JPH08309940A - Destaticized film - Google Patents

Abstract

PURPOSE: To obtain a destaticized film having excellent back surface transferability of antistatic agent and obtaining high destaticization even by a relatively thin destaticized coating film by using the agent represented by a specific chemical structure and to use the destaticized film for a magnetic card, a packaging material, a graphic material, an OHP film or a magnetic recording medium. CONSTITUTION: An antistatic agent containing a copolymer of 10 to 99mol% of ethylene unit represented by a formula I, 0 to 80 mol% of acrylic acid unit represented by a formula II and 1 to 40mol% of a unit containing a cationic nitrogen group at a side chain and represented by a formula III as main ingredients is synthesized with the one surface of a polyester film. A destaticized film is provided with a destaticized coating film formed by coating with aqueous coating fluid containing the agent, drying it and orienting it. In the formula II, R<1> , R<2> are H or CH3 , X is H, 1-10C saturated hydrocarbon group or the part of the H indicates a hydroxyl group, and a saturated hydrocarbon group in which the part of the H is substituted for a hydroxyl group, an alkoxy group or a glycidyl group. In the formula III, R<1> , R<2> are H or CH3 , R<3> is 2-10C saturated hydrocarbon, and Y is halogen ion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antistatic film,
More specifically, magnetic cards (for example, telephone cards, prepaid cards), electronic materials, graphic materials, plate-making films, OHP films, magnetic recording, which have excellent antistatic properties, back surface transfer properties, abrasion resistance, blocking resistance, and recovery properties, The present invention relates to an antistatic film useful as a material (for example, a magnetic tape such as an audio tape and a video tape, a magnetic disk such as a floppy disk), and particularly useful for a magnetic card.

[0002]

Films made of polyester such as polyethylene terephthalate and polyethylene naphthalate are widely used for magnetic cards, general industrial materials such as packaging materials, photographic materials and graphic materials, and magnetic recording materials such as magnetic tapes. Has been done. However, such a polyester film has a drawback that it has a large surface resistivity and is easily charged by friction or the like. When the film is charged, dust or dirt is attached to the surface of the film, which causes troubles. In addition, electric discharge occurs in the processing step, and there is a risk of ignition if an organic solvent is used.

As one of the methods for preventing such troubles due to charging, various methods for forming an antistatic coating film on the film surface have been proposed and put into practical use. As the antistatic agent to be contained in the antistatic coating film, a low molecular weight type and a high molecular weight type are known, but each has its own advantages and disadvantages. Therefore, the antistatic agent is used properly according to its characteristics.

For example, as a low molecular type antistatic agent, a long-chain alkyl compound having a sulfonate group (Japanese Patent Laid-Open No. 4-
No. 28728) and the like, and surfactant type anionic antistatic agents are known, and as a polymer type antistatic agent, a polymer having an ionized nitrogen element in its main chain (Japanese Patent Application Laid-Open No. 3-301). 255139, JP-A-4-28812.
No. 7, JP-A-6-172562), sulfonate-modified polystyrene (JP-A-5-320390) and the like are known.

However, in an antistatic coating film using a low-molecular type antistatic agent, a part of the antistatic agent migrates in the coating film and accumulates on the interface to migrate to the opposite surface of the film or the like. There is a problem that the antistatic property (antistatic property) deteriorates with time. On the other hand, in the antistatic coating film using a polymer type antistatic agent, it is necessary to add a large amount of antistatic agent in order to obtain good antistatic property, or a thick antistatic coating film. It is not economical because it is necessary to form In addition, when scrap film that does not become a product (for example, the edge of a film that has been cut and removed from the product) is collected and used as a recycled material for film production, the coating film components contained in the recycled material during the melt film formation will not be heated. There is a problem that the film is deteriorated and the obtained film is markedly colored and is not practical (recovery is poor). Further, there are drawbacks such that the films are difficult to peel off (blocking) and the coating film is easily scraped off.

[0006]

The object of the present invention is to solve the problems of the prior art and to provide an antistatic film excellent in antistatic property, back surface transfer property, recovery property, abrasion resistance and blocking resistance. To provide.

[0007]

The object of the present invention is, according to the invention, to at least one side of a polyester film,
10 to 99 mol% of a structural unit (i) represented by the following formula (I), 0 to 80 mol% of a structural unit (ii) represented by the following formula (II), and a structural unit (iii) represented by the following formula (III). ) 1-4
An antistatic coating film is prepared by applying an aqueous coating solution containing an antistatic agent (A) containing 0 mol% of the copolymer (A-1) as a main component, drying and stretching. Achieved by antistatic film.

[0008]

[Chemical 4]

[0009]

Embedded image

[In the formula (II), R ¹ and R ² are H or CH ₃ ;
X represents H, a saturated hydrocarbon group having 1 to 10 carbon atoms or a saturated hydrocarbon group having 1 to 10 carbon atoms in which a part of H is substituted with a hydroxyl group, an alkoxy group or a glycidyl group]

[0011]

[Chemical 6]

[In the formula (III), R ¹ and R ² are H or C
H ₃ ; R ³ is an alkylene group having 2 to 10 carbon atoms; R ⁴ , R
⁵ , R ⁶ is a saturated hydrocarbon group having 1 to 15 carbon atoms or a saturated hydrocarbon group having 1 to 15 carbon atoms in which a part of H is substituted with a hydroxyl group, an alkoxy group or a glycidyl group; Y ⁻ is a halogen ion , Mono- or poly-halogenated alkyl ion, nitrate ion, sulfate ion, alkyl sulfate ion, sulfonate ion or alkyl sulfonate ion] The present invention is described in detail below.

[Base Film] In the present invention, the base film is a polyester film, and the polyester constituting the 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.

The glycol component is, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol. , Cyclohexanedimethanol, polyethylene glycol, polytetramethylene glycol and the like can be mentioned, and ethylene glycol is particularly preferable.

As such polyester, a film having excellent mechanical properties such as polyethylene terephthalate or polyethylene-2,6-naphthalate having a high Young's modulus, and excellent thermal properties such as good heat resistance and dimensional stability is obtained. It is preferable because it can

The above polyester may be a polyester obtained by copolymerizing the above-mentioned dicarboxylic acid component or glycol component, etc., and is a range in which the polyester is substantially linear with a trifunctional or higher polyvalent carboxylic acid component or polyol component. It may be a polyester copolymerized in a small amount (for example, 5 mol% or less).

Such a polyester can be produced by a conventional method, and it is preferable that the intrinsic viscosity of the polyester is 0.45 or more because the mechanical properties such as the rigidity of the film are good.

The above polyester has a mean particle size of 0.1 as a lubricant in order to make the film slippery.
Organic or inorganic fine particles of about 01 to 20 μm can be contained at a blending ratio of, for example, 0.001 to 5% by weight. Specific examples of such fine particles include silica, alumina, kaolin, calcium carbonate, calcium oxide, titanium oxide, graphite, carbon black, zinc oxide,
Preferable examples include silicon carbide, tin oxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles, and crosslinked silicone resin particles.

