JPH09169089A - Laminated film - Google Patents

Abstract

(57) [PROBLEMS] To provide a laminated film which is excellent in slipperiness, abrasion resistance and blocking resistance and which is useful for a base film of a magnetic recording medium, a general industrial film, and the like. SOLUTION: A coating film prepared by applying an aqueous coating solution containing a binder resin and fine particles having a core hair structure having an average particle size of 5 to 2000 nm to at least one surface of a polyester film, and drying and stretching the coating film is provided. Laminated film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film, and more particularly to a laminated film which is excellent in slipperiness, abrasion resistance and blocking resistance and is useful as a base film for magnetic recording media, a general industrial film and the like.

[0002]

Films made of polyester such as polyethylene terephthalate and polyethylene naphthalate are used as films for magnetic recording materials such as magnetic cards and magnetic tapes, and also for general industrial materials such as packaging materials, photographic films, graphic films and process materials. Widely used as a film. However, since the film surface of the polyester film is flat, the slipperiness between the films is poor and there is a drawback that wrinkles are formed when wound into a roll.

In order to solve this drawback, a method for forming protrusions on the film surface by blending inorganic fine particles or organic fine particles with polyester, or providing a slippery coating film containing inorganic fine particles or organic fine particles on the film surface is provided. Method is used.

However, it is difficult to uniformly disperse the fine particles in the film by the method of blending the inorganic fine particles and the organic fine particles with the polyester, and thus it is difficult to obtain a film having uniform surface characteristics.

Further, a method of providing a slippery coating film in which inorganic fine particles (for example, fine particles of silica, alumina, titanium oxide, etc.) and organic fine particles (for example, fine particles of crosslinked acrylic resin or crosslinked polystyrene) are mixed on the surface of the film is fine particles. Is easily scraped from the coating film, and the scraped fine particles cause various troubles. To improve the sharpness of the fine particles, a method of adding a binder resin as a component of the slippery coating film is used, but in this method, the films wound in a roll block each other and the film is taken out from the roll. In addition, new problems such as defects on the film surface and film breakage occur.

Further, in order to improve the slipperiness of the film, a method of forming a coating film having projections composed of organic fine particles having a shell-core structure on the surface of the film (JP-A-7-23).
No. 2420) has been proposed. However, even with this method, fine particles are easily scraped off from the coating film when a severe frictional force is applied to the surface of the coating film, and improvement thereof is desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art and to provide a laminated film excellent in slipperiness, abrasion resistance and blocking resistance.

[0008]

According to the present invention, such an object of the present invention is to provide an aqueous coating liquid containing a binder resin on at least one surface of a polyester film and fine particles having a core hair structure having an average particle diameter of 5 to 2000 nm. It is achieved by a laminated film provided with a coating film prepared by coating, drying and stretching. Hereinafter, the present invention will be described in detail.

[Base Film] In the present invention, a polyester film is used as the base film. The polyester constituting the base film is a linear polyester composed of a dicarboxylic acid component and a glycol component.

Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, 4,4'-diphenyldicarboxylic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid. Among them, terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferable because they have excellent mechanical properties and thermal properties of the polyester film.

Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol. , 1,4-cyclohexanedimethanol, polyethylene glycol, polytetramethylene glycol, dipropylene glycol, triethylene glycol, bisphenol, and the like. In particular, ethylene glycol is used for the mechanical properties and thermal properties of the polyester film. It is preferable because it is excellent.

As the polyester, polyethylene terephthalate or polyethylene-2,6-naphthalate can be preferably exemplified. The polyethylene terephthalate or polyethylene-2,6-naphthalate may be a polyester obtained by copolymerizing the above-mentioned dicarboxylic acid component or glycol component, and the polyester may be a polyfunctional carboxylic acid component having a functionality of 3 or more or a polyol component. It may be a polyester copolymerized in a small amount in a linear range (for example, 5 mol% or less). Such a polyester can be produced by a conventional method, and it is preferable that the average molecular weight is 10,000 or more because the mechanical properties of the film will be good.

The above polyester may contain organic or inorganic fine particles as a lubricant, for example, in an amount of 0.001 to 5% by weight in order to improve the slipperiness of the film. Specific examples of such fine particles include calcium carbonate, calcium oxide, titanium oxide, graphite, kaolin, silica, alumina, silicon oxide, zinc oxide, carbon black, silicon carbide, tin oxide, acrylic resin particles, crosslinked polystyrene resin particles, melamine resin. Particles and crosslinked silicone resin particles can be preferably mentioned.

