteristics of the thermoplastic resin A by concentrating and containing particles of a specific size, the film surface is efficiently, densely and It becomes possible to form projections with a uniform height, and it is possible to greatly improve running properties, scratch resistance, abrasion resistance, etc., and further laminate the specific aqueous substance of the present invention on this substrate on at least one side By doing so, it has become possible to significantly improve the antistatic property, adhesiveness, and the like.

That is, an object of the present invention is to laminate a film A mainly composed of a thermoplastic resin A and particles on one surface of a film B mainly composed of a thermoplastic resin B,
Has a thickness of 0.005 to 5 μm, and the average particle diameter of the particles contained in the film A is 0.1 to
10 times, the content of the particles in the film A is 0.05 to 5
0 is the weight percent biaxial off of oriented thermoplastic resin laminated film
A layer (C layer) made of at least one aqueous material selected from the group consisting of an acrylic resin, a vinyl resin, a urethane resin, a polyester resin and their grafts or blocks is provided on the film B side. The main feature is a laminated film.

The thermoplastic resin A in the present invention is not particularly limited, such as polyester, polyolefin, polyamide, and polyphenylene sulfide. Particularly, polyester, especially ethylene terephthalate, ethylene α,
When at least one structural unit selected from β-bis (2-chlorophenoxy) ethane-4,4, -dicarboxylate and ethylene 2,6-naphthalate units is the main constituent, the film surface This is preferable because the formation of projections having a high density and a uniform height is further improved. When the thermoplastic resin constituting the present invention is crystalline, the thermoplastic resin A
Is very desirable because it makes it easier to form target protrusions on the layer surface. The term "crystallinity" as used herein means that it is not amorphous, and quantitatively, the cold crystallization temperature Tcc in the crystallization parameter is detected, and the crystallization parameter ΔTcg is 150 ° C. These are: Further, when the heat of fusion (change in enthalpy of fusion) measured by a differential scanning calorimeter shows a crystallinity of 7.5 cal / g or more, the thermoplastic resin A layer is extremely desirable in forming surface projections. Further, the case of polyester containing ethylene terephthalate as a main component is particularly preferable because the surface protrusion forming characteristics of the thermoplastic resin A layer are further improved. Further, when ethylene 2,6-naphthalate is used as a main component, the heat resistance of the film is improved in addition to the ability to form surface projections. Note that two or more kinds of thermoplastic resins may be mixed or a copolymer may be used as long as the present invention is not impaired.

The shape of the particles in the thermoplastic resin A of the present invention is not particularly limited, but particles having a particle diameter ratio (particle long diameter / short diameter) of 1.0 to 1.3, particularly, In the case of spherical particles, it is desirable because projections on the film surface having a uniform height are easily formed.

The particles in the thermoplastic resin A of the present invention form projections of uniform height at a high density when the single particle index in the film is 0.7 or more, preferably 0.9 or more. It is particularly desirable because it is easy to do.

The type of particles in the thermoplastic resin A of the present invention is not particularly limited. However, in order to satisfy the above preferable particle characteristics, alumina silicate, silica in which primary particles are aggregated, and internally precipitated particles are used. Not preferred. Preferable particles include substantially spherical silica particles resulting from colloidal silica, particles of a crosslinked polymer (for example, crosslinked polystyrene), and the like. In particular, the temperature when the weight is reduced by 10% by weight (a thermogravimetric analyzer Shimadzu TG- It is particularly desirable to use crosslinked polymer particles having a high degree of crosslinking until the temperature rise rate is 20 ° C./min or higher (measured using 30 M. The temperature rise rate is 20 ° C./min) because the film surface projection forming characteristics are further improved. In the case of spherical silica originating from colloidal silica, substantially spherical silica having a low sodium content and produced by the alkoxide method is desirable. However, other particles, such as particles of calcium carbonate, titanium dioxide, alumina, etc., can be adequately used by appropriate control of film thickness and average particle size.

The thickness of the film layer mainly comprising the thermoplastic resin A of the present invention is 0.005 to 5 μm, preferably 0.01 to 1 μm.
μm, more preferably 0.03 to 0.5 μm. When the film thickness is smaller than the above range, the durability as a laminated film layer cannot be secured. Conversely, when the film thickness is large, it is difficult to form surface projections of an appropriate height with high density due to the relationship with contained particles. Become.

The size of the particles contained in the thermoplastic resin A film is such that the average particle size in the laminated film containing the particles is 0.1 to 10 times, preferably 0.5 to 10 times the thickness of the laminated film. The range is 5 times, more preferably 1.1 to 3 times. If the average particle diameter / film thickness ratio is smaller than the above range, the unevenness of the formed film surface projections becomes large, and the effect of improving scratch resistance and abrasion resistance becomes poor. Ununiformity and a decrease in the particle concentration ratio on the film surface, which will be described later, are apt to be caused, and the effect of improving the scratch resistance and the abrasion resistance is also unfavorable.

The average particle diameter (diameter) of the particles in the thermoplastic resin A in the film is 0.005 to 3 μm, preferably
When the thickness is in the range of 0.02 to 0.45 μm, the effect of improving the scratch resistance and abrasion resistance of the film surface is further improved, which is desirable.

Then, such particles are contained in an amount of 0.05 to 50% by weight, preferably 0.075 to 10% by weight, more preferably 0.1 to 10% by weight.
５5% by weight contained in the thermoplastic resin A film.
If it is smaller than this, the film surface projection formation density becomes too low, so that good unevenness transfer characteristics to the magnetic surface cannot be obtained.On the contrary, if it is too high, the ratio of the contained particles becomes too high,
It is not preferable because the laminated film layer itself becomes too brittle. Further, the average height of the surface projections of the laminated film layer of the thermoplastic resin A formed by the particles is not less than 1 / 3.5 of the average particle size of the particles. The surface protrusions having such an average height can be obtained by appropriately selecting and setting the average particle diameter of the contained particles with respect to the thickness of the laminated film from the above-described range.