In addition to the fine particles, colorants, known antistatic agents, antioxidants, organic lubricants (slipping agents), catalysts, optical brighteners, plasticizers, crosslinking agents, ultraviolet absorbers, other resins, etc. It can be added if necessary.

As the base film of the present invention, a transparent polyester film or a white polyester film can be used depending on the use of the antistatic film. This transparent polyester film has a light transmittance of 60% or more after stretching, and particularly preferably 80% or more. The white polyester film is a polyester blended with, for example, titanium oxide, barium sulfate, silicon oxide or the like in an amount of 5 to 30% by weight, and has a light transmittance after stretching of less than 60%, particularly 30% or less. Those are preferable. A white antistatic film using a white polyester film as a base film is particularly preferably used for a magnetic card.

The polyester film of the present invention is
It can be manufactured by a conventionally known method. For example, a method in which the polyester is melted and cast on a cooling drum to form an unstretched film, and the unstretched film is sequentially biaxially stretched in the machine direction and then in the transverse direction, or simultaneously biaxially stretched in the machine direction and the transverse direction. It can be manufactured by the method. Further, it may be stretched again in the machine direction and / or the transverse direction.
The stretching treatment is preferably carried out at a temperature higher than the second-order transition point (Tg) of the polyester by stretching in each direction at least 2 times, more preferably at least 3 times. At that time, the area stretching ratio is preferably 8 times or more, and more preferably 9 times or more. The upper limit of the area draw ratio depends on the use of the film, but is 35
It is preferably doubled, more preferably 30 times. It is preferable that the oriented crystallization is completed by heat treatment after stretching.

[Antistatic Agent (A)] In the present invention, the antistatic coating film contains the antistatic agent (A) containing the copolymer (A-1) as a main component on at least one surface of the polyester film. It is prepared by applying an aqueous coating solution, drying and stretching.

[Copolymer (A-1)] The copolymer (A-1) in the present invention is a copolymer composed of the above structural units (i), (ii) and (iii), and is as follows. It can be obtained by the method of.

For example, ethylene is used as a monomer to introduce the structural unit (i) into the copolymer (A-1), and ethyl acrylate is used as a monomer to introduce the structural unit (ii). Acrylic acid, Butyl acrylate, Sodium acrylate
Da, ammonium acrylate, methyl methacrylate, methacrylic acid, butyl methacrylate and the like can be used, and for example, the following method can be used to introduce the structural unit (iii).

That is, the weight average molecular weight is 10,000 to 5
Water was added to a copolymer of ethylene / acrylic acid ester (ethyl ester, methyl ester, propyl ester, etc.) of 0,000, and the mixture was reacted in an autoclave at a high temperature under pressure to decompose and degrade it. 2,000
An ethylene / acrylic acid / acrylic acid ester copolymer of from 100,000 is produced. Next, this ethylene / acrylic acid / acrylic acid ester copolymer was added to N, N
-Dialkylaminoalkylamines (eg N, N-
It is possible to introduce a quaternary cation ion pair by reacting with dimethylaminopropylamine, N, N-diethylaminopropylamine and the like to amidate and finally performing a quaternary alkylation reaction.

The structural unit (iii) is represented by the above formula (III).
In the formula (III), R ¹, R²Is H or C
H₃; R³Is an alkylene group having 2 to 10 carbon atoms; R^Four, R
^Five, R⁶Is a saturated hydrocarbon group having 1 to 15 carbon atoms or H
Place partly with hydroxyl group, alkoxy group or glycidyl group
A substituted saturated hydrocarbon group having 1 to 15 carbon atoms; Y^-Ha
Rogen ion (Cl^-, Br^-Etc.), mono or poly
Halogenated alkyl ion (CH₂Cl^-, CHCl₂
^-, CH₂CH₂Cl^-Etc.), nitrate ions (N
O₃ ^-), Sulfate ion (HOSO₃ ^-), Al
Killsulfate ion (CH₃OSO₃ ^-Etc.),
Honate ion (HSO₃ ^-) Or an alkyl sulfonate
Toion (CH₃SO₃ ^-Etc.).

In the copolymer (A-1), other monomer components such as acrylamide, N-methoxymethylacrylamide, styrene, vinyl chloride, sodium methallylate, etc. may be copolymerized in a small amount. You can

The copolymerization ratio of the copolymer (A-1) is such that the structural unit (i) is from 10 to 99 mol% and the structural unit (ii) is from 0 to 99 mol%.
80 mol% and 1 to 40 mol% of the structural unit (iii), and a more preferable copolymerization ratio is 30 for the structural unit (i).
˜97 mol%, the structural unit (ii) is 0 to 70 mol%, and the structural unit (iii) is 2 to 25 mol%.

If the proportion of the structural unit (i) is less than 10 mol%, the heat resistance of the antistatic coating film is insufficient and the recoverability is poor.
If it exceeds 9 mol%, the adhesiveness between the coating film and the base film will deteriorate. On the other hand, if the structural unit (ii) exceeds 80 mol%, the antistatic property and heat resistance of the antistatic coating film will be insufficient. Further, if the constituent unit (iii) is less than 1 mol%, the antistatic property of the antistatic coating film will be insufficient, and if it exceeds 40 mol%, the heat resistance of the antistatic coating film will be insufficient.

The copolymerization ratio of the copolymer (A-1) is
Structural unit (i) 50 to 96 mol%, structural unit (ii) 0
25 mol% and 4 to 25 mol% of the structural unit (iii), and Y ⁻ in the formula (III) is an alkyl sulfonate ion represented by R ⁷ SO ₃ ^— (wherein R ⁷ has 1 to 10 carbon atoms).
5 is a saturated hydrocarbon group 5), the adhesiveness between the coating film and the base film and the antistatic property of the coating film are excellent, and particularly, the heat resistance of the coating film is excellent, so that the recoverability is extremely excellent. Therefore, it is preferable.

The average molecular weight (number average molecular weight) of the copolymer (A-1) is optional, but it is 1,000 to 300,000.
Is preferred. This average molecular weight is 1,000
If the amount is less than the above range, the back surface transferability of the antistatic agent (A) tends to be deteriorated, and if the average molecular weight exceeds 500,000, the viscosity of the aqueous coating solution becomes too high and it becomes difficult to uniformly coat the film, which is not preferable. .

[Copolymer (A-2)] Antistatic Agent (A)
Preferably contains the copolymer (A-1) and the copolymer (A-2) as components because the antistatic property becomes good. The proportion of the copolymer (A-2) is the copolymer (A-1).
It is preferable that it does not exceed.

This copolymer (A-2) is a copolymer having a phosphate group and / or a sulfonate group in the molecule. Such a copolymer (A-2) can be obtained, for example, by polymerizing a monomer having an unsaturated double bond in the molecule and having a phosphate group and / or a sulfonate group in the molecule.

Examples of the monomer having an unsaturated double bond in the molecule and having a phosphate group in the molecule include the following compounds.