In addition to the above-mentioned fine particles, antistatic agents, antioxidants, organic lubricants, catalysts, colorants, pigments, optical brighteners, plasticizers, crosslinking agents, lubricants, ultraviolet absorbers, other resins, etc. are required. Can be added according to

The polyester film of the present invention is
It can be manufactured by a conventionally known method. For example, the polyester is melted and cast on a cooling drum to obtain an unstretched film, and then the unstretched film is stretched 2 to 7 times in the machine direction to form a uniaxially stretched film, and the uniaxially stretched film is coated with an aqueous coating solution. After that, a biaxially stretched laminated film can be obtained in which the film is applied while being dried and stretched 2 to 7 times in the transverse direction. The stretching temperature of the film may be a temperature of the second-order transition temperature (Tg) of the polyester of not less than -10 ° C, and the biaxially stretched laminated film may be further stretched in the machine direction and / or the transverse direction, if necessary. it can. The area stretching ratio of the biaxially stretched film is 8 times or more,
Further, it is desirable to set it to 9 times or more, and the upper limit of the area stretching ratio depends on the use of the film, but it is up to 35 times, especially 3 times.
It is preferably up to 0 times. The oriented crystallization can be completed by heat treatment after stretching.

[Fine Particles of Core Hair Structure] In the present invention, an aqueous coating liquid containing a binder resin and fine particles of core hair structure having an average particle diameter of 5 to 800 nm is applied to at least one surface of the polyester film, A coating film formed by drying and stretching is provided.

The fine particles having a core hair structure are fine particles in which hair made of graft chains (copolymerized macromer chains) is formed on the surface of resin fine particles forming a core.

The fine particles having such a core-hair structure can be prepared by any method, and can be obtained, for example, by graft-polymerizing a macromonomer to the polymer constituting the core.

Examples of the polymer constituting the core include thermosetting resins such as urea resin, melamine resin, phenol resin, epoxy resin, unsaturated polyester resin, alkyd resin and urethane resin. In particular, highly crosslinked and / or crosslinkable polymers of the same kind or different kinds such as divinylbenzene type resin, polystyrene type resin and acrylic type resin are preferable. Examples of the highly crosslinked polymer include a styrene / divinylbenzene binary copolymer and a styrene / divinylbenzene / ethylvinylbenzene terpolymer. Examples of the crosslinkable polymer include a self-crosslinking acrylic copolymer that can form a three-dimensional network structure. Such a self-crosslinking acrylic copolymer is obtained by copolymerizing a functional group-containing vinyl polymerizable monomer, a hydrocarbon vinyl polymerizable monomer, a hydrocarbon-based non-conjugated divinyl polymerizable monomer, etc. Examples of the functional group-containing vinyl-polymerizable monomer that can be used include acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylol acrylamide, N-butoxymethyl acrylamide, diacetone acrylamide,
2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate and the like can be mentioned.

Examples of the above macromonomers include compounds represented by the following general formulas (1) to (9).

[0021]

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In the formula (1), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, p is an integer of 0 to 20 and n is an integer of 1 to 100. Indicates.

[0023]

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In the formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 100.

[0025]

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In the formula (3), R ⁴ is hydrogen atom, hydroxyl group, N
(CH ₃ ) ₃ OH group or N (C ₂ H ₅ ) ₃ OH group, wherein R ⁵ and R ⁶ are independently a hydrogen atom or a carbon number of 1
-10 is an alkyl group, m is an integer of 0-100, n
Indicates an integer of 1 to 100.

[0027]

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In the formula (4), R ⁷ and R ⁸ independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 100, and n is an integer of 1 to 100. Indicates.

[0029]

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In the formula (5), R ⁹ and R ¹⁰ independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 100, and n is an integer of 1 to 100. Indicates.

[0031]

[Chemical 6]

In the formula (6), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, m is an integer of 0 to 100,
n shows that it is an integer of 1-100.

[0033]

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In the formula (7), R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 100,
n shows that it is an integer of 1-100.

[0035]

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In the formula (8), R ¹³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 100.

[0037]

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In the formula (9), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹⁵ represents the following formulas (10) to
The group shown by Formula (12) is shown, and n shows that it is an integer of 1-100.

[0039]

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[0040]

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In the formula (11), R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0042]

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In the formula (12), R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Specific examples of such macromonomers are shown in the following formulas (1-1) to (9-3).