That is, the laminated film layer of the thermoplastic resin A in the present invention contains particles having an average particle diameter near or larger than the film thickness. In other words, the ultra-thin laminated film contains microparticles having an average particle size near or greater than the film thickness.
Therefore, the particles can be substantially concentrated only on the laminated film layer in the thickness direction of the entire biaxially oriented thermoplastic resin film and distributed. As a result, the density of the particles placed in the laminated film can be easily increased, and the density of protrusions on the film surface formed by the particles can be easily increased. In addition, the particles are contained in the laminated film, whereby the position is regulated in the thickness direction with respect to the entire biaxially oriented thermoplastic resin film, and the thickness and the average particle size of the laminated film are further increased. Is as described above, the height of the surface projections formed by the particles becomes extremely uniform. The formation of high-density and uniform-height surface projections greatly enhances the scratch resistance and abrasion resistance of the film surface.

The film mainly composed of the thermoplastic resin A and the particles is laminated on the film mainly composed of the plastic resin B. The thermoplastic resin B is the same as the thermoplastic resin A described above, and the thermoplastic resin B and the thermoplastic resin A
May be of the same type or different. The film layer of the thermoplastic resin A is laminated on one side of the film layer made of the thermoplastic resin B. In other words, this is the case where the laminated configuration is A / B (here, the types of thermoplastic resins A and B may be the same or different ) . As the thermoplastic resin B, a crystalline polymer is desirable. In particular, when the crystalline parameter ΔTcg is in the range of 20 to 100 ° C., for example, the durability of the entire base film as a magnetic recording medium is improved. It is desirable because it becomes even better. Specific examples include polyesters, polyamides, polyphenylene sulfides, and polyolefins. Polyesters are particularly desirable because the durability of the film as a whole is further improved. As the polyester, ethylene terephthalate, ethylene α, β-bis (2-chlorophenoxy) ethane-4,4, -dicarboxylate, ethylene 2,2
A film having at least one structural unit selected from 6-naphthalate units as a main component is preferable as a film for a magnetic recording medium. However, other components may be copolymerized within a range that does not impair the present invention and within a range that does not impair desired crystallinity, preferably within 5 mol%.

The thermoplastic resin B of the present invention may be blended with other polymers as long as the object of the present invention is not impaired, and may be an antioxidant, a heat stabilizer, a lubricant, an ultraviolet absorber. Organic additives such as agents may be added to the extent that they are usually added. It is not particularly necessary that the film containing the thermoplastic resin B as a main component contains particles, but when this film forms one surface of the film surface, the average particle size is 0.007 to 2 μm, particularly 0.02 to 0.45 μm. 0.001 particles
0.2 to 0.2% by weight, especially 0.005 to 0.15% by weight, and even 0.
When the content is 005 to 0.12% by weight, for example, in a base film for a magnetic recording medium, not only the coefficient of friction and the scratch resistance are improved, but also the winding appearance of the film is improved, which is extremely desirable. It is desirable to use the kind of particles contained in the thermoplastic resin A that is desirably used. The types and sizes of the particles contained in the thermoplastic resins A and B may be the same or different.

Thermoplastic resin A containing particles as described above
And a thermoplastic resin B are laminated by co-extrusion, molded into a sheet, and then biaxially stretched to form a biaxially oriented thermoplastic resin film. Lamination by co-extrusion in the present invention means that the thermoplastic resin A containing particles and the thermoplastic resin B are extruded by different extruders and laminated before discharging the laminated sheet from the die. Say. This lamination may be performed in a die (for example, a manifold) for forming and discharging into a sheet shape. However, since the laminated film layer is extremely thin as described above, the inside of the polymer tube before being introduced into the die is formed. It is preferable to carry out in. In particular, it is particularly preferable that the lamination portion in the polymer tube is formed in a rectangular shape, since the lamination can be uniformly performed in the width direction. The molten polymer laminated in the rectangular laminated portion in the polymer pipe is widened to a predetermined width in the sheet width direction by the manifold in the die, discharged in a sheet form from the die, and then biaxially stretched. Therefore, even if the laminated film after biaxial orientation is extremely thin, the particle-containing thermoplastic polymer is laminated with a considerable thickness in the rectangular laminated portion in the polymer tube, so that it can be laminated easily and accurately. it can.

In the biaxially oriented thermoplastic resin film comprising the thermoplastic resin A and the thermoplastic resin B, the particle concentration ratio of the surface layer on the side of the laminated film containing the particles is 0.1 or less. Is preferred. The surface particle concentration ratio indicates how the particles forming the film surface projections are covered with the thin film of the thermoplastic resin A on the film surface, as shown in the measurement method described below, and the particles are formed on the film surface. The higher the degree of substantial direct exposure, the higher the surface layer particle concentration ratio, and the higher the degree of surface protrusions formed but covered with the thermoplastic resin A thin film, the lower the surface particle concentration ratio. Since the particles forming the protrusions are covered with the thin film of the thermoplastic resin A, even when the particles are densely distributed in the ultrathin laminated film layer,
The particles are firmly held by the laminated film layer, and thus the base film layer of the thermoplastic resin B.
Therefore, when the surface layer particle concentration ratio is equal to or less than the above value, the particles are prevented from falling off, and the durability of the film surface is maintained high. Such a surface particle concentration ratio can be achieved by performing lamination by coextrusion.

Incidentally, depending on the coating method,
That is, it is possible to coat a resin layer with an extremely thin thickness with respect to the base film layer and to make the resin layer contain particles, but the concentration ratio of the surface layer particles becomes extremely high (that is, the particles are substantially reduced). The degree of direct exposure to the surface is significantly increased), and the surface tends to be extremely brittle compared to the film of the present invention.

Then, an acrylic resin, a vinyl resin, or the like is provided on the layer B side of the laminated structure of the film layer of the thermoplastic resin A and the film layer of the thermoplastic resin B as described above.
The laminated film of the present invention is completed by laminating (C layer) at least one kind of easily adhesive substance selected from the group consisting of a urethane resin, a polyester resin and a graft thereof.

The laminated structure is an A / B / C structure.
You. When the film of the present invention is used as a magnetic recording medium, the magnetic layer is preferably provided on the C layer side.