[0036]

CH ₂ ═CHOR ⁹ OP (═O) (OM) ₂ CH ₂ ═CHOR ⁹ OP (═O) (OM) (OR ⁹ ) CH ₂ ═CHCONH (CH ₂ ) ₃ OP (═O) ( O
M) ₂ CH ₂ = CHCONH (CH ₂ ) ₃ OP (= O) (O
M) (OR ⁹ ) [wherein R ⁸ is an alkylene group or phenylene group having 2 to 10 carbon atoms; R ⁹ is an alkyl group or polyalkylene oxide group having 1 to 4 carbon atoms; M is a monovalent metal element, Indicates an ammonium group or a primary to quaternary ammonium group]

Further, examples of the monomer having an unsaturated double bond in the molecule and having a sulfonate group include the following compounds.

[0038]

CH ₂ ═CHSO ₃ M CH ₂ ═CHR ¹⁰ SO ₃ M [where M is a monovalent metal element, an ammonium group or a primary to quaternary ammonium group; R ¹⁰ is —C ₆ H ₄ - (o
-Phenylene group, m-phenylene group or p-phenylene group)]

[A compound having a quaternary amine salt (A-
3)] Further, the antistatic agent (A) is a copolymer (A-1).
It is preferable that the compound (A-3) having a quaternary amine salt is contained as a component because the antistatic property of the antistatic coating film becomes good. Compound (A-3) having quaternary amine salt
It is preferable that the ratio of is not more than that of the copolymer (A-1). A compound having this quaternary amine salt (A-
3) is a compound represented by the following general formula.

[0040]

[Chemical 9]

[In the above general formula, R¹¹, R¹², R¹³, R
¹⁴Is an alkyl group having 1 to 30 carbon atoms, an aryl group, or ara.
Alkyl group, alicyclic group, alkyl group having hydroxyl group, or
Polyalkylene oxide group; Z^-Is NO₃ ^-, R^FifteenOS
O₃ ^-, R^FifteenSO₃ ^-, Cl ^-Or R^FifteenCOO^-(However
Then R^FifteenIs an alkyl group having 1 to 12 carbon atoms, aryl
Group, aralkyl group or alicyclic group). ] Specific examples of such compounds include the following compounds.
Can do

[0042]

[Chemical 10]

[Binder Resin (B)] In the antistatic coating film of the present invention, the antistatic agent (A) and the binder resin (B) are used in order to strengthen the adhesion between the coating film and the base film. And are preferably included. As the binder resin, polyester resin (B-1), acrylic resin (B-2), acrylic modified polyester resin (B-
3) and the like can be exemplified, and it is preferable to use one or more resins selected from these resins. In particular, it is preferable to use the polyester resin (B-1) or the acrylic resin (B-2) because the adhesion between the antistatic coating film and the base film is improved, and the polyester resin (B-1) and the acrylic resin ( The combined use with B-2) is preferable because the adhesiveness is good and coloring of the recycled film can be suppressed when the antistatic film is collected and reused. When the polyester resin (B-1) and the acrylic resin (B-2) are used in combination, it is preferable to use the polyester resin (B-1) in an amount larger than that of the acrylic resin (B-2).

[Polyester Resin (B-1)] The polyester resin (B-1) is a linear polyester having a dicarboxylic acid component and a glycol component as constituent components.

As the dicarboxylic acid component, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4 '
-Diphenyldicarboxylic acid, adipic acid, sebacic acid,
Preferable examples include dodecanedicarboxylic acid and hexahydroterephthalic acid.

As the glycol component, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diglycol Preferable examples include propylene glycol, triethylene glycol, bisphenol A-alkylene oxide adduct, hydrogenated bisphenol A-alkylene oxide adduct, 1,4-cyclohexanedimethanol, polyethylene glycol, and polytetramethylene glycol.

The polyester resin (B-1) can be copolymerized with a component having a sulfonate group in order to impart hydrophilicity. When hydrophilicity is imparted to the polyester resin (B-1), dispersibility in an aqueous coating solution becomes good. Examples of such components include 5-Na sulfoisophthalic acid and 5-K sulfoisophthalic acid.

The polyester resin (B-1) may be obtained by copolymerizing a small amount (for example, 5 mol% or less) of a polyfunctional compound having a functionality of 3 or more in such a range that it becomes a substantially linear polymer. Examples of such trifunctional or higher polyvalent compounds include trimellitic acid, pyromellitic acid, dimethylolpropionic acid, glycerin, and trimethylolpropane.

[Acrylic resin (B-2)] Acrylic resin (B-2) includes ethyl acrylate, methyl acrylate,
Acrylic acid, butyl acrylate, sodium acrylate, ammonium acrylate, ethyl methacrylate, methyl methacrylate, methacrylic acid, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, methacrylamide, N-methoxymethyl acrylamide , A polymer or a copolymer containing an acrylic monomer as a main component, such as N-methylol acrylamide, for example, styrene, α-methylstyrene, sodium styrenesulfonate, vinyl chloride, vinylidene chloride, vinyl acetate. It may be a copolymer obtained by copolymerizing copolymer components such as vinyl ether, sodium vinyl sulfonate and sodium methallylate.

[Acrylic modified polyester resin (B-
3)] The acrylic modified polyester resin (B-3) is ethyl acrylate, methyl acrylate, acrylic acid, butyl acrylate, sodium acrylate, ammonium acrylate, ethyl methacrylate, methacrylic acid in the presence of the polyester resin. Made by polymerizing acrylic monomers such as methyl, methacrylic acid, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, methacrylamide, N-methoxymethyl acrylamide, and N-methylol acrylamide. Is a graft copolymer, styrene, α-methylstyrene, sodium styrenesulfonate,
It may contain a monomer such as vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ether, sodium vinyl sulfonate, sodium methallylate as a copolymerization component.

[Other Binder Resin] The antistatic coating film may contain a binder resin other than the above in order to adjust the adhesiveness between the coating film and the base film. Examples of the resin include polyurethane resin and epoxy resin. Examples thereof include resins, vinyl resins, polyether resins, water-soluble resins and the like.

[Surfactant (C)] In the antistatic coating film of the present invention, the adhesion between the coating film and the base film should be strong, and the antistatic film should have good blocking resistance. Therefore, the surfactant (C) can be blended. Examples of the surfactant (C) include alkylene oxide homopolymers, alkylene oxide copolymers, aliphatic alcohol / alkylene oxide adducts,
Long chain aliphatic substituted phenol / alkylene oxide addition polymer, polyhydric alcohol fatty acid ester, nonionic surfactant such as long chain aliphatic amide alcohol, compound having quaternary ammonium salt, compound having alkylpyridinium salt, sulfonic acid Examples thereof include a cationic or anionic surfactant such as a compound having a salt, and in particular, a nonionic surfactant is excellent in the effect on the adhesion between the coating film and the base film and the blocking resistance of the antistatic film. preferable.

[Antistatic Coating] The antistatic coating in the present invention is a coating containing the above-mentioned antistatic agent (A), but a coating comprising a composition further containing a binder resin (B). Is preferred. The proportion of the antistatic agent (A) contained in the antistatic coating film is preferably 5% by weight or more, and more preferably 10% by weight or more in order to improve the antistatic property. The proportion of antistatic agent (A) is 5% by weight
If it is less than this, the antistatic property is insufficient.

