JP3072932B2 - Plastic film laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic film laminate, and more particularly to a plastic film laminate having excellent adhesion, transparency and antistatic properties.

[0002]

BACKGROUND OF THE INVENTION Polyethylene terephthalate biaxially oriented films have excellent transparency, dimensional stability, mechanical properties, electrical properties, and chemical resistance. It is used as a support for drawing materials and photographic materials. However, when polyethylene terephthalate or the like is used as the support, since the support itself is an insulator, the electrostatic charge is remarkable and the surface is highly crystallized, so that various paints, adhesives, inks and photosensitive materials are used. Had the disadvantage of poor adhesion. Processing of the polyester surface has been carried out in order to eliminate such drawbacks as antistatic properties and poor adhesion.

For example, in order to improve antistatic performance,
As an antistatic agent in the support, for example, metal powder, tin oxide
A method of kneading or applying an antimony-based conductive agent, a cationic surfactant having an antistatic ability, a polymer having a sulfonic acid represented by polystyrenesulfonic acid or a salt thereof, or the like has been adopted. In order to improve the adhesiveness, a method of subjecting the film surface to a physical treatment such as corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, flame treatment, electron beam irradiation, or an acid, alkali, amine aqueous solution, trichloroacetic acid, etc. And the like.

[0004]

However, when a tin oxide-antimony-based conductive agent is used, there is a problem that if the content is increased to obtain conductivity, the transparency of the base deteriorates. Also, when a surfactant is used, it bleeds out to the surface or interface over time and the transparency is reduced, and the conductivity is lost when treated at a high temperature when applied to the base and dried. There was a problem. When a polymer having polystyrene sulfonic acid or a salt thereof is used, since the softening temperature is high, when the coated or kneaded base is stretched, stress concentrates on that portion and the transparency of the base is lost. was there.

[0005] When a physical treatment is performed to improve the adhesion, there is a problem that the effect is deactivated with the passage of time. Further, when the chemical treatment is performed, there is a problem in environmental hygiene depending on a chemical used, and there is a problem that the chemical cannot be disposed as it is.

As a method of improving these disadvantages, for example, Japanese Patent Application Laid-Open No. 64-9242 discloses a technique using a combination of an acrylic polymer and a sulfonated polystyrene, but under a low humidity of 20% or less. Did not provide sufficient conductivity. Therefore, when the film thickness is increased in order to impart antistatic properties, there is a drawback that cracks occur due to heat treatment for crystallization of the base after biaxial stretching.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a plastic film laminate having easy adhesion, transparency, and excellent conductivity even under low humidity. It is in.

[0008]

An object of the present invention is to provide at least one layer containing at least a polar polymer having a conductive property and polyglycerin on an unstretched or uniaxially stretched thermoplastic resin film. This is achieved by a plastic film laminate characterized in that it has been stretched at least uniaxially.

As the polyester film of the substrate used in the present invention, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene naphthalate film and the like can be mentioned. Among them, a polyethylene terephthalate film is preferable.

[0010] These polyesters may be used alone, or may be appropriately mixed if necessary, and are usually melt-extruded or dissolved in a solvent and cast to obtain a polyester film (base film).
Is obtained. The base film used is uniaxially stretched if necessary.

The polar polymer having a conductive property used in the present invention includes sulfonic acid groups, sulfate groups,
Examples include polymers having at least one polar group selected from quaternary ammonium salts, tertiary ammonium salts, and carboxyl groups. Especially sulfonic acid group, carboxyl group,
A polymer having a sulfate group or / and a salt thereof is preferred. The polar group requires at least 5 mol% per polymer molecule. In the polar polymer having the conductive performance,
Hydroxyl groups, amino groups, epoxy groups,
It may contain an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, and a vinyl sulfone group.

The molecular weight of the polymer is preferably 500 or more, more preferably 700 to 50,000.

Hereinafter, specific examples of the polar polymer having a conductive property used in the present invention will be described, but the present invention is not limited thereto.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

Among the repeating units constituting the conductive polymer of the present invention, particularly preferred repeating units include the following, but the present invention is not limited thereto.

[0023]

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The polyglycerin used in the present invention is
General formula (I) below General formula (I) (N is an integer of 2 or more). In the present invention, n in the formula is preferably an integer of 2 or more and 20 or less.