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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The average particle diameter of the core hair structure fine particles in the present invention is 5 to 1000 nm. Average particle size is 100
If it exceeds 0 nm, the surface irregularities of the film become too large, and the surface characteristics become poor when used as a base film of a magnetic recording medium or a general industrial film. Further, if the average particle size is less than 5 nm, the slipperiness of the laminated film becomes poor.

[Binder Resin] As the binder resin in the present invention, for example, polyester resin, acrylic resin, acrylic modified polyester resin, epoxy resin,
Examples thereof include vinyl resins, polyurethane resins, polyether resins, cellulosic resins, water-soluble silicone resins, and the like, with polyester resins, acrylic resins, and acrylic modified polyester resins being particularly preferred.

The above polyester resin is a polyester composed of a polyvalent carboxylic acid component and a polyvalent hydroxy compound component. Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid and 5-Nasulfoisophthalic acid. Sulfonic acid such as 5-Nasulfoisophthalic acid. Those containing a dicarboxylic acid having a base as a copolymerization component are preferable because the polyester resin is easily dissolved in hot water or a solvent. Examples of the polyvalent polyvalent hydroxy compound component include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, and bisphenol A / alkylene oxide adduct. It is preferable that the polyester resin is a copolymer polyester composed of these polyvalent carboxylic acid component and polyvalent hydroxy compound component because the adhesion between the coating film and the base film can be adjusted to an appropriate level.

Such polyester resin can be prepared by a conventional method and has an average molecular weight of 10,000 to 50,000.
A value of 0 is preferable because the coating film has good abrasion resistance and good blocking resistance. The polyester resin preferably has a second-order transition point of 20 ° C. or higher and 110 ° C. or lower.

The above acrylic resin is an acrylic copolymer obtained by polymerizing an acrylic acid ester monomer. Examples of the acrylic acid ester-based monomer include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl crotonic acid, glycidyl methacrylate, 2-hydroxyethyl acrylate. , Acrylic acid 2
-Ethylhexyl and the like can be mentioned.

This acrylic copolymer comprises at least one of the above acrylic ester monomers and acrylamide, methacrylamide, acrylic acid, methacrylic acid, sodium acrylate, potassium methacrylate, ammonium acrylate, N- It may be a copolymer obtained by polymerizing an acrylic acid-based monomer such as methylol acrylamide or N-methoxymethyl acrylamide.

In addition to the above, monomers such as vinyl chloride, vinyl acetate, styrene, vinyl ether, butadiene, isoprene, and sodium vinyl sulfonate can be used as a copolymerization component in the acrylic copolymer.

The acrylic copolymer includes acrylate component, methacrylate component, acrylic acid component, acrylamide component, 2-hydroxyethyl acrylate component,
It is preferable that a hydrophilic component such as an N-methylol acrylamide component be contained as a copolymerization component because the dispersibility and solubility in the aqueous coating solution will be good. Further, it may be a copolymer having a functional group in the side chain of the molecule.

The acrylic resin has a second-order transition point of 40 ° C.
It is preferably 100 ° C. or lower and 100 ° C. or lower. Such an acrylic copolymer uses a hard component such as methyl methacrylate or ethyl methacrylate as a main component, and a soft component such as an acrylate ester as a copolymerization component such that the secondary transition point is within the above range. It can be obtained by copolymerizing with. Further, the secondary transition point of the acrylic copolymer can be adjusted by using a component having a methylol group, a methoxymethyl group or the like as a copolymerization component and crosslinking these groups.

The average molecular weight of the acrylic copolymer is 10,
It is preferably 000 to 500,000 because the coating film has good abrasion resistance and good blocking resistance.

The above acrylic modified polyester resin is
A modified copolymer obtained by polymerizing the above-mentioned polyester resin with the above-mentioned acrylic acid ester-based monomer and / or acrylic acid-based monomer, for example, the above-mentioned acrylic acid is added to the polyester resin in an aqueous liquid. It can be obtained by graft-polymerizing an ester monomer and / or an acrylic acid monomer using a radical initiator. This modified copolymer may have a functional group on the side chain of the molecule. The modified copolymer has an average molecular weight of 10,000 to
It is preferably 500,000 because the coating film has good abrasion resistance and good blocking resistance. Also,
The modified copolymer preferably has a second-order transition point of 30 ° C. or higher and 100 ° C. or lower. The secondary transition point is 20 ° C or higher 1
Acrylic-modified polyester resin at 50 ° C or lower is a hard component such as methyl methacrylate or ethyl methacrylate and a soft component such as acrylate ester with respect to the copolyester having a secondary transition point of 20 ° C or higher and 150 ° C or lower. The secondary transition point of acrylic modified polyester resin is 20 ℃
It can be obtained by copolymerizing at a ratio of not lower than 150 ° C. and not higher than 150 ° C.