The antistatic coating of the present invention comprises 10 to 80% by weight of the above-mentioned antistatic agent (A) and binder resin (B).
20 to 80% by weight and a composition containing 25% by weight or less of a surfactant (C), wherein the antistatic agent (A) is 60 to 95 mol% of the structural unit (i) represented by the formula (I). Formula (II) (wherein R ¹ and R ² are H or CH
₃ ; X is H, 0 to 25 mol% of a structural unit (ii) represented by a saturated hydrocarbon group having 1 to 6 carbon atoms and the above formula (III)
(However, in formula (III), R ¹ and R ² are H or CH ₃ ; R ³ is an alkylene group having 2 to 10 carbon atoms; R ⁴ , R ⁵ , and R ⁶ are saturated carbon atoms having 1 to 5 carbon atoms. hydrogen radical; Y ^- is R ⁷ SO ₃ ^-
An alkyl sulfonate ion represented by R ⁷ is a structural unit represented by a saturated hydrocarbon group having 1 to 5 carbon atoms (iii)
Copolymer consisting of 5 to 15 mol% (hereinafter referred to as "copolymer A-
1-1 ”), the binder resin (B) is an acrylic resin (B-2) having a second-order transition point of 20 to 100 ° C. (hereinafter referred to as“ acrylic resin (B-2-1) ”, Surface energy of antistatic coating is 37-73 dyne / cm
And the water contact angle is 40 to 110 degrees, when the antistatic film is used for, for example, a magnetic card, the adhesiveness between the coating film and the base film, the blocking resistance of the antistatic film, the heat resistance, It is particularly preferable because it has excellent antistatic properties at low humidity.

In the above antistatic coating film, when the antistatic agent (A) is in the range of 10 to 80% by weight, the adhesion between the coating film and the base film and the antistatic property are good, and the binder resin ( When B) is in the range of 20 to 80% by weight, the antistatic property and the adhesiveness between the coating film and the base film are good, and when the content of the surfactant (C) is 25% by weight or less, the coating film and the base film. The adhesiveness with and the blocking resistance of the antistatic film are excellent.

The copolymer (A- used for the above antistatic coating film
1-1) shows that the formula (II) is methyl methacrylate or meta.
Ethyl acrylate, methyl acrylate, ethyl acrylate
And a structure derived from butyl acrylate.
Y in (III)^-Is CH₃SO₃ ^-, C₂H_FiveSO₃ ^-Well
Or C₃H₇SO₃ ^-It is preferred that

The acrylic resin (B-2-1) used for the above antistatic coating film has a second-order transition point of 20 to 100 ° C. and is an unsaturated monomer containing an acrylic acid ester monomer as a main component. Are preferred copolymers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl crotonic acid, glycidyl methacrylate, and 2-hydroxyethyl acrylate. , 2-ethylhexyl acrylate, acrylamide, methacrylamide, acrylic acid, methacrylic acid, sodium acrylate,
The main component is a monomer such as potassium methacrylate, ammonium acrylate, N-methylol acrylamide, N-methoxymethyl acrylamide, and if necessary vinyl chloride, vinyl acetate, styrene, vinyl ether, butadiene, isoprene, sodium vinyl sulfonate. A copolymer obtained by using the above as a copolymerization component can be mentioned. If the second-order transition temperature of the acrylic resin (B-2-1) is less than 20 ° C, the blocking resistance may be poor, and 100 ° C.
If it exceeds, the abrasion resistance may decrease.

Here, the blocking resistance is a characteristic that sticking (blocking) between the films does not easily occur when the long film is rolled and stored, and the abrasion resistance is a coating film applied. It is a characteristic that the coating film is not easily detached (scraped) from the base film when the film is subjected to friction or pressure by rolls in the processing step.

The average molecular weight of the copolymer (A-1-1) is preferably 3,000 to 1,000,000.

Furthermore, the surface energy of the antistatic coating film is 37.
˜73 dyne / cm and a water contact angle of 40 to 110 degrees are preferable because the antistatic property and the adhesiveness to the ultraviolet curable ink are excellent. The antistatic coating film whose surface energy and water contact angle fall within the above ranges is a copolymer (A-1-
It can be obtained by combining the composition ratios of 1), the acrylic resin (B-2-1) and the surfactant (C) within the above range.

For example, since the copolymer (A-1-1) acts to increase the surface energy of the antistatic coating film, the acrylic resin (B-2-1) is blended, and if necessary, an interface is added. The activator (C) may be added to adjust the amount within the above range. Further, since the copolymer (A-1-1) acts in the direction of increasing the water contact angle of the antistatic coating film, the acrylic resin (B-2-1) is blended, and the surface active agent may be added if necessary. The agent (C) can be added to adjust the amount within the above range.

[Aqueous Coating Liquid] In the present invention, an antistatic coating film is applied using an aqueous coating liquid containing the antistatic agent (A). A lubricant may be added in order to improve the surface slipperiness and the blocking resistance of the film. Examples of such lubricants include polystyrene resin, acrylic resin, melamine resin, silicone resin, fluororesin, urea resin,
Examples thereof include fine particles of benzoguanamine resin, polyamide resin, polyester resin and the like. The fine particles of these resins may be thermoplastic or thermosetting as long as they are contained in the antistatic coating in the form of fine particles.

In the aqueous coating liquid, a surfactant, an antioxidant, an antistatic agent other than the antistatic agent (A), a colorant, a pigment, an optical brightening agent, a plasticizer, a crosslinking agent, and the like are further added to the aqueous coating liquid. A slip agent (a slipperiness-imparting agent such as wax) and an ultraviolet absorber can be added.

The solid content concentration of the aqueous coating solution is 1 to 30% by weight.
Is preferable, and 2 to 20% by weight is particularly preferable. When the solid content concentration is within this range, the viscosity of the aqueous coating liquid becomes suitable for coating. The aqueous coating solution used in the present invention can be used in any form such as an aqueous solution, an aqueous dispersion, and an emulsion. Also,
The aqueous coating liquid may contain a small amount of solvent.

The aqueous coating liquid may further contain other components such as a surfactant, an antioxidant, an antistatic agent other than the antistatic agent (A), a colorant, a pigment, an optical brightening agent, a plasticizer, a crosslinking agent, and A slip agent (a slipperiness-imparting agent such as wax) and an ultraviolet absorber can be added.

The solid content concentration of the aqueous coating solution is 1 to 30% by weight.
Is preferable, and 2 to 20% by weight is particularly preferable. When the solid content concentration is within this range, the viscosity of the aqueous coating liquid becomes suitable for coating. The aqueous coating solution used in the present invention can be used in any form such as an aqueous solution, an aqueous dispersion, and an emulsion. Also,
The aqueous coating liquid may contain a small amount of solvent.