In the present invention, the amount of polyglycerin used is preferably 0.1% by weight or more and 50% by weight or less in the total solid content of the layer containing the polar polymer having conductive properties and polyglycerin.

In the present invention, several kinds of polyglycerins, which are compounds having different numbers of n, can be used in combination. In this case, the average value of the number n is preferably 2 or more and 20 or less.

The ratio of the polar polymer having conductive properties and polyglycerin in the coating solution of the present invention is from 30:70 by weight.
The ratio is preferably 95: 5, more preferably 50:50 to 90:10.

In the present invention, a water-soluble polymer may be further contained.

The water-soluble polymer used in the present invention includes, for example, a synthetic water-soluble polymer and a natural water-soluble polymer, and any of them can be preferably used in the present invention. Among them, examples of the synthetic water-soluble polymer include those having a nonionic group in the molecular structure, those having an anionic group, and those having a nonionic group and an anionic group. Examples of the nonionic group include an ether group, an ethylene oxide group, and a hydroxy group, and examples of the anionic group include a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and the like. Is raised. Examples of the natural water-soluble polymer include those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure.

As the water-soluble polymer, any of a synthetic water-soluble polymer and a natural water-soluble polymer, those having an anionic group and those having a nonionic group and an anionic group can be preferably used. The water-soluble polymer used in the present invention includes water at 20 ° C.
There is no particular limitation as long as it dissolves at least 0.05 g per 100 g, but preferably at least 0.1 g.

The natural water-soluble polymer is described in detail in the comprehensive technical data collection of the water-soluble polymer water-dispersible resin (publishing department of the Management Development Center), but it contains lignin, starch, brulan, cellulose, alginic acid, dextran, Dextrin, guar gum, gum arabic, glycogen,
Laminaran, lichenin, nigeran and the like, and derivatives thereof are preferred.

As the derivative of the natural water-soluble polymer, sulfonated, carboxylated, phosphorylated, sulfoalkylated, or carboxyalkylated, alkylphosphorylated, and salts thereof are particularly preferable.

In the present invention, the natural water-soluble polymer is 2
They may be used in combination of two or more.

Among the natural water-soluble polymers, glucose polymers and derivatives thereof are preferred. Among the glucose polymers and derivatives thereof, starch, glycogen, cellulose, lichenin, dextran, nigeran and the like are preferred, and dextran is particularly preferred. And derivatives thereof are preferred.

Dextran is obtained by converting α-1,6-linked D-
It is a polymer of glucose and can be generally obtained by culturing dextran-producing bacteria in the presence of saccharides.Leukonostock, mestranoides, etc. And can be obtained. In addition, these native dextrans can be reduced to a desired molecular weight by a partial decomposition polymerization method using an acid or an alkaline enzyme to obtain those having an intrinsic viscosity in the range of 0.03 to 2.5.

The dextran-modified product is a dextran sulfate in which a sulfate group is present in an ester bond in a dextran molecule, or a salt thereof, a carboxyalkyldextran in which a carboxyalkyl group is present in an ether bond in a dextran molecule, or dextran. A carboxyalkyl dextran sulfate in which a sulfate group is an ester bond and a carboxyalkyl group is an ether bond in the molecule, and a salt thereof; a dextran phosphate ester and a salt thereof in which a phosphate group is present in the dextran molecule by an ester bond; Examples thereof include hydroxyalkyl dextran in which a hydroxyalkyl group is introduced into a dextran molecule.

Among these dextrans and modified products thereof, particularly preferred is the latex dispersion stability.
Dextran sulfate, carboxyalkyl dextran sulfate, and dextran phosphate into which an anionic group has been introduced, and dextran sulfate is most preferred.

In the synthesis of these dextran-modified products, the above-mentioned dextran is used as a raw material, and a dextran sulfate ester is obtained by reacting with a sulfating agent such as chlorosulfonic acid in the presence of a basic organic solvent such as pyridine or formamide. it can. Further reaction with a carboxyalkylating agent such as monochlorocarboxylic acid gives carboxyalkyldextran sulfate.