The lamination of the layer C is possible in each step of the biaxially oriented thermoplastic resin film production process.
Since the layer is an ultra-thin layer, after the C layer is laminated, the surface of the C layer is roasted before being molded and fixed as the C layer or the whole film.
It is preferable to prevent contact between the tool and the like. Therefore, for example, it is preferable to laminate the layer C before or after the stretching in the width direction in the sequential biaxial stretching in which the stretching in the longitudinal direction and subsequently in the width direction is performed, or before the stretching in the homogeneous biaxial stretching. Coating in a continuous manufacturing process, so-called in-line coating or the like, is industrially preferable, but may be performed off-line in a separate dedicated process.

The base film is formed by laminating (C layer) at least one aqueous material selected from the group consisting of the acrylic resin, vinyl resin, urethane resin, polyester resin and their grafts as the C layer. With the synergistic effect of the above, excellent smoothness and smoothness, excellent abrasion resistance, etc., and further improvement in adhesion to a magnetic layer when used for a magnetic recording medium, etc., electromagnetic characteristics, durability of a magnetic surface, etc. Can be.

The coating liquid used for forming the layer C in the present invention is an aqueous, that is, water-soluble or water-dispersible acrylic resin,
It is a coating liquid containing at least one aqueous substance selected from the group consisting of vinyl resins, urethane resins, polyester resins and their grafts. The water-soluble or water-dispersible resin in the present invention may be any resin that dissolves or disperses in water, and is not particularly limited in thermoplasticity and thermosetting. The term “water-soluble or water-dispersible” as used herein means a slight amount, and the amount is not particularly limited, but is usually 20% by weight or less, preferably 10% by weight or less, and may contain substances other than water such as various organic solvents. good.

As the acrylic resin in the present invention, at least 40% of acrylic and / or methacrylic monomer and 0.1 to 20% by mole of other functional group-containing monomer are used.
One or more halogen-free ethylenically unsaturated monomers of about 0-49.9 mole percent and a copolymer, or at least 25 mole percent of acrylic acid, methacrylic acid or an alkyl ester of acrylic acid, methacrylic acid Copolymers derived from comonomers and 1 to 50 mol% of vinyl sulfonic acid and p-styrene sulfonic acid and comonomers selected from salts of these acids can be mentioned.

The vinyl resin has a general formula

Embedded image (Where R ₁ and R ₂ are hydrogen or an alkyl group, M
₁ and M ₂ represent hydrogen, an alkali metal, an alkaline earth metal, ammonium (including substituted ammonium) or an alkyl group, and M ₁ and M ₂ are not simultaneously an alkyl group. ).

Examples of the urethane resin include polyurethane whose affinity for water is increased by a carboxylic acid group, a sulfonic acid group or a half-sulfuric acid base. However, the amount of a base such as a carboxylate group, a sulfonate group or a half-sulfate base is preferably 0.5 to 15% by weight. Examples of the polyhydroxy compound used for the synthesis of polyurethane include polyethylene glycol, polyethylene propylene glycol, polytetramethylene glycol, hexamethylene glycol, 1,5-pentaneddiol, diethylene glycol, and the like. Triethylene glycol, polycaprolactone, polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentane Eristol, glycerin and the like can be mentioned. Examples of the polyisocyanate compound include hexamethylene diisocyanate and diphenylmethane diisocyanate.
, Tolylene diisocyanate, isophorone diisocyanate, adducts of tolylene diisocyanate and trimethylolpropane, adducts of hexamethylene diisocyanate and trimethylolethane, and the like. .
Examples of the carboxylic acid-containing polyol include dimethylo-
Examples thereof include rupropionic acid, dimethylolbutyric acid, dimethylolvaleric acid, and trimellitbis (ethylene glycol) ester. Examples of the amino acid-containing carboxylic acid include β-aminopropionic acid, γ-aminobutyric acid, p-aminobenzoic acid, and the like. Examples of the hydroxyl group-containing carboxylic acid include 3-hydroxypropionic acid, γ-hydroxybutyric acid, p- (2-hydroxyethyl) benzoic acid, and malic acid. Examples of the compound having an amino group or a hydroxyl group and a sulfone group include, for example, aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 2-amino-5-methylbenzene-2-sulfonic acid, sodium β-hydroxyethanesulfonic acid, and aliphatic Di-primary amine compound propane sultone,
A butane sultone addition product and the like are preferable, and a propane sultone adduct of an aliphatic diprimary amine compound is preferable. Examples of the compound containing an amino group or a hydroxyl group and a sulfuric acid half-ester group include aminoethanol sulfate, ethylenediamineethanol sulfate, aminobutanol sulfate, hydroxyethanol sulfate, γ-hydroxypropanol sulfate, α -Hydroxybutanol sulfate and the like.

Alternatively, Japanese Patent Publication No. 42-24194,
JP-B-46-7720, JP-B-46-10193
JP, JP-B-49-37839, JP-A-50-378
Examples thereof include polyurethane resins having an anionic group known in JP-A-123197, JP-A-53-126058, JP-A-54-138098 and the like, or polyurethane resins similar thereto.

Here, the main constituent components of the polyurethane forming component are polyisocyanate, polyol, chain extender, crosslinking agent and the like. Moreover, molecular weight 300-2000
Preferred are resins comprising a polyol having 0, a polyisocyanate, a chain extender having a reactive hydrogen atom, a group having a group which reacts with an isocyanate group, and a compound having at least one anionic group. Anionic groups in the polyurethane resin is preferably _{-SO 3 H, -OSO 2 H,} -
COOH and their ammonium and lithium salts,
Used as sodium, potassium or magnesium salts. The amount of the anionic group in the polyurethane resin is preferably 0.05 to 8% by weight.

Examples of the polyester resin include a polyester copolymer composed of a dicarboxylic acid containing a metal sulfonic acid group in an amount of 0.5 to 15 mol% of all dicarboxylic acid components, and a polyhydric alcohol. However, examples of the above-mentioned dicarboxylic acid containing a sulfonic acid metal base include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5 [4-sulfophenoxy] isophthalic acid. And the like. Particularly preferred are 5-sodium sulfoisophthalic acid and sodium sulfoterephthalic acid.