[Aqueous Coating Liquid] In the present invention, an aqueous coating liquid containing the binder resin and fine particles having a core hair structure is used for coating a coating film on the base film. This aqueous coating liquid is used as an aqueous liquid such as an emulsion and a dispersion, but if necessary, a dispersant, an emulsifier, a stabilizer and the like can be used.

In addition to the above-mentioned components, the aqueous coating liquid may further include fillers, surfactants, antioxidants, antistatic agents, colorants, pigments, optical brighteners, plasticizers, crosslinking agents, lubricants, and ultraviolet absorbers. Etc. can be added.

The ratio of the binder resin to the core / hair structure fine particles is 65 to 97% by weight of the binder resin and the core / hair structure fine particles of 3 to 35% by weight based on the total solid components in the aqueous coating liquid. It is preferable. More than 97% by weight of binder resin and 3% by weight of fine particles with core hair structure
If the amount is less than 60%, the slipperiness of the coating film may be insufficient, and if the binder resin is less than 65% by weight and the fine particles of the core / hair structure exceed 35% by weight, the abrasion resistance of the coating film may be insufficient. .

The aqueous coating solution usually has a solid content concentration of 1 to 30% by weight, and is preferably used at 2 to 20% by weight in order to improve the drying property and coatability of the aqueous coating liquid.
The aqueous coating solution may contain a small amount of organic solvent.

[Coating of coating film] In the present invention, the coating film is coated by coating the above-mentioned aqueous coating liquid on at least one side of the polyester film, followed by heat drying and stretching. As the method, any known coating method can be applied, for example, a gravure coating method, a reverse roll coating method, a die coating method, a kiss coating method, a reverse kiss coating method, an offset gravure coating method, a Mayer bar coating method, a roll brush method, a spray. The coating method, the air knife coating method, the impregnation method, the curtain coating method and the like can be applied alone or in combination. The wet coating amount of the aqueous coating liquid is 1 to 1 m ² of the running film.
20 g, especially 2 to 12 g is preferred. When the coating amount is within this range, the aqueous coating liquid is easily dried and coating spots are less likely to occur, which is preferable.

The polyester film to which the aqueous coating solution is applied in the present invention is, for example, an unstretched film obtained by heat-melting polyester to form a film as it is; the unstretched film in the longitudinal direction (longitudinal direction) or the lateral direction (width direction). A uniaxially stretched film which has been stretched in one of the two directions; a biaxially stretched film which is obtained by sequentially stretching a uniaxially stretched film in the longitudinal direction or the transverse direction in the transverse direction or in the longitudinal direction (further stretchable), or an unstretched film in the longitudinal direction. And a biaxially stretched film which is simultaneously stretched in two transverse directions (which can be further stretched);
A biaxially stretched heat-treated film in which the biaxially stretched film is heat-set and / or heat-relaxed (further stretchable) can be mentioned.

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

The aqueous coating solution is applied to a stretchable film of the polyester films, for example, a uniaxially stretched film, particularly a longitudinal uniaxially stretched film, and dried and stretched to obtain a film having strong adhesion. And is preferable because the laminated film can be produced efficiently. For example, polyester is heat-melted, extruded into a sheet and cooled to obtain an unstretched film, and the unstretched film is stretched in the machine direction to form a uniaxially stretched film, and then an aqueous coating solution is applied and dried to obtain a transverse direction. The film is stretched, and if necessary, re-stretched in the longitudinal and transverse directions and then heat-treated to form a laminated film having a coating film applied thereon.

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

[Drying and Stretching Conditions] After applying the aqueous coating liquid in the present invention, the drying temperature is preferably 70 to 130 ° C. because the coating liquid can be dried quickly. The heating for this drying can also serve as the heating during the process of stretching the polyester film. The stretching temperature of the polyester film may be 80 to 170 ° C, and the heat treatment temperature may be 170 to 260 ° C.

[0083]

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

1. The coefficient of static friction at 22 ° C measured with a friction coefficient measuring device by matching the coated and uncoated surfaces of the slippery film (in the case of films without coating, the uncoated surfaces). Was measured.