The carboxyalkyl dextran can be obtained by reacting dextran as a raw material with a carboxyalkylating agent such as monochlorocarboxylic acid under an alkali. Further, by reacting this with a sulfurizing agent such as chlorosulfonic acid in the presence of a basic solvent such as pyridine or formamide, a carboxyalkyldextran sulfate can be obtained. In addition, oxides of alkali metals such as sodium and potassium,
By reacting an oxide or hydroxide of an alkaline earth metal such as calcium or magnesium, ammonia or the like, salts of dextran sulfate or carboxyalkyl sulfate can be obtained respectively.

Since dextran has three hydroxyl groups that can be substituted per anhydroglucose unit, it can theoretically substitute a sulfate group and a carboxyalkyl group having a maximum degree of substitution up to 3, but the reaction conditions are selected. By doing so, one having an arbitrary degree of substitution can be produced within the range of the degree of substitution of 3 or less. However, the sum of the degree of substitution between the sulfate group and the carboxyalkyl group cannot exceed 3.

The carboxyalkyl dextran, dextran sulfate, and carboxyalkyl dextran sulfate thus produced can be produced in various types depending on the intrinsic viscosity of the raw material dextran and various combinations of the degree of substitution of the sulfate and the degree of carboxyalkyl substitution of the product. Can be manufactured.

The cellulose derivative used in the present invention is
A typical example is a structure in which at least one hydrogen atom of a hydroxyl group of cellulose is replaced by an alkyl group, a hydroxyalkyl group and / or an acyl group. Specific examples of the cellulose derivative include hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose hexahydrophthalate, methylcellulose, ethylcellulose, and propylcellulose.

In the present invention, a polyvinyl alcohol derivative can be further contained. Specific examples of the polyvinyl alcohol derivative used in the present invention include, for example, polyvinyl alcohol having a saponification degree of 20 to 50%,

[0044]

Embedded image Etc.

Acrylamide, methacrylamide,
Examples of the monomer unit of an acrylic ester having a hydroxyl group and a methacrylamide having a hydroxyl group include those represented by the following general formula [I].

[0046]

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Examples of the monomer giving the monomer unit represented by the above general formula [I] include acrylamide, p-hydroxyphenyl methacrylamide, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and the like.

In the present invention, copolymers containing acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylic ester having a hydroxyl group or methacrylester having a hydroxyl group as monomer units are as follows: It is sufficient that at least one of these monomer units is contained. Further, the ratio of these monomer units in the copolymer is preferably 30% by weight or more. Specific examples of the homopolymer or copolymer containing at least one of the above structural units include the following.

The numbers in parentheses indicate the weight ratio of the monomer units. A- [1] Polyhydroxyethyl methacrylate A- [2] Poly-p-hydroxyphenyl methacrylamide A- [3] Copolymer of hydroxyethyl methacrylate / butyl acrylate / styrene (40:15:35) A- [4] ] Hydroxyethyl methacrylate / butyl acrylate / acrylic acid / styrene (40: 25: 10: 2
Copolymer of 5) A- [5] Copolymer of p-hydroxyphenyl methacrylamide / acrylonitrile / butyl acrylate / acrylic acid (20: 20: 40: 20) A- [6] Butyl methacrylate / acrylic acid / styrene Copolymer of (25:50:25) A- [7] Copolymer of methyl methacrylate / butyl acrylate / acrylic acid / styrene (10: 10: 50: 30) A- [8] Butyl acrylate / acrylic acid / Copolymer of hydroxyethyl acrylate (30:30:40) A- [9] Butyl acrylate / methacrylic acid (50:
50) Copolymers These may be used alone or as a mixture of two or more.

A crosslinking agent may be added to the coating layer working liquid used in the present invention. Examples of the crosslinking agent used in the present invention include an epoxy compound, an aziridine compound, a blocked isocyanate compound, and a blocked methylol compound, and an epoxy compound, a blocked isocyanate compound, and an aziridine compound having two or more functional groups are preferable. The crosslinking agents may be used in combination.

The epoxy compound used in the present invention is not particularly limited as long as it is a compound having an epoxy group, but is preferably a compound having two or more epoxy groups.

Specific examples of typical epoxy compounds are shown below. C-1 sorbitol polyglycidyl ether C-2 sorbitan polyglycidyl ether C-3 polyglycerol polyglycidyl ether C-4 diglycerol polyglycidyl ether C-5 glycerol polyglycidyl ether C-6 ethylene glycol diglycidyl ether C-7 polyethylene glycol Diglycidyl ether C-8 Propylene glycol diglycidyl ether C-9 Polypropylene glycol diglycidyl ether Denacol series (manufactured by Nagase Kasei Kogyo Co., Ltd.) such as Denacol EX-614B and EX-651
A, EX-512, EX-521, EX-421, EX-313, E
X-830, EX-841, EX-861, EX-911, EX-92
0 etc. can be easily obtained. In the present invention, two or more epoxy compounds may be used in combination.