Alternatively, an aqueous polyester resin having at least one kind of free carboxylic acid group and carboxylic acid group in the molecule, a crosslinking agent having two or more epoxy groups, and a compound containing a reaction accelerating compound if necessary. Can be. However, in order to introduce a carboxylic acid group into the molecule of the aqueous polyester resin, for example, trimellitic anhydride, trimellitic acid, pyromellitic anhydride, pyromellitic acid, trimesic acid, cyclobutanetetracarboxylic acid, dimethylol It is preferable to use a polyvalent compound such as propionic acid as one of the polymer production raw materials. Also,
The carboxylate can be introduced by neutralizing the carboxylic acid group introduced into the polymer with an amino compound, ammonia, an alkali metal or the like.

Examples of the various graft resins include comb-type graft polymers having polymethyl methacrylate as a main chain and poly 2-hydroxyethyl methacrylate as a branch chain.

Alternatively, there may be mentioned an acrylic graft polyester in which the backbone polymer is a polyester and the branch polymer is an acrylic copolymer. However, the polyester serving as the backbone polymer of the aqueous polyester-acrylic graft polymer is a substantially linear polymer synthesized from a polybasic acid or an ester-forming derivative thereof and a polyol or an ester-forming derivative thereof. . Examples of the polybasic acid component of the polymer include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, and pyromellitic acid. Examples include melitic acid and dimer acid. Two or more of these components can be used. Further, a small proportion of unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid are used together with these components. Can be. The proportion of the unsaturated polybasic acid component or hydroxycarboxylic acid component is at most 10 mol%, preferably 5 mol% or less.

The polyol component includes ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol.
1,6-hexanediol 1,4-cyclohexanedimethanol, xylylene glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, poly (ethylene oxide) glycol, poly (tetramethylene oxide) ) Glycol and the like.
Two or more of these can be used.

Examples of the monomer of the acrylic polymer include alkyl acrylate and alkyl methacrylate (where the alkyl group is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group). Group,
t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.):
Hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate: acrylamide, methacrylamide, N-methyl methacryl Amide, N-methylacrylamide, N-methylolacrylamide, N-methylo-
Amide group-containing monomers such as methacrylamide, N-dimethylolacrylamide, N-methoxymethylacrylamide and N-phenylacrylamide: N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, Epoxy group-containing monomers such as glycidyl methacrylate: monomers containing a carboxyl group such as acrylic acid, methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt) or salts thereof. These can be used in combination with other monomers. Other monomers include, for example, monomers containing an epoxy group such as allyl glycidyl ether: sulfonic acid groups such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt) or salts thereof. Monomer: a monomer containing a carboxyl group such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (sodium salt, potassium salt, ammonium salt) or a salt thereof: maleic anhydride;
Monomers containing acid anhydrides such as itaconic anhydride: vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid Monoester, acrylonitrile, methacrylonitrile, alkyl itaconate monoester, vinylidene chloride, vinyl acetate, vinyl chloride and the like can be mentioned. The above-mentioned monomers are copolymerized using one kind or two or more kinds.

As the block polymer, an aqueous acrylic copolymer-polyester block polymer can be exemplified. However, as the monomer of the acrylic copolymer constituting the block polymer, for example, alkyl acrylate
Alkyl methacrylate, wherein the alkyl group is a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.):
Hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate: acrylamide, methacrylamide, N-methyl methacryl Amide, N-methylacrylamide, N-methylolacrylamide, N-methylo-
Amide group-containing monomers such as methacrylamide, N-dimethylolacrylamide, N-methoxymethylacrylamide and N-phenylacrylamide: N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, Epoxy group-containing monomers such as glycidyl methacrylate: monomers containing a carboxyl group such as acrylic acid, methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt) or salts thereof. These can be used in combination with other monomers. Other monomers include, for example, monomers containing an epoxy group such as allyl glycidyl ether: sulfonic acid groups such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt) or salts thereof. Monomer: a monomer containing a carboxyl group such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (sodium salt, potassium salt, ammonium salt) or a salt thereof: maleic anhydride;
Monomers containing acid anhydrides such as itaconic anhydride: vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid Monoester, acrylonitrile, methacrylonitrile, alkyl itaconate monoester, vinylidene chloride, vinyl acetate, vinyl chloride and the like can be mentioned. The above-mentioned monomers can be copolymerized by using one kind or two or more kinds. From the viewpoint of imparting hydrophilicity to an acrylic polymer, dispersion stability of an aqueous solution, adhesion to a polyester film, etc., hydroxyl groups, Those having a functional group such as an amide group, a carboxyl group or a salt thereof (sodium salt, potassium salt, ammonium salt) are preferable.

The polyester, another component of the aqueous block polymer, is a substantially linear saturated polyester synthesized from a polybasic acid or an ester-forming derivative thereof and a polyol or an ester-forming derivative thereof. is there. The polybasic acid component of this polymer includes terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-
Naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid,
Examples thereof include pyromellitic acid and dimer acid.
Two or more of these can be used. In addition, hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used together with these components.

The polyol components include ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol.
1,6-hexanediol 1,4-cyclohexanedimethanol, xylylene glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, poly (ethylene oxide) glycol, poly (tetramethylene oxide) ) Glycol and the like.
Two or more of these can be used.

The polyester is preferably an aqueous polymer, for example, organic sulfonates, carboxylate salts,
Those containing a compound having a hydrophilic group, such as diethylene glycol and polyalkylene ether glycol, are advantageous for producing an aqueous dispersion and are preferred. The introduction of this carboxylate usually uses a trifunctional or higher carboxylic acid,
Since the carboxylic acid undergoes branching in the polymerization step and tends to gel, it is desirable to reduce the copolymerization ratio.
In that respect, introduction of a hydrophilic group by sulfonic acid, diethylene glycol, polyalkylene ether glycol, or the like does not have these problems and is more advantageous.