[Coating of Antistatic Coating] In the present invention,
At least one surface of the polyester film is coated with the water-based coating solution, dried by heating, and stretched to apply an antistatic coating film.As a method for applying the water-based coating solution, any known coating method is applied. For example, gravure coating method, reverse roll coating method, die coating method, kiss coating method, reverse kiss coating method, offset gravure coating method, Meyer bar coating method, roll brush method, spray coating method, air knife coating method, impregnation method, curtain The coating method and the like can be applied alone or in combination. WET coating amount of the aqueous coating liquid is the running film 1
1 to ²⁰ g, particularly ^{2 to} 12 g per m ² is preferable. When the coating amount is in this range, drying is easy and coating spots are less likely to occur, which is preferable.

The polyester film to which the aqueous coating liquid is applied in the present invention is a stretchable polyester film, 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 a uniaxially-stretched film stretched in either the transverse direction (width direction); a biaxially-stretched film in which a longitudinally or transversely uniaxially stretched film is sequentially stretched in the transverse or longitudinal direction (further stretchable). Or a biaxially stretched film obtained by simultaneously stretching (unstretchable) an unstretched film in two directions, the longitudinal direction and the transverse direction. The stretched polyester film preferably has a thickness of 1 to 300 μm.

When the aqueous coating solution is applied to a uniaxially stretched film of the above-described stretchable polyester film, particularly a uniaxially stretched film in the longitudinal direction, the adhesion of the antistatic coating becomes strong and the coating efficiency is high. This is preferable because an antistatic film can be produced. 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 prepare an antistatic film coated with an antistatic coating.

In the present invention, the temperature for drying after applying the aqueous coating liquid is preferably 80 to 160 ° 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 temperature for heat-treating the polyester film may be 180 to 250 ° C.

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

[Magnetic Card] The antistatic film of the present invention is useful for a magnetic card, and a white antistatic film using a white polyester film as a base film is particularly preferably used for a magnetic card. The magnetic card mentioned here is a card in which, for example, a magnetic recording layer (magnetic layer) is provided on one surface of an antistatic film and a printing layer is provided on the other surface with UV ink or the like. This magnetic layer can be applied, for example, by coating the base film with a magnetic paint composed of magnetic iron oxide, modified vinyl chloride resin, polyurethane resin, polyisocyanate, dispersant, etc. and drying it, and it is used as a magnetic card. Can be used by further providing a protective layer on the magnetic layer. Also,
For the printing layer of UV ink, for example, an ink prepared by blending a photosensitizer and a colorant with a polyurethane oligomer having an acrylic group at the end or a vinyl polymer having an acrylic group at the end is coated with an antistatic coating film of the base film. It can be provided by printing on the installation surface and irradiating with ultraviolet rays to cure.

The thickness of the antistatic film used for the magnetic card is, for example, 50 to 300 μm, particularly 150 to 250 μm.
It is preferable that the card has good rigidity of the card.

[Transparent Antistatic Film] A transparent antistatic film using a transparent polyester film as a base film is a magnetic recording material such as a magnetic tape or a magnetic disk, an electronic material, a graphic film, a plate-making film, and OH.
It is preferably used for a P film, and the thickness of the film varies depending on the use, but is, for example, 15 to 160 μm, particularly 25.
Those having a thickness of up to 100 μm are preferably used.

[0075]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. Each characteristic value was measured by the following method. The average molecular weight in the examples means the number average molecular weight.

1. Surface resistivity After holding the sample film at 21 ° C. × 52% RH for 19 hours, the surface resistivity of the film coated surface was measured using a vibration capacitance type potentiometer TR-84M type (manufactured by Takeda Riken). The applied voltage was 100 Volt.

2. Backside transferability The surface of the sample film coated with the aqueous liquid and the surface not coated with the liquid are overlapped with each other, a load of 6 Kg / cm ² is applied, and the sample is left to stand at 50 ° C × 70% RH for 8 hours. (θ: substitute property of backside transferability) was measured and evaluated according to the following criteria. A: θ ≧ 55 ° …… Good backside transferability B: 55 °> θ ≧ 48 ° …… Slightly good backside transferability C: 48 °> θ …… Poor backside transferability Water contact angle is the same as the above sample film. The measurement was carried out by setting the liquid non-coated surface on a contact angle measuring device (manufactured by Elma Co.) and reading the contact angle 1 minute after dropping a water drop at a temperature of 23 ° C. The water contact angle of the film having no rear surface transfer is 60 to 75 °, the water contact angle of the film having good rear surface transfer property is 55 ° or more, and the water contact angle of the film having remarkable rear surface transfer (rear surface transfer property is poor). The contact angle is less than 48 °.

3. Coloring degree of recycled film (recoverability) Film without coating is crushed and extruded to about 300
Melted at ℃ and made into chips. Next, the obtained chip was used to perform melt film formation to prepare a blank film. The coloring degree of this film was set as a blank. On the other hand, the sample film provided with a coating film was crushed and melted at about 300 ° C. by an extruder to be made into chips. Next, the obtained chip was used to perform melt film formation to prepare a recycled film. The coloring degree of this film was evaluated according to the following criteria.

Rank A: The degree of coloring is similar to that of a blank film. Rank B: The film is slightly colored. Rank C: The degree of coloring of the film is large and lacks practicality.

4. Saturation electrification voltage After applying an applied voltage of 10 KVolt to the coated surface of the coating film of the sample film kept at 22 ° C. × 44% RH for 10 hours,
The electrification voltage of the coated surface was measured over time, and the electrification voltage when no change in electrification voltage was observed was taken as the saturation electrification voltage. It should be noted that the following criteria were used for evaluation based on the measured value of the saturation electrostatic voltage.

Rank A: 1 KV ≧ saturation electrification voltage (no problem in practical use) Rank B: 2 KV ≧ saturation electrification voltage> 1 KV (somewhat problematic in practical use) Rank C: saturation electrification voltage> 2 KV (problem in practical application) )

5. Ink adhesion UV-curable ink (mixture of bisacrylic polyurethane oligomer, photopolymerization initiator, photosensitizer and red colorant) is applied to the coating surface of the sample film with a thickness of 8 μm and irradiated with ultraviolet rays. After curing, a cellophane tape was attached to the surface of the cured ink layer, and the peeled state between each layer when a peeling force was applied to the cellophane tape was observed and evaluated as follows.

Rank A: Peeling between cellophane tape and ink layer (good ink adhesion) Rank B: Partial peeling between coating film and ink layer in cohesive failure (somewhat good ink adhesion) Rank C: Coating film Ink layers were separated in layers (poor ink adhesion)

6. Heat resistance 12 g of the sample film provided with a coating film was heated to 300 ° C. under a nitrogen atmosphere, melted, held for 15 minutes and then rapidly cooled to form a disc-shaped sample, and the degree of coloring was observed. Separately, a disc-shaped sample was prepared as a blank under the same conditions using a film without a coating film. It was evaluated as follows by comparing the degree of coloring with the blank. Rank A: Ultra-light yellow with a coloring degree almost equal to that of the blank (good heat resistance) Rank B: Coloring with a slightly lighter yellow color than the blank (slightly poor heat resistance ) Rank C: The coloring degree is markedly higher than that of the blank, and it is colored yellow (poor heat resistance)

7. Blocking resistance Using a film sample cut into a width of 10 mm, the coated film surface and the uncoated surface of the film are overlapped with each other at 50 kg /
After applying a load of cm ² and holding at 50 ° C for 10 hours,
The peeling force between the coated surface and the non-coated surface was measured, and the blocking resistance was evaluated as follows.