As the blocked isocyanate compound,
Those having two or more functionalities are preferable, and for example, there is an elastron series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a commercial product,
Elastron H-3, E-37, C-9, F-29, H-3
8, W-11, MF-25, BN-08, BN-11, etc., but the present invention is not limited thereto. Further, two or more kinds of blocked isocyanate compounds may be used in combination. A reaction promoting catalyst may be used to further promote the reaction. Examples of the catalyst include Elastron Catalyst 64 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), but are not limited thereto.

The aziridine compound is preferably a bifunctional or higher functional one, and particularly preferably a bifunctional or trifunctional one having a molecular weight of 1,000 or less.

Specific examples of typical aziridine compounds are shown below, but the present invention is not limited thereto.

[0056]

Embedded image Two or more aziridine compounds may be used in combination.

The surfactants used in the coating layer working fluid used in the present invention include the following general formulas D- [I] and D- [I].
[II], D- [III], D- [IV], D- [V], D-
[VI] and the like.

[0058]

Embedded image [Wherein, R ₁ represents an alkyl group having 1 to 18 carbon atoms, R ₂ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, l ₁ represents 0 or 1, and n ₁ represents 0 ~ 5
M ₁ represents an integer of 0 to 4, m ₁ represents an integer of 0 to 4, and M ₁ represents a cation of an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a quaternary ammonium salt ion. ]

[0059]

Embedded image (Wherein, R ₃ represents an alkyl group or an alkenyl group having 6 to 20 carbon atoms, l ₂ represents 0 or 1, n ₂ represents an integer of 0 to 50, and m ₂ represents an integer of 0 to 4 And M
₂ has the same meaning as M _{1 in} formula D- [I]. Hereinafter, specific examples of the anionic surfactant represented by the general formula D- [I] or D- [II] will be shown, but the present invention is not limited thereto.

[0060]

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[0061]

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[0062]

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[0063]

Embedded image (In the formula, R ₅ represents an alkyl group or an alkenyl group having 8 to 25 carbon atoms, and n ₄ , n ₅ and n ₆ each represent an integer of 5 to 100, provided that n ₄ and n ₅ , N ₆ is 5 or more.)

[0064]

Embedded image (In the formula, n ₇ and n ₉ represent an integer of 5 to 100, and n ₈ represents an integer of 1 to 50.)

[0065]

Embedded image (In the formula, R ₆ represents an alkyl group or an alkenyl group having 6 to 20 carbon atoms, and n ₁₀ and n ₁₁ represent an integer of 5 to 100 in total, provided that at least 1 of n ₁₀ and n ₁₁ One is 5 or more.)

The following formulas D- [III] to D-
Specific examples of the nonionic surfactant represented by [VI] are shown below, but the present invention is not limited thereto.

[0067]

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[0068]

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The content of the above-mentioned surfactant was determined in the
It is preferable to add 0.01 to 50 g per kg, particularly preferably 0.05 to 10 g.

A matting agent or the like may be added to the coating layer processing liquid according to the present invention.

Further, the plastic film laminate of the present invention is prepared by applying the coating layer processing liquid according to the present invention to at least one surface of the plastic film before the completion of the orientation crystallization, drying, and then stretching the film in at least one direction. Heat set,
It is preferable to obtain by cooling and completing orientation crystallization.

When the coating layer processing liquid according to the present invention is applied to a plastic film, it is applied in a normal application step, that is, in a separate step after the oriented crystallization is completed, separated from the production step of the film. Although a layer processing liquid can be applied, this requires a separate step, which is disadvantageous in terms of cost. Therefore, in the present invention, it is preferable to apply the coating layer processing liquid in the plastic film manufacturing process from such a viewpoint. In particular, it is preferable to apply the coating layer processing liquid to at least one surface of the film at any point before the completion of the orientation crystallization in the film production process. As an example, the unstretched film obtained by melt-extruding into a film form from a die, for example, a polyester resin is cooled on a cooling drum. A method of pre-heating, stretching horizontally, heat-fixing and cooling. In the present invention, the plastic film may be subjected to a surface treatment such as corona discharge or glow discharge before applying the coating layer working liquid.