In order to introduce a sulfonate group into a polyester molecule, for example, 5-Na sulfoisophthalic acid, 5-ammonium sulfoisophthalic acid, 4-Na sulfoisophthalic acid, 4-methylammonium sulfoisophthalic acid, It is preferable to use a sulfonic acid alkali metal salt or sulfonic acid amine compound such as -Na sulfoterephthalic acid, 5-K sulfoisophthalic acid, 4-K sulfoisophthalic acid, 2-K sulfoterephthalic acid, or Na sulfosuccinic acid. . The polyhydric carboxylic acid or polyhydric alcohol having a sulfonic acid salt group accounts for 0.5 to 20 mol%, more preferably 1 to 18 mol%, of the total polyhydric carboxylic acid component or polyhydric alcohol component. Is preferred.

In the water-soluble or water-dispersible resin layer of the present invention, various crosslinking agents may be used, if necessary. The type is not particularly limited, but as a typical one,
Isocyanate-based crosslinking agents, isocyanurate-based crosslinking agents,
Melamine-based crosslinking agents, urea-based crosslinking agents, and epoxy-based crosslinking agents can be exemplified. Specific examples of the epoxy-based crosslinking agent include polyepoxy compounds, diepoxy compounds, monoepoxy compounds, and the like.Examples of polyepoxy compounds include sorbitol, polyglycidyl ether, polyglycerol glycidyl ether, and pentane. Erythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycero-
Examples of the dipolyglycidyl ether, trimethylolpropane polyglycidyl ether and diepoxy compound include neopentyl glycol diglycidyl ether,
1,6-hexanediol glycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether -Tell,
Polytetramethylene glycol-diglycidyl ether,
Examples of the monoepoxy compound include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether.

Further, as the isocyanate-based crosslinking agent,
For example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, 4,4, -diphenylmethane diisocyanate, hexamethylene diisocyanate And xylylene diisocyanate.

As the urea-based crosslinking agent, for example, dimethylo-
Urea, dimethylol ethylene urea, dimethylol propylene urea, tetramethyl acetylene urea, 4 methoxy 5 dimethyl propylene urea dimethylol and the like.

As the melamine-based cross-linking agent, a methyl alcohol melamine derivative obtained by condensing melamine and formaldehyde is reacted with methyl alcohol, ethyl alcohol, isopropyl alcohol or the like as a lower alcohol to form an ether. Compounds and mixtures thereof are preferred. Examples of the methylol-melamine derivative include monomethylol-melamine, dimethylol-melamine, trimethylol-melamine, tetramethylol-melamine, pentamethylol-melamine, and hexamethylol-melamine. These crosslinking agents may be used alone or in some cases as 2
More than one species may be used in combination.

The thickness of the easy-adhesion layer of the present invention is not particularly limited, but is 0.001 to 1 μm, particularly 0.01 to 0.1 μm.
2 μm is preferred. If necessary, the easily adhesive coating composition of the present invention may contain, if necessary, an organic lubricant such as a flame retardant, a heat stabilizer, an ultraviolet absorber, a pigment, a dye, a fatty acid ester, or a wax. And inorganic particles such as clay, mica, titanium oxide, calcium carbonate, kaolin, wet and dry silica, colloidal silica, calcium phosphate, barium sulfate, and alumina, and acrylic acids and styrene for the purpose of imparting slipperiness and the like. Organic particles or the like having such components as constituents may be blended.

Next, a method for producing the film of the present invention will be described.

First, as a method for incorporating particles into the thermoplastic resin A, any method may be used after polymerization, during polymerization, or before polymerization, but the method of kneading the polymer with a vent-type twin-screw extruder is the present method. It is effective for obtaining a film having a surface morphology within the scope of the invention. Further, as a method of adjusting the content of particles, a high-concentration master is prepared by the above method, and the content is adjusted by diluting it with a thermoplastic resin substantially free of particles during film formation. The method is effective for obtaining a film having a surface morphology within the scope of the present invention. Further, the method of controlling the melt viscosity, copolymerization component, etc. of the high-concentration master polymer of the particles so as to keep the crystallization parameter ΔTcg in the range of 30 to 80 ° C. has a small stretching tear and has a surface morphology within the range of the present invention. It is effective to obtain a film. Thus, after sufficiently drying the pellet A containing the particles, it is supplied to a known melt extruder, and extruded in a sheet form from a slit die,
An unstretched film is produced by cooling and solidifying on a castin roll. That is, two extruders, using the combination block or die for two layers, laminating these thermoplastic resins. In the case of using the merging block method, the laminated portion is rectangular as described above, and the difference (absolute value) between the viscosities of both thermoplastic resins is 0 to 2000 poise, preferably 0 to 1000 poise.
It is effective to keep the film having the surface morphology within the range of the present invention stably, without unevenness in the width direction, and to industrially manufacture the film in the poise range. Next, this multilayer unstretched film is biaxially stretched and biaxially oriented. The method of biaxial stretching may be any of simultaneous biaxial stretching and sequential biaxial stretching, but in the case of sequential biaxial stretching in which the film is stretched in the longitudinal direction and width direction in order to stabilize the film of the surface morphology in the range of the present invention. Therefore, it is effective for industrial production without unevenness in the width direction. In the case of sequential biaxial stretching, stretching in the longitudinal direction is performed three to six times in a range of 40 to 150 ° C. and at a stretching speed of 1000 to 5000% / min in three stages, particularly four or more stages. The method is effective in obtaining a film having a surface morphology within the scope of the present invention. The stretching temperature and speed in the width direction are preferably in the range of 80 to 170 ° C and 1000 to 20000% / min. The stretching ratio is preferably 3 to 10 times. Further, if necessary, the film can be further stretched in at least one of the longitudinal direction and the width direction. Further, it is also possible to use a method in which an extremely thin layer containing particles is provided as necessary, and then stretching is performed at an area stretching ratio (magnification in the longitudinal direction × magnification in the width direction) of 9 times or more. Next, this stretched film is heat-treated. The heat treatment conditions in this case are 140 to 28 in any of the following conditions:
The heating is preferably performed at 0 ° C., preferably in the range of 160 to 260 ° C. for 0.5 to 60 seconds, but it is preferable to use microwave heating in combination with the heat treatment because the film having the surface morphology of the present invention is easily obtained.