Rank A: Peeling force ≤ 7 g (good blocking resistance) Rank B: 7 <Peeling force ≤ 10 g (blocking resistance slightly bad) Rank C: 10 ≤ Peeling force (poor blocking resistance)

8. Scraping resistance A film sample cut into a width of 20 mm was used, the coated surface of the film was applied to a cylindrical stainless steel fixed bar having a diameter of 10 mm, and the film was run for 80 m under a load of 200 g, and then adhered to the bar. The white powder of the formed coating film was observed and the abrasion resistance was evaluated as follows.

Rank A: No white powder adhered to the bar (good abrasion resistance) Rank B: Some white powder adhered to the bar (slight abrasion resistance was poor) Rank C: Large amount of white powder adhered to the bar (imperfect abrasion resistance)

Example 1 Polyethylene terephthalate having an intrinsic viscosity of 0.63 was melted, cast on a cooling drum, and then stretched at 92 ° C. by 3.6 times in the machine direction to obtain a uniaxially stretched film. On one side of this uniaxially stretched film, ethylene component 76 mol%, ethyl acrylate component 11 mol%, ethyl methacrylate component 4 mol% and the following formula (III-
Components shown in _{1) (- [CH 2 CHCONH} (C
H ₂ ) ₃ N ⁺ (CH ₃ ) ₃ ] [CH ₃ OSO ₃ ^- ]-)
70% by weight of 9 mol% copolymer (a-1), terephthalic acid (54 mol%) and isophthalic acid (46 mol%) as dicarboxylic acid component, ethylene glycol (42 mol%) and diethylene glycol (12 mol%) as glycol component. %), Neopentyl glycol (41 mol%) and polyethylene glycol (5 mol%), a polyester resin (b-1) which is a copolymer (average molecular weight: 19,700).
18% by weight and polyoxyethylene nonylphenyl ether (number of repeating units of polyoxyethylene = 9)
(C-1) A 5% by weight aqueous solution of 12% by weight was applied by a gravure coater. Then, the coated film is dried at 98 ° C., and then stretched 3.8 times in the transverse direction at 105 ° C.
A film having a thickness of 75 μm was heat-treated to form an antistatic coating film. The thickness of the antistatic coating of the film is 0.34
μm, the light transmittance was 84%. The characteristics of this film are shown in Table 1.

[0090]

[Chemical 11]

[Comparative Example 1] Table 1 shows the characteristics of the film obtained in the same manner as in Example 1 except that the aqueous liquid was not applied.

[Examples 2 to 7 and Comparative Examples 2 to 3] The characteristics of the film obtained in the same manner as in Example 1 are shown except that the composition of the coating liquid and the coating thickness are changed as shown in Table 1. Shown in 1.

Example 8 Polyethylene terephthalate containing 12% by weight of titanium oxide and having an intrinsic viscosity of 0.65 was used, the film thickness was 150 μm, and the composition of the coating liquid and the coating thickness were changed as shown in Table 1. A film having a light transmittance of 2% was obtained in the same manner as in Example 1 except for the above. The characteristics of this film are shown in Table 1.

[Examples 9 to 11] Table 1 shows the characteristics of the film obtained in the same manner as in Example 1 except that the composition of the coating liquid and the coating thickness were changed as shown in Table 1.

[0095]

[Table 1]

In the antistatic coating composition of Table 1, the antistatic agents [a-1], [a-2], [a-3], [a-4],
[A-5], binder resin [b-1], [b-2],
[B-3] and other components [c-1] are the following copolymers, compounds or mixtures, respectively.

[A-1]: 76 mol% of ethylene component, 11 mol% of ethyl acrylate component, 4 mol% of ethyl methacrylate component and the component represented by the formula (III-1) (-[C-1
H ₂ CHCONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃ ] [C
H ₃ OSO ₃ ^- ]-) 9 mol% copolymer (average molecular weight: 7,200) [a-2]: ethylene component 86 mol%, ethyl acrylate component 7 mol%, ethyl methacrylate component 2 mol% And a component represented by the following formula (III-2) (-[CH ₂ CHCON
H (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ C ₂ H ₅ ] [C ₂ H ₅
OSO ₃ ⁻ ] −) 5 mol% of copolymer ((average molecular weight:
6,400)

[0098]

[Chemical 12]

[A-3]: 45 mol% styrene component, 42 mol% soda styrene sulfonate component, 6 mol% methyl acrylate component and 2-hydroxyethyl acrylate
Copolymer of 7 mol% of component (average molecular weight: 54,60
0) [a-4]: 79 mol% of ethylene component and the above formula (III-
Components shown in _{1) (- [CH 2 CHCONH} (C
H ₂ ) ₃ N ⁺ (CH ₃ ) ₃ ] [CH ₃ OSO ₃ ^- ]-)
21 mol% copolymer (average molecular weight: 7,700) [a-5]: mixture of 82% by weight of sodium octylsulfate and 18% by weight of decylbenzene sulfonate caum.

[B-1]: dicarboxylic acid components are terephthalic acid (54 mol%) and isophthalic acid (46 mol%),
The glycol component is ethylene glycol (42 mol%),
Copolymer of diethylene glycol (12 mol%), neopentyl glycol (41 mol%) and polyethylene glycol (5 mol%) (average molecular weight: 19,700) [b-2]: Polyester [b-1] 61 wt% And 16 mol% of ethyl acrylate component, 4 mol% of potassium acrylate component, 53 mol% of methyl methacrylate component, 12 mol% of glycidyl methacrylate component, 7 mol% of 2-hydroxyethyl acrylate component and 8 mol of N-methoxymethyl acrylamide component. Mixture of 39% by weight of copolymer of mol% [b-3]: Methyl acrylate (19 mol%), ammonium acrylate (8 mol%), ethyl methacrylate with respect to 58% by weight of polyester [b-1] (62 mol%) and glycidyl methacrylate (11 mol%) 42 wt% graft weight The copolymer (average molecular weight: 41,
500) [c-1]: polyoxyethylene nonylphenyl ether (number of repeating units of polyoxyethylene = 9)