In the present invention, the plastic film before the completion of the orientation crystallization refers to an unstretched film obtained by melting a plastic polymer by heat and forming the film as it is, or any one of the vertical and horizontal films. Refers to a uniaxially stretched film stretched in one direction. Both the vertical stretching and the horizontal stretching are usually performed at a magnification of 2.0 to 5.0 times.

The concentration of the coating layer processing liquid is usually 15% by weight or less, preferably 10% by weight or less. The coating amount is 1 to ²⁰ g, preferably 5 to 15 g, in terms of the weight of the coating layer processing liquid per 1 m2 of the film.

As the coating method, various known methods can be applied. For example, a roll coating method, a gravure roll method, a spray coating method, an air knife coating method, a bar coating method,
The impregnation method and the curtain coating method can be applied alone or in combination.

The plastic film before the completion of the orientation crystallization applied as described above is dried, and then led to steps such as stretching and heat setting. The plastic film laminate of the present invention in which the coating layer processing liquid is applied on a plastic film substrate exhibits good adhesion and water resistance to hydrophilic colloids such as polyvinyl alcohol and gelatin.

The plastic film laminate of the present invention comprises:
At least one hydrophilic colloid layer is provided thereon as a photographic support, and can be applied to various films. For example, a photographic light-sensitive material can be prepared by providing at least one silver halide photographic emulsion layer on at least one surface of the plastic film laminate of the present invention.
Examples of the hydrophilic colloid used in the hydrophilic colloid layer include proteins such as gelatin, albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Although gelatin can be used, gelatin is preferably used.
Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull Society Science Photography Japan (Bull. Soc. Sci. Phot. Japan), No.
Oxygen-treated gelatin as described in pages 16 and 30 (1966) may be used, or hydrolysates or enzymatic degradation products of gelatin may be used. Further, gelatin derivatives, gelatin and other polymers may be used. Can also be used.

As the silver halide emulsion used in the silver halide emulsion layer, various conventional silver halide emulsions can be arbitrarily used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye. Further, an antifoggant, a stabilizer, a hardener and the like can be added to the silver halide emulsion.
As the binder for the emulsion, the above-mentioned hydrophilic colloid is used, and it is particularly preferable to use gelatin.

The silver halide emulsion layer and other hydrophilic colloid layers can be increased in film strength by using a hardening agent. Examples of such hardening agents include aldehyde, aziridine, isoxazole and epoxy. , Vinyl sulphone-based, acryloyl-based, carbodiimide-based, triazine-based, polymer-based, and other maleimide-based, acetylene-based, and methanesulfonic ester-based hardeners can be used alone or in combination. Also, a plasticizer, a dispersion (latex) of a water-insoluble or hardly soluble synthetic polymer, a coupler, a coating aid, an antistatic agent, a formalin scavenger, a fluorescent brightener, a matting agent, a lubricant, an image stabilizer,
A surfactant, a color fogging inhibitor, a development accelerator, a development retarder, a bleaching accelerator and the like can be contained.

In the photographic light-sensitive material, as a hydrophilic colloid layer other than the silver halide emulsion layer, for example, a protective layer,
Auxiliary layers such as a filter layer, a back coating layer, an antihalation layer, an antiirradiation layer, and an intermediate layer can be provided as necessary.

Further, the plastic film laminate of the present invention is used not only as a photographic support, but also as an IC packaging material, a magnetic recording material, a material for various plate making,
It is particularly suitably used as a tracing film, a film for electrophotography, a film for an overhead projector, and a base film for easy adhesion for an ink for an offset printing machine, an ultraviolet curable ink, a cellophane ink, and the like.

[0082]

The present invention will be described in more detail with reference to the following examples.
The present invention is not limited by these.