In the present invention, the method of laminating the layer C is most preferably a method in which the layer is applied during the film production process and stretched together with the substrate. For example, the melt-extruded film before crystal orientation is stretched about 2.5 to 5 times in the longitudinal direction, a surface to be continuously applied is subjected to corona discharge treatment, and a coating liquid is applied to the treated surface. The coated film is dried while passing through a stepwise heated zone, and has a width of 2.5 to 5 in the width direction.
It is stretched about twice. Further, it is obtained by a method of being continuously guided to a heating zone at 150 to 250 ° C. to complete the crystal orientation. The coating solution used in this case is preferably an aqueous solution in view of environmental pollution and explosion-proof properties. As a method of coating on the substrate film, a known coating method, for example, a reverse coating method, a gravure coating method, a rod coating method, a die coating method, a wire bar method, or the like can be used. . Known additives such as a heat stabilizer, an oxidation stabilizer, a weather stabilizer, and the like in the coating layer (easily adhesive layer) within a range not impairing the effects of the present invention.
An ultraviolet absorber, an organic lubricant, a pigment, a dye, organic or inorganic fine particles, a filler, an antistatic agent, a nucleating agent, and the like may be blended.

Winding property of the laminated film thus obtained,
The slitting properties are good, and by applying a coating material according to the application on the coating layer side, various applications, for example, for printing various inks such as magnetic recording materials, cellophane inks, offset inks, ultraviolet curing inks, etc. It is suitably used as a base film for photographic toners, easy adhesion of chemical mat paints, easy adhesion of diazo paints, inorganic coatings for vapor deposition, and the like.

[0056]

[Method of measuring and evaluating characteristic values] The method of measuring characteristics and the method of evaluating effects in the present invention are as follows.

(1) Average Particle Diameter The thermoplastic resin is removed from the film by a plasma low-temperature incineration method (for example, PR-503, manufactured by Yamato Scientific Co., Ltd.) to expose the particles. The processing conditions are selected so that the thermoplastic resin is ashed but the particles are not damaged. This is SEM
(Scanning electron microscope), link the image of the particles (shading of light generated by the particles) to an image analyzer (for example, QTM900 manufactured by Cambridge Instrument), To obtain the average particle size.

D = ΣDi / N where Di is the circle equivalent diameter of the particles and N is the number.

(2) Content of Particles A solvent in which the thermoplastic resin is dissolved but the particles are not dissolved is selected, the particles are centrifuged from the thermoplastic resin, and the particle content is defined as a ratio (% by weight) to the total weight of the particles. I do.
In some cases, the combined use of infrared spectroscopy is also useful.

(3) Glass transition point Tg, cold crystallization temperature T
cc, crystallization parameter ΔTcg, melting point Measured using a DSC (differential scanning calorimeter) type II manufactured by PerkinElmer. The measurement conditions of DSC are as follows. That is, 10 mg of a sample is set in a DSC device, and 300
After melting at a temperature of ° C. for 5 minutes, it is quenched into liquid nitrogen.
The quenched sample is heated at a rate of 10 ° C./min, and the glass transition point Tg is detected. Further, the temperature was kept rising, and the crystallization exothermic peak temperature from the glassy state was taken as the cold crystallization temperature Tcc.
The temperature was further raised and the melting peak temperature was taken as the melting point. Also,
The difference between Tcc and Tg (Tcc-Tg) is defined as the crystallization parameter ΔTcg.

(4) Average height of surface projections Film surface in a two-detector scanning electron microscope [ESM-3200, manufactured by Elionix Inc.] and a cross-section measuring device [PMS-1, manufactured by Elionix Inc.] The height measurement value of the projection when scanning was performed with the height of the flat surface as 0 was sent to an image processing device [IBAS2000, manufactured by Carl Zeiss Co., Ltd.], and a film surface projection image was reconstructed on the image processing device. . Next, a circle-equivalent diameter is obtained from the area of each projection obtained by binarizing the projection portion on the surface projection image, and this is defined as the average diameter of the projection. The highest value among the binarized individual projections is defined as the height of the projection, and this is determined for each individual projection. Change this measurement in different places
The number of protrusions was determined 500 times, and the average value of the heights of all the measured protrusions was defined as the average height. Further, the magnification of the scanning electron microscope is selected to be a value between 1000 and 8000 times. In some cases, a high-precision optical interference type three-dimensional surface analyzer (TOPO-3D manufactured by WYKO, objective lens:
The height information obtained by using 40 to 200 times (use of a high resolution camera is effective) may be replaced with the SEM value and used.

(5) Surface Particle Concentration Ratio Using secondary ion mass spectroscopy (SIMS), the concentration ratio between the highest concentration element among the elements originating from the particles in the film and the carbon element of the thermoplastic resin was determined. Concentration,
Perform analysis in the thickness direction. The ratio of the particle concentration A at the outermost layer particle concentration (point at depth 0) measured by SIMS to the maximum concentration B obtained by continuing the analysis in the depth direction, A
/ B was defined as the surface particle concentration ratio. The measuring device and conditions are as follows.

Measurement device Secondary ion mass spectrometer (SIMS) A-DIDA3000 manufactured by ATOMIKA, West Germany Measurement conditions Primary ion species: O ₂ ⁺ Primary ion acceleration voltage: 12 kv Primary ion current: 200 nA Raster area: 400 μm □ Analysis area: Gate 30% Measurement vacuum degree: 6.0 × 109 Torr E-GUN: 0.5 KV-3.0 A (6) Single particle index The cross section of the film is observed with a transmission electron microscope (TEM), and the particles are observed. Is detected. When the observation magnification is set to about 100,000, one particle that cannot be further divided can be observed. When the total area occupied by the particles is A, and the area occupied by the aggregate in which two or more particles are agglomerated is B, (A
-B) / A is defined as a single particle. The TEM conditions are as follows. One visual field area: 2 μm ² , measuring 500 visual fields at different locations.

• Apparatus: JEM-1200EX manufactured by JEOL Ltd. • Observation magnification: 100,000 times • Section thickness: about 1000 angstroms (7) Particle size ratio Average value of the major axis of each particle in the measurement of (1) above
It is the ratio of the average value of the minor axis. That is, it is obtained by the following equation.