Example 12 Polyethylene terephthalate having an intrinsic viscosity of 0.62 was melted and cast on a cooling drum, and then stretched 3.4 times in the machine direction at 93 ° C. to obtain a uniaxially stretched film. On one side of this uniaxially stretched film,
86 mol% of ethylene component, 8 mol% of ethyl acrylate component and a component represented by the following formula (III-3) (-[CH ₂ CH
CONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃ ] [CH ₃ SO
₃ ^- ]-) 6 mol% of copolymer (a-6: average molecular weight 5,500) 38 wt%, dicarboxylic acid component terephthalic acid (56 mol%) and isophthalic acid (44 mol%),
The glycol component is ethylene glycol (72 mol%),
Copolymer of diethylene glycol (10 mol%), neopentyl glycol (12 mol%) and polyethylene glycol (6 mol%) (average molecular weight: 18,500)
9% by weight of the polyester resin (b-4), 51 mol% of methyl methacrylate component, and 39 of ethyl acrylate component
An acrylic resin (b) which is a copolymer (average molecular weight: 45,500) of mol%, hydroxyethyl acrylate component 4 mol% and N-methylolacrylamide component 6 mol%.
-5) 43 wt% and polyoxyethylene nonylphenyl ether (the number of repeating units of polyoxyethylene =
9: c-1) A 5 wt% aqueous solution having a composition of 10 wt% was applied with a gravure coater. Then, the coated film was dried at 102 ° C., then stretched 3.9 times in the transverse direction at 105 ° C. and heat-treated at 225 ° C. to apply an antistatic coating to a thickness of 7
A 5 μm coated film was made. The film had an antistatic coating thickness of 0.13 μm and a light transmittance of 88%. The characteristics of this film are shown in Table 2.

[0102]

[Chemical 13]

[Comparative Example 4] Table 2 shows the characteristics of the film obtained in the same manner as in Example 12 except that the aqueous liquid was not applied.

[Examples 13 to 18 and Comparative Example 5] Table 2 shows the characteristics of the film obtained in the same manner as in Example 12 except that the composition of the coating liquid and the coating thickness were changed as shown in Table 2. Show.

Example 19 Polyethylene terephthalate containing 11% by weight of titanium oxide and having an intrinsic viscosity of 0.62 was used for the base film, the film thickness was 180 μm, and the composition of the coating liquid and the coating thickness are shown in Table 2. A film having a light transmittance of 1% was obtained in the same manner as in Example 12 except that the above changes were made. The characteristics of this film are shown in Table 2.

[Example 20] Example 12 was repeated except that the film obtained in Example 12 was crushed and a chipped material was used.
A film coated with an antistatic coating film was obtained in the same manner as in. The obtained film had little coloring and had a good hue.

[Comparative Example 6] Instead of [a-7], [a-
8] was used, but the surface specific resistance of the coating film-coated surface of the film obtained in the same manner as in Comparative Example 5 was 4.6 × 10 ¹¹ Ω. A film coated with an antistatic coating was obtained in the same manner as in Example 12 except that this film was crushed and a chipped material was used. The obtained film was colored in pale yellow and had a poor hue.

[0108]

[Table 2]

In the antistatic coating composition of Table 2, antistatic agents [a-6], [a-7], [a-8], binder resins [b-4], [b-5] and other Ingredient [c-2]
Are the following copolymers, compounds or mixtures, respectively.

[A-6]: Ethylene component 86 mol%, a
8 mol% of ethyl acrylate component and the above formula (III-1)
Components (-[CH₂CHCONH (CH₂)₃N
⁺(CH ₃)₃] [CH₃SO₃ ^-]-) 6 mol% of co
Polymer (average molecular weight: 5,500) [a-7]: styrene component 56 mol%, styrene sulfo
Sodium acid salt component 35 mol%, methyl acrylate component 7 mol
% And 2-hydroxyethyl acrylate component 2 mol
% Copolymer (average molecular weight: 26,800)

[0111]

Embedded image

[B-4]: dicarboxylic acid component is terephthalic acid (56 mol%) and isophthalic acid (44 mol%),
The glycol component is ethylene glycol (72 mol%),
Copolymer of diethylene glycol (10 mol%), neopentyl glycol (12 mol%) and polyethylene glycol (6 mol%) (average molecular weight: 18,500) [b-5]: methyl methacrylate component 51 mol%, acrylic Copolymer of ethyl acid component 39 mol%, hydroxyethyl acrylate component 4 mol% and N-methylolacrylamide component 6 mol% (average molecular weight: 45,500) [c-1]: polyoxyethylene nonylphenyl ether (Number of repeating units of polyoxyethylene = 9)

Example 21 Polyethylene terephthalate containing 13% by weight of titanium oxide and having an intrinsic viscosity of 0.63 was melted, cast on a cooling drum, poured, and stretched at a temperature of 3.4 times in the longitudinal direction to form a uniaxial film. It was a stretched film. On one side of this uniaxially stretched film, an ethylene component of 84 mol%, a methyl acrylate component of 9 mol% and a component (-[CH ₂ CHCONH (CH ₂ ) ₃ N ⁺ (C
H ₃ ) ₃ ] [CH ₃ SO ₃ ⁻ ]-) 7 mol% copolymer (a-9: average molecular weight 5,870) 32 wt%, methyl methacrylate component 30 mol%, ethyl methacrylate component 42 mol %, 3 mol% methyl acrylate component, 11 mol% ethyl acrylate component, 1 mol% acrylic acid component, 5 mol% glycidyl methacrylate component, 3 mol% 2-hydroxyethyl acrylate component, 2 mol% acrylamide component and Copolymer of 3 mol% of N-methoxymethylacrylamide component (b-6: average molecular weight 46,500, Tg
= 56 ° C.) 58% by weight and 10% by weight of ethylene oxide / propylene oxide / block copolymer (c-2: average molecular weight 4,050) were used to apply a 5% by weight aqueous liquid with a gravure coater. Next, the coated film was dried at 104 ° C., then stretched 3.9 times in the transverse direction at 108 ° C., and heat-treated at 222 ° C. to prepare a coated film having a thickness of 195 μm on which an antistatic coating was applied. The film had an antistatic coating thickness of 0.12 μm and a light transmittance of 0%. The characteristics of the film are shown in Table 3. The evaluation results of blocking resistance and abrasion resistance of this film are all A
Met.

[Examples 22 to 30, Comparative Example 7] The results of the coating film characteristics of the film obtained in the same manner as in Example 21 except that the composition of the coating liquid and the coating thickness were changed as shown in Table 3 were obtained. Table 3
Shown in Table 4 shows the evaluation results of the blocking resistance, abrasion resistance, ink adhesion and heat resistance of this film.

[0115]

[Table 3]

[0116]

[Table 4]

In the antistatic coating composition shown in Table 3, antistatic agents [a-9] and [a-10], binder resin [b-
6], [b-7], [b-8] and [b-9], surfactants [c-2], [c-3] and [c-4] are the following copolymers, respectively. .