(Adjustment of Coating Layer Processing Liquid) Coating layer processing liquids were prepared so as to have the following compositions. However, the number n of polyglycerin indicates the average value of the polyglycerin represented by the general formula (I) used. Therefore, pure products were not used. Coating layer processing liquid 1 Polar polymer (Exemplified Compound B-24) 50 parts by weight Polyglycerin (n = 4) 30 parts by weight Methylcellulose (Shin-Etsu Chemical Co., Ltd. product name SM-15) 20 parts by weight Coating layer processing liquid 2 Polar polymer ( Exemplified compound B-13) 40 parts by weight Polyglycerin (n = 6) 40 parts by weight Polyvinyl alcohol derivative (Exemplified compound A-4) 15 parts by weight Crosslinking agent (Exemplified compound C-3) 5 parts by weight Coating layer processing liquid 3 Polarity 35 parts by weight of polymer (exemplified compound B-3) 25 parts by weight of polyglycerin (n = 10) 15 parts by weight of PVA (trade name of Gosenol AH-17 manufactured by Nippon Synthetic Chemical Co., Ltd.) 5 parts by weight of crosslinking agent (exemplified compound C-5) Coating layer processing liquid 4 Polar polymer (Exemplified compound B-4) 40 parts by weight Polyglycerin (n = 4) 35 parts by weight Methylcellulose (trade name SH-20, manufactured by Shin-Etsu Chemical Co., Ltd.) 20 parts by weight Crosslinking agent (Exemplified compound C-3) ) 5 parts by weight

Example 1 (Preparation of Plastic Film Laminate) Polyethylene terephthalate having an intrinsic viscosity of 0.65 was melt-extruded from a T-die at 280 ° C. into a film and electrostatically applied.
Was quenched on a cooling drum. The obtained unstretched film (thickness: 1000 μm) was preheated to 75 ° C. and then stretched three times in the machine direction to obtain a uniaxially stretched plastic film. Next, the surface of the obtained film was subjected to a corona discharge treatment, and then coating layer processing liquids 1 to 4 were applied. Furthermore, after preheating for drying in a tenter, the film was stretched in the transverse direction at 100 ° C. three times, and then heat-set at 220 ° C. to obtain a biaxially stretched polyethylene terephthalate film having a coating layer having a film thickness shown in Table 1. The obtained films are referred to as plastic film laminate samples 1 to 4, respectively.

Example 2 (Preparation of Acrylic Polymer) Methyl methacrylate / ethyl acrylate / methacrylic acid / hydroxyethyl acrylate = 47.5 mol% / 47.5 so that the molecular weight becomes 500,000.
An acrylic polymer having a composition of mol% / 2.5 mol% / 2.5 mol% was synthesized.

A plastic film laminate sample 5 was prepared in the same manner as in Example 1 except that the coating layer processing liquid was changed to the following coating layer processing liquid 5 and the thickness of the coating layer was changed to 0.1 μm. Coating layer processing liquid 5 Acrylic polymer 80 parts by weight Polystyrene sulfonic acid 20 parts by weight Colloidal silica (0.12 μm) 0.3 parts by weight

Example 3 A plastic film laminate sample 6 was prepared in the same manner as in Example 2 except that the thickness of the coating layer was changed from 0.1 μm to 1 μm.

A plastic film laminate sample 7 was prepared in the same manner as in the preparation of the plastic film laminate sample 2 in Example 1 except that the coating layer processing liquid 7 shown below was used as the coating layer processing liquid. Coating layer processing liquid 7 Polar polymer (Exemplary compound B-13) 67 parts by weight Polyvinyl alcohol derivative (Exemplary compound A-4) 25 parts by weight Crosslinking agent (Exemplary compound C-3) 8 parts by weight Sample of obtained plastic film laminate 1 to 7 were evaluated according to the evaluation methods described below. Table 1 shows the results.

(Evaluation of Adhesiveness of Coated Layer) A cut was made with a razor at an angle of 45 ° on the coated layer surface of the plastic film laminate, and then a cellophane tape was pressed and rapidly peeled off in the direction of 135 °. The peeled area of the laminate was evaluated on the following five levels. Evaluation Criteria 1: The adhesion was very weak and completely peeled off. 2: 50% or more peeled off. 3: About 10 to 50% peeled off. 4: The adhesive strength was so strong that less than 10% was peeled off. 5: The adhesion was very strong and was not peeled at all. If the evaluation is 4 or more, it can be said that the adhesive strength is practically sufficient.