Major axis = ΣD1i / N Minor axis = ΣD2i / N D1i and D2i are the major axis (maximum diameter) and the minor axis (shortest axis) of each particle, and N is the total number.

(8) Thickness of Thermoplastic Resin A Layer in Laminated Film Using a secondary ion mass spectrometer (SIMS), the element and heat originating from the particles having the highest concentration among the particles in the film are measured. The concentration ratio (M ⁺ / C ⁺ ) of the carbon element of the thermoplastic resin is defined as the particle concentration, and the analysis is performed in the depth (thickness) direction from the surface of the thermoplastic resin A layer. In the surface layer, the particle concentration is low due to the interface of the surface, and the particle concentration increases as the distance from the surface increases. In the case of the film of the present invention, the particle concentration which has reached the maximum value once at the depth [I] starts to decrease again. Based on this concentration distribution curve, the depth [I
I] (where II> I) was taken as the lamination thickness. The conditions are the same as in the measurement method (5).

In the case where the particles most contained in the film are organic polymer particles, it is difficult to measure them by SIMS. Therefore, XPS (X-ray photoelectron spectroscopy), IR (infrared spectroscopy) or It is also possible to measure the depth profile and obtain the lamination thickness from the same method as described above.

(9) Scratch resistance A film obtained by slitting a film into a tape having a width of 1/2 inch was guided on a guide pin (surface roughness: 100 nm by Ra) using a tape running tester. Let it run. (Running speed 10
00 m / min, 10 passes, winding angle: 60 °, traveling tension: 70 g). At this time, the scratches in the film were observed with a microscope, and if the number of scratches with a width of 2.5 μm or more was less than 2 per tape width, it was judged as excellent, and 2 or more and less than 10 were good, and 10 or more were bad. Although excellent is desirable, even good is practically usable.

(10) Abrasion resistance A laser blade was vertically pressed against a film obtained by slitting a film into a 30 cm long, 1/2 inch wide tape.
A microscopic photograph (× 160) of the width in the depth direction of the shaving powder adhering to the laser blade when running at a load of 500 g / 0.5 inch and a speed of 2 m / min with a 0.5 mm push-in state.
Times). When the width of the shavings in the depth direction is less than 5 μm (◎), 5 μm or more and less than 10 μm (○), 10 μm
The above was defined as (x). It goes without saying that the smaller the adhesion depth of the shaving powder, the better the shaving resistance.

(11) Intrinsic viscosity of copolymerized polyester:
[Η] It was measured at 25 ° C. using an o-chlorophenol solvent.

(12) Easy-adhesive property An easy-adhesive substance is applied on a film substrate, and a magnetic material paint (Dieferacoat CAD-430) is applied to a surface provided with an easy-adhesive layer.
1: 100 parts by weight of Dainichi Seika Kogyo Co., Ltd.) and 1 part by weight of Sumidur N75 (manufactured by Sumitomo Bayer Ltd.) as a curing agent.
It was applied on a tar and dried at 100 ° C. for 5 minutes to form a coating layer.

Separately, Seikabond (E270), an adhesive manufactured by Dainichi Seika Co., Ltd., was applied to a PET film (50 μm) substrate.
/ C-26 = 10/2 (weight ratio)) was applied with a bar coater so as to have a thickness of 8 μm after drying, and dried at 60 ° C. for 1 minute to form a coating layer. Two PET coated with this adhesive
The sample on which the magnetic paint is applied is sandwiched between the substrates, and bonded by a roller so that air bubbles do not enter. Further, one reciprocation is performed between press rolls of a laminator having a surface temperature of 100 ° C. After aging this sample at 40 ° C. for 48 hours or more, a strip-shaped sample having a width of 15 mm was peeled at 90 ° between the easy-adhesion layer and the magnetic paint by a Tensilon tensile tester (pulling speed 200 mm / min) to improve the adhesion. It was measured. It was determined according to the following criteria.

◎: 250 g / 15 mm width or more ○: 200 g / 15 mm width or more, 250 g / 15 mm
Less than width △: 150 g / 15 mm width or more, 200 g / 15 mm
Less than width ×: Less than 150 g / 15 mm width (13) Blocking resistance The easily adhesive layer surface of the film provided with the easily adhesive layer and the biaxially oriented PE
T-film superimposed (overlap area: 3cm × 4
cm) with a load of 500 g / 12 cm ² at 40 ° C. 8
After standing for 24 hours in 0% RH, the shear stress at the overlapped portion was measured using a Tensilon tensile tester at a tensile speed of 20%.
It was measured at cm / min and judged according to the following criteria. ◎:
0 kg / cm ² (none ^{blocking) ○: 0.1kg / cm 2 ~1kg} / cm 2 or less ^{△: 1kg / cm 2 ~3kg /} cm 2 or less ×: 3kg / cm ² or more (14) lubricity (static friction Coefficient μs, dynamic friction coefficient μd) The coefficient of friction between films is ASTM-D-1894-
According to 63, the static friction coefficient μs and the dynamic friction coefficient μd were measured using a surface property measuring device HEIDON-14DR manufactured by Shinto Kagaku Co., Ltd. at a sample moving speed of 200 mm / min and a load of 20.
0 g, measured under the conditions of a contact area of 63.5 mm × 63.5 mm, and an analyzing recorder TYPE: HEIDO
It was recorded and evaluated according to N3655E-99, and the slipperiness was determined according to the following criteria.

○: μs = less than 0.8 △: μs = 0.8 or more to less than 1.3 ×: μs = 1.3 or more (15) Thickness of Coating Layer Hitachi Transmission Electron Microscope Model HU-12 manufactured by Hitachi, Ltd. Was used to observe the ultrathin section of the laminated film to determine the thickness.

(16) Surface Roughness According to JIS-B-0601, using a stylus type surface roughness meter ET-10 manufactured by Kosaka Laboratory Co., Ltd., a cut-off of 0.02
The average surface roughness Ra was determined at 5 mm and the measurement length was 4 mm.

Next, the present invention will be described based on examples, but the present invention is not necessarily limited thereto.