2. Scraping resistance: The coated film surface of the film cut to a width of 13 mm (or the uncoated surface in the case of a film without a coated film) has a diameter of 5
Apply to a stainless steel pin of mm, wrap angle 180
After repeatedly running three times for 150 m under the conditions of a load of 120 g and a speed of 50 m / min, the amount of shavings accumulated on the pins was observed and evaluated as follows. A: Almost no powder is observed. … Good scraping resistance B: Slight powder is recognized …… Shaving resistance is slightly good C: Powder is clearly recognized …… Scrap resistance is poor

3. Blocking resistance A coated film surface and a non-coated surface of a film with a width of 50 mm (coated
If the film does not have a coating, how is the surface not coated?
)), 50 ℃ × load 50kg / cm ^TwoCondition
After holding for 12 hours under, peeling strength of the mating surface
It was measured at a speed of 200 mm / min and evaluated as follows. A: Peel strength ≦ 7 g (good blocking resistance) B: 7 g <Peel strength ≦ 12 g (slightly good blocking resistance) C: 12 g <Peel strength (poor blocking resistance)

[Example 1] Polyethylene terephthalate having an intrinsic viscosity of 0.64 (containing 0.4% by weight of silica fine particles having an average particle size of 0.1 µm) was melted and cast on a cooling drum, and then 3 in the longitudinal direction. The film was stretched 6 times to give a uniaxially stretched film. On one surface of this uniaxially stretched film, a hair having an average particle diameter of 50 nm obtained by graft-polymerizing the macromonomer (n = 50) represented by the formula (1-1) as a hair portion to the crosslinkable polystyrene of the core portion. Core type fine particles (P
-1) 20 parts by weight; as a binder resin, a dicarboxylic acid component is a terephthalic acid component (43 mol%), an isophthalic acid component (46 mol%) and a 5-Ksulfoisophthalic acid component (11 mol%), and a glycol component is ethylene. Copolyester of glycol component (47 mol%), diethylene glycol component (2 mol%), neopentyl glycol component (45 mol%) and 1,4-butanediol component (6 mol%) (B-1, average molecular weight: 20, 00
0) 70 parts by weight and ethylene oxide / propylene oxide / block copolymer (average molecular weight: 3,900)
A 3 wt% aqueous coating solution having a composition of 10 parts by weight was applied by a gravure coater, dried at 110 ° C., and then applied in a lateral direction to 3.
Stretched 8 times and further heat treated at 225 ℃ to give a total thickness of 50μ
m, and a coating film thickness of 0.20 μm was prepared.
The properties of this laminated film are shown in Table 1.

[Comparative Example 1] A biaxially stretched film was obtained in the same manner as in Example 1 except that no coating film was applied. Table 1 shows the characteristics of this film.

[Examples 2 to 8 and Comparative Example 2] Laminated films were obtained in the same manner as in Example 1 except that the composition and thickness of the coating film were changed as shown in Table 1. The characteristics of this laminated film are shown in Table 1.

[0090]

[Table 1]

As is clear from the results shown in Table 1, the laminated film of the present invention was excellent in slipperiness, abrasion resistance and blocking resistance.

[P-2] and [P-3] in the coating composition shown in Table 1 represent the following fine particles. [P-2]: Average particle obtained by graft-polymerizing the macromonomer (m = 20, n = 30) represented by the above formula (3-2) as a hair part to the crosslinkable polymethylmethacrylate of the core part. Hair / core type fine particles having a diameter of 100 nm [P-3]: Fine particles having a shell / core structure (average particle size 100 nm) in which a core portion is made of a crosslinkable acrylic resin and a shell portion is made of a thermoplastic acrylic resin.

[0093]

In the present invention, since a coating film using an aqueous coating solution containing a binder resin and fine particles having a core / hair structure is applied on at least one side of a polyester film, slipperiness, abrasion resistance and abrasion resistance are improved. A laminated film excellent in blocking property can be obtained.

Claims (3)

[Claims] 1. A coating film prepared by coating a polyester resin film with an aqueous coating solution containing a binder resin and fine particles having a core hair structure having an average particle size of 5 to 2000 nm, and drying and stretching the coating film. Laminated film provided. 2. An aqueous coating solution comprising 65 to 97% by weight of a binder resin as solids and 3 to 3 of fine particles having a core hair structure.
The laminated film according to claim 1, wherein the laminated film contains 5% by weight. 3. The core / hair structure fine particles are urea resin,
At least one thermosetting resin selected from the group consisting of melamine resin, phenol resin, epoxy resin, unsaturated polyester resin, alkyd resin and urethane resin,
The laminated film according to claim 1, which is obtained by graft polymerization of a macromonomer.