[Evaluation of the presence or absence of cracks in the coating layer] The coating layer surface of the biaxially stretched polyester film provided with the coating layer was dyed with a cationic dye such as methylene blue, and then the state of the coating layer surface was observed with an optical microscope. Evaluation was performed according to the standard. Evaluation criteria 1: Coarse cracks 2: Fine cracks 3: No cracks

[Surface resistivity] Using a Teraohmmeter VE-30 manufactured by Kawaguchi Electric Co., Ltd., applied voltage 100 V, 23 ° C., 35% R
It was measured under the condition of H.

[Transparency] TURBIDI manufactured by Tokyo Denshoku Co., Ltd.
The haze was measured with METER MODEL-2600DA.

[Easy Adhesion] (a) Adhesion to Gelatin A biaxially stretched polyethylene terephthalate film laminate was coated with an aqueous gelatin solution containing a hardener, and adhered to gelatin in the same manner as in the evaluation of the adhesion of the coating layer described above. The sex was evaluated. (B) Adhesion to UV-curable ink FDD (red) manufactured by Toyo Ink Co., Ltd.
O The printer was set. 2% to 90% of halftone dots of 150 lines were printed on the produced film. Next, after curing by UV exposure, adhere a cellophane tape to the halftone dots and 90 °
The smallest halftone dot percentage that did not peel off was observed. (C) Adhesiveness of Polyvinyl Alcohol (PVA) Film Polyvinyl alcohol (trade name: Gocenol, manufactured by Nippon Synthetic Chemical Co., Ltd.) was dissolved in water, and applied and dried so that the thickness of the applied film after drying was 5 μm. For this, the same test as the evaluation of the adhesiveness of the coating layer described above was performed and evaluated. (D) Adhesion to magnetic paint γ-Fe ₂ O ₃ powder 68 parts by weight Carbon black 7 parts by weight Vinyl chloride-vinyl acetate-vinyl alcohol copolymer 26 parts by weight Acrylonitrile-butadiene copolymer 5 parts by weight Polyisocyanate 2 parts by weight Part Methyl isobutyl ketone 75 parts by weight Toluene 75 parts by weight The thickness of the coating layer after drying the coating solution having the above composition is 2.5.
It was applied and dried to a thickness of μm. With respect to this, the same test as the evaluation of the adhesion of the coating layer was performed and evaluated.

[Odor test] Photocopier U-BIX 3035 manufactured by Konica Corp.
The odor after passing through 100 sheets of the plastic film laminate of the present invention of 4 sizes was classified and evaluated on a scale of 0 to 5.
However, “0” indicates that no odor was detected and “5” indicates that strong odor was detected.

[0095]

[Table 1] As is clear from Table 1, it was found that the plastic film laminate sample of the present invention gave satisfactory results in all evaluations.

[0096]

As described in detail above, according to the present invention, a plastic film laminate having easy adhesion, transparency and excellent conductivity even under low humidity can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshihiro Wada 1 Sakuracho, Hino-shi, Tokyo Inside Konica Corporation (72) Inventor Kaoru 1 Sakuracho, Hino-shi, Tokyo Inside Konica Corporation (72) Inventor Noriaki Tachibana 1 Konica Corporation, Hino City, Tokyo (72) Inventor Hitoshi Kawamoto 4-1 Kanebocho, Hofu City, Yamaguchi Prefecture Kanebo Stock Company (72) Inventor Yoshimichi Ozawa Hofu City, Yamaguchi Prefecture 4-1 Kanebocho Kanebo Co., Ltd. (72) Inventor Hiroshi Naito 4-1 Kanebocho, Hofu City, Yamaguchi Prefecture Kanebo Co., Ltd. (72) Inventor Makoto Mori 1-6-5, Senba Nishi, Minoh City, Osaka Prefecture Kanebo NSC Co., Ltd. (72) Inventor Yukio Ebisawa 1-6-5, Senba Nishi, Minoh-shi, Osaka Kanebo NSC Co., Ltd. (56) Bibliography Patent Sho 58-124651 (JP, A) JP Akira 60-238365 (JP, A) (58 ) investigated the field (Int.Cl. ^7, DB name) B32B 1/00 - 35/00 G03C 1 / 76-1/95

Claims (1)

(57) [Claims] An unstretched or uniaxially stretched thermoplastic resin film is provided with at least one layer containing at least a polar polymer having a conductive property and polyglycerin.
A plastic film laminate characterized by being stretched at least uniaxially after providing the layer.