[0077]

EXAMPLES Examples 1 and 2 and Comparative Examples 1 to 5 An ethylene glycol slurry containing crosslinked polystyrene particles having different average particle diameters and spherical silica particles originating from colloidal silica was prepared, and this ethylene glycol slurry was prepared. Was heat-treated at 190 ° C. for 1.5 hours, transesterified with dimethyl terephthalate, polycondensed, and made of polyethylene terephthalate (hereinafter abbreviated as PET) containing 0.01 to 55% by weight of the particles. Pellets were made. Using the pellets, a thermoplastic resin A is prepared, and spherical silica particles having a diameter of 0.03 μm
A PET containing a weight percentage of PET was manufactured, and was designated as a thermoplastic resin B. Each of these polymers was dried under reduced pressure (3 Torr) at 180 ° C. for 3 hours. The thermoplastic resin A is supplied to the extruder 1 and melted at 285 ° C., and the thermoplastic resin B is further added to the extruder 2
Supply, melted at 280 ° C., merges stacking these polymers at the joining block with rectangular lamination portion, cooled and solidified wound around a casting drum having a surface temperature of 30 ° C. using a electrostatic casting method, 2 An unstretched film having a layer structure was produced. At this time, the discharge amount of each extruder was adjusted to adjust the total thickness and the thickness of the thermoplastic resin A layer (however, Comparative Example 4 had a single A layer, Comparative Example 5 had a single B layer). This unstretched film was stretched 4.5 times in the longitudinal direction at a temperature of 80 ° C.
This stretching was performed in four steps with a difference in peripheral speed between two sets of rolls. Each of the uniaxially stretched films was coated in-line on the layer B side so as to have the structure of the layer C shown in Table 1 (in Comparative Example 2, coating was also performed on the layer A side;
In step 4, the monoaxially stretched film was coated on the A-layer single-layer film.
Stretched 4.0 times in the width direction at 100 ° C. at 000% / min, and heat-treated at 200 ° C. for 5 seconds under a tension of 2 kg / m in the longitudinal direction to obtain a total thickness of 10 μm and a thickness of the thermoplastic resin A layer. Various
The applied amount of the changed and heat-treated C layer is 0.05 g /
An m ² biaxially oriented laminated film was obtained. The parameters of the present invention for these films are as shown in Table 1.

The scratch resistance, abrasion resistance and the like of the C layer side of the obtained film were evaluated, and the adhesion to the magnetic layer and the like were evaluated. A magnetic layer was applied to the surface of layer C of the obtained film to form a tape, which was wound under a normal winding tension to form a magnetic tape. Table 1 also shows the evaluation results. When the parameters of the present invention were within the range, each characteristic showed a good value as shown in Table 1, but when it was not, an excellent film satisfying all the characteristics could not be obtained.

The composition of each resin used in the C layer is as follows.

[Resin A] Acrylic copolymer of 65 mol% and 35 mol% of methyl methacrylate and ethyl acrylate. However, carboxylic acid and methylol groups are contained in 2 mol% each.

[Resin B] Terephthalic acid / 5-sodium sulfoisophthalic acid // ethylene glycol / diethylene glycol = 87.5 / 12.5 // 97/3 mol%
A water-soluble copolymerized polyester comprising:

[Resin C] Terephthalic acid / isophthalic acid /
Trimellitic acid / sebacic acid // ethylene glycol /
Water-dispersible copolymerized polyester comprising neopentyl glycol / 1,4-butanediol and trimethylolpropane.

[0083]

[Resin E] Polyoxyethylene glycol (MW = 2000) -tolylene diisocyanate-ethylenediamine dimethylolamine amine salt-based polyurethane.

[0085]

Comparative Example 6 As shown in Table 1, the laminated film having the structure used in Example 1 was wound as it was without laminating the C layer. The evaluation results of this film are shown in Table 1, and the film was inferior in magnetic paint adhesion and the like.

[0087]

[Table 1]

[0088]

Effects of the Invention Film A film A composed mainly of a thermoplastic resin A and the particles as a main component a thermoplastic resin B B
The thickness of the laminated film of the thermoplastic resin A is 0.005 to 5 μm, the average particle diameter of the particles contained in the laminated film is 0.1 to 10 times the laminated thickness,
Film B side of a biaxially oriented thermoplastic resin film having a content of the particles in a laminated film of 0.05 to 50% by weight
A laminated film in which a layer made of at least one aqueous material selected from the group consisting of an acrylic resin, a vinyl resin, a urethane resin, a polyester resin and a graft thereof is laminated on the side, and has a smooth smoothness and an adhesion property. It has excellent properties and abrasion resistance, and is preferably used for magnetic recording materials, various photographic materials, thermal transfer materials, packaging materials, electrical insulating materials, general industrial materials, and the like.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-6-16850 (JP, A) JP-A-2-77431 (JP, A) JP-A-4-358828 (JP, A) JP-A-4-358828 253738 (JP, A) JP-A-6-263902 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (4)

(57) [Claims] 1. A film A mainly composed of a thermoplastic resin A and particles and a film B mainly composed of a thermoplastic resin B.
And the thickness of the film A is 0.005 to
5 μm, the average particle diameter of the particles contained in the film A is 0.1 to 10 times the thickness of the film A, and the content of the particles in the film A is 0.05 to 50% by weight. A layer (C) comprising at least one aqueous material selected from the group consisting of acrylic resin, vinyl resin, urethane resin, polyester resin and their grafts or blocks on the film B side of the axially oriented thermoplastic resin laminated film.
A laminated film comprising: 2. A method of applying an aqueous coating liquid containing the aqueous substance in a state where the oriented crystallization of the thermoplastic resin film has not been completed, and then performing drying, stretching and heat treatment to complete the oriented crystallization. The laminated film according to claim 1, characterized in that: 3. The laminated film according to claim 1, wherein a magnetic paint is further laminated on the C layer. 4. The film base is made of ethylene terephthalate.
4. The polymer according to claim 1, wherein said polymer comprises ethylene or ethylene 2,6-naphthalate as a main component.
3. The laminated film according to item 1.