[A-9]: Ethylene component 84 mol%, a
9 mol% of methyl acrylate component and the above formula (III-3)
Components (-[CH₂CHCONH (CH₂)₃N
⁺(CH ₃)₃] [CH₃SO₃ ^-]-) 7 mol% of
Polymer (average molecular weight: 5,870) [a-10]: 89 mol% ethylene component, ethyl acrylate
5 mol% and a component represented by the following formula (III-4) (-
[CH₂CHCONH (CH₂)₃N⁺(CH ₃)₂C
₂H_Five] [C₂H_FiveSO₃ ^-]-) 6 mol% of copolymer
(Average molecular weight: 5,750)

[0119]

[Chemical 15]

[B-6] Methyl methacrylate component 30 mol%, ethyl methacrylate component 42 mol%, methyl acrylate component 3 mol%, ethyl acrylate component 11 mol%, acrylic acid component 1 mol%, glycidyl methacrylate Component 5 mol%, 2-hydroxyethyl acrylate Component 3
Copolymer of mol%, acrylamide component 2 mol% and N-methoxymethylacrylamide component 3 mol% (average molecular weight 46,500, Tg = 56 ° C.) [b-7]: ethyl methacrylate component 78 mol%, acrylic acid Methyl component 8 mol%, butyl acrylate component 1 mol%, acrylic acid component 1 mol%, glycidyl methacrylate component 5 mol%, 2-hydroxyethyl acrylate component 3 mol%, acrylamide component 1 mol% and N-methylol Copolymer of acrylamide component 3 mol% (average molecular weight: 29,600, Tg = 66 ° C.) [b-8]: Polydimethylsiloxane having a hydroxyl group in 32 parts by weight of copolymer [b-7] (acid value 67 ) A block copolymer obtained by copolymerizing 68 parts by weight. (Average molecular weight: 4
4,500) [b-9]: dicarboxylic acid component is isophthalic acid (14 mol%), adipic acid (5 mol%) and 5-Ksulfoisophthalic acid (81 mol%), and glycol component is diethylene glycol (93 mol%). ) And 1,4-butanediol (7 mol%) (average molecular weight: 14,200) [c-2]: ethylene oxide / propylene oxide block copolymer (average molecular weight: 4,050) [c -3]: ethylene oxide / propylene oxide block copolymer (average molecular weight: 6,560) [c-4]: ethylene oxide / propylene oxide block copolymer (average molecular weight: 4,710)

[Example 31] A magnetic layer containing magnetic iron oxide was applied to the surface of the coating film obtained in Example 21 on which the antistatic coating was not applied, and a protective layer was applied on the opposite surface. An ultraviolet-curable ink was offset-printed on (the surface on which the antistatic coating film was applied) and irradiated with ultraviolet rays to cure the ink. A card was produced by cutting this film, but there were no problems in the process, and there was no problem in practical use in terms of handleability of the card and adhesion of the magnetic layer and the ink layer.

[0122]

Since the antistatic film of the present invention uses an antistatic agent having a specific structure, the antistatic agent has excellent backside transferability and high antistatic property can be obtained even with a relatively thin antistatic coating film. Therefore, it is useful for magnetic cards, packaging materials, photographic materials, graphic materials, plate-making films, OHP films, magnetic recording media and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 27/08 B32B 27/08 27/18 27/18 D C08J 7/04 CFD C08J 7/04 CFDD

Claims (9)

[Claims] 1. A constitutional unit (i) 10 to 99 represented by the following formula (I) on at least one side of a polyester film.
Mol%, structural units (ii) 0 to 8 represented by the following formula (II)
0 mol% and the structural unit (iii) 1 represented by the following formula (III)
An antistatic coating film is prepared by applying an aqueous coating solution containing an antistatic agent (A) containing 40 to 40 mol% of the copolymer (A-1) as a main component, drying and stretching. Anti-static film. Embedded image Embedded image [In the formula (II), R ¹ and R ² are H or CH ₃ ; X is H, a saturated hydrocarbon group having 1 to 10 carbon atoms or a part of H is a hydroxyl group,
It represents a saturated hydrocarbon group having 1 to 10 carbon atoms, which is substituted with an alkoxy group or a glycidyl group. [In formula (III), R ¹ and R ² are H or CH ₃ ; R ³ is an alkylene group having 2 to 10 carbon atoms; R ⁴ , R ⁵ , and R ⁶ are saturated hydrocarbon groups having 1 to 15 carbon atoms. Or a saturated hydrocarbon group having 1 to 15 carbon atoms in which a part of H is substituted with a hydroxyl group, an alkoxy group or a glycidyl group; Y ⁻ is a halogen ion, a mono- or polyhalogenated alkyl ion, a nitrate ion, a sulfate ion, Indicates an alkyl sulfate ion, sulfonate ion or alkyl sulfonate ion] 2. The copolymer (A-1) comprises the structural unit (i) represented by the above formula (I) in an amount of 50 to 96 mol%, and the above formula (I).
A copolymer of the structural unit (ii) 0 to 25 mol% represented by I) and the structural unit (iii) 4-25 mol% represented by the above formula (III), wherein Y ⁻ in the formula (III) is The antistatic film according to claim 1, which is an alkylsulfonate ion represented by R ⁷ SO ₃ ^— (wherein R ⁷ is a saturated hydrocarbon group having 1 to 5 carbon atoms). 3. The antistatic agent (A) is a copolymer (A-
1) and a copolymer (A-2) having a phosphate group and / or a sulfonate group in the molecule or a compound (A-3) having a quaternary amine salt in the molecule as a component. Antistatic film. 4. An antistatic agent (A) 5-10 is used as the aqueous coating liquid.
0% by weight, polyester resin (B-1), acrylic resin (B-2) and acrylic modified polyester resin (B-
The antistatic film according to claim 1, comprising 0 to 95% by weight of a composition of at least one binder resin (B) selected from the group consisting of 3). 5. The copolymer (A-1) is represented by the above formula (I).
The structural unit (i) represented is 60 to 95 mol%, and the above formula (I
I) (however, in the formula (II), R¹, R²Is H or CH₃; X
Is H or a saturated hydrocarbon group having 1 to 6 carbon atoms)
0 to 25 mol% of the structural unit (ii) and the above formula (III) (provided that
In formula (III), R¹, R²Is H or CH ₃; R³Is carbon
An alkylene group having a number of 2 to 10; R^Four, R^Five, R⁶Is carbon
A saturated hydrocarbon group having a number of 1 to 5; Y^-Is R⁷SO₃ ^-Indicated by
Alkyl sulfonate ion, R⁷Has 1 carbon
To a saturated hydrocarbon group), the structural unit (iii) 5
It is 15 mol% and the acrylic resin (B-2) undergoes a secondary transition.
An acrylic resin having a point of 20 to 100 ° C. and an antistatic coating
The film is 10 to 80% by weight of antistatic agent (A), binder resin
20 to 80% by weight of fat (B) and 0 to surfactant (C)
Apply an aqueous coating solution containing 25% by weight of the composition and dry.
Made by drying and stretching, the surface energy is 37-73d
Magnetic with yne / cm and water contact angle of 40-110 degrees
The antistatic film according to claim 4, which is used for a card. 6. The antistatic film according to claim 1, wherein the polyester film is a white polyester film for magnetic cards. 7. The antistatic film according to claim 1, wherein the polyester film is a transparent polyester film. 8. The antistatic film according to claim 1, which is used for a magnetic card in which a magnetic layer is laminated on one surface of an antistatic film in which an antistatic coating is provided on at least one surface of a polyester film. 9. The antistatic film according to claim 8, wherein an ultraviolet curable ink layer is provided on the opposite surface of the laminated magnetic layer.