JP2003231230A - White laminated polyester film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a white laminated polyester film having high surface strength and excellent in whiteness, the adhesion with various inks, water- resistance adhesion, antistatic properties and scratch resistance. <P>SOLUTION: The white laminated polyester film is constituted by providing a coating layer (C-layer) at least on the single surface of a substrate material comprising a white polyester film having a two or more-layered laminated structure. The substrate material is formed by laminating a polyester resin composition layer (A-layer), which comprises a polyester resin (II) and a master batch polyester resin (III) containing a white pigment, on at least the single surface of a layer (B-layer) mainly comprising a polyester resin (I) and the intrinsic viscosities of the polyester resins (I)-(III) satisfy a specific relational expression. The C-layer is provided just above the A-layer and contains a modified resin and a specific high-molecular antistatic agent. The breaking strength and the surface intrinsic resistance value of the C-layer are set to specific ranges. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a white laminated polyester film in which a coating layer is provided on a white polyester film substrate having a laminated structure of two or more layers. More specifically, white color suitable for information recording materials and printing materials, especially for IC card base materials, which has high surface strength, whiteness, adhesion to various inks, water-resistant adhesion, antistatic property, and scratch resistance. It relates to a laminated polyester film.

[0002]

2. Description of the Related Art Biaxially stretched polyester films have excellent properties such as mechanical properties, electrical properties, and dimensional stability, so that they are used for magnetic recording materials, packaging materials, electrical insulating materials,
It is used as a base film in many fields such as photosensitive materials, drawing materials, and photographic materials.

However, since the surface of the biaxially stretched polyester film is highly crystallographically oriented, it has drawbacks such as poor adhesion to various paints, adhesives, inks and the like. In particular, in label applications and card applications such as magnetic cards and IC cards that use a biaxially oriented polyester film containing a white pigment to impart whiteness, the usage and storage conditions of the final product may vary depending on the individual. Significantly different, for example, the label or card may temporarily bend during storage. At this time, if the adhesiveness between the substrate film and the coating material (printing ink layer, magnetic recording layer, etc.) is poor, it peels off at the interface, impairing the appearance of the product, or losing the function as a card. Therefore, conventionally, studies have been made to impart adhesiveness to the surface of the polyester film by various methods.

As a method of imparting adhesiveness to the film surface, a surface activation method such as a method of corona discharge treatment, a method of irradiating with ultraviolet rays, a method of plasma treatment, etc., acid, alkali, A surface etching method using an aqueous amine solution or the like, and a method of providing various kinds of resins such as acrylic resin, polyester resin and urethane resin as a coating layer on the film surface are known (for example, refer to Patent Documents 1 to 3).

[0005]

[Patent Document 1] JP-A-55-15825

[Patent Document 2] JP-A-58-78761

[Patent Document 3] Japanese Patent Laid-Open No. 60-248232

In particular, a coating layer is formed by a coating method, a polyester film before crystal orientation is completed is coated with a coating solution containing the above resin component, dried, stretched in at least one direction, and heat treated to crystallize. A method of completing the alignment (in-line coating method) is generally used.

Many methods are known for applying an aqueous coating material containing a polyester resin to a biaxially stretched polyester film (see, for example, Patent Documents 4 and 5).

[0008]

[Patent Document 4] Japanese Patent Laid-Open No. 50-39375

[Patent Document 5] Japanese Patent Laid-Open No. 60-11358

However, although the coating layer formed from the conventional polyester resin aqueous coating material has excellent adhesiveness to the polyester film as the substrate, it has good adhesiveness to the coating material such as printing ink, and further when it is bent. However, it has a drawback that it has poor adhesiveness.

Also in various conventional ink-adhesive type polyester coating films, there are many methods in which a coating layer made of a specific resin is provided on the surface of a base polyester film. As the constituent resin of the coating layer, for example, a polyester resin, a polyurethane resin, an acrylic resin, etc. may be used alone or as a mixture of two or more, and the resin and a specific cross-linking agent (melamine, isocyanate, etc.) Examples include a mixture of and.

However, although most of the coating layers have good adhesion to oxidative polymerization (or solvent) type inks, adhesion of ultraviolet curing type inks (hereinafter sometimes abbreviated as UV curing inks) Inferior in sex, or U
Good adhesion with V-cured ink, but poor adhesion with oxidative polymerization (or solvent) type ink.
At present, no coating layer having excellent adhesion has been obtained for any of the inks.

Further, in many coating layers having excellent adhesion to ink, the glass transition temperature of the coating layer is set to room temperature or lower in order to enhance the affinity with ink, and therefore, generally scratches are likely to occur. There is a problem such as becoming. Furthermore, in the case of a white polyester film, a white pigment or the like is added, and as compared with a normal transparent film, the film surface finally obtained tends to be hard and brittle, and soft,
Or, there is a problem in that a brittle ordinary coating layer is particularly likely to be scratched.

Further, when it is used as a label or a card base material, there are some applications in which it is required that the ink adhesion does not change as much as possible under any storage environment or distribution environment during distribution. When used for that purpose, the easy-adhesion layer is also required to have excellent ink adhesion at high temperature and high humidity, but it has excellent ink adhesion regardless of the type of ink and at high temperature and high humidity. A laminated polyester film which is excellent in ink adhesion has not been obtained by the conventional easy-adhesion polyester film.

Further, both the polyester film as the base material and the easily-adhesive polyester film provided with a coating layer for improving the adhesive property are liable to be charged, and not only troubles in the film forming process but also electrostatic damage in the processing process. There is also a drawback that it is easy to cause.

In order to improve these problems caused by static electricity, a low molecular weight compound such as an alkylbenzene sulfonate group or an alkyl phosphate group, or an antistatic agent such as a surfactant type may be contained in the base film or coated with a coating agent. It is generally practiced to incorporate an antistatic agent into the base film for coating. However, the above low molecular weight compound is inferior in antistatic property when the content thereof is small, and when the content is increased in order to obtain good antistatic property,
On the contrary, there is a problem that a low molecular weight compound bleeds out on the film surface or interface to deteriorate the adhesiveness.

On the other hand, information recording materials and printing materials, which are used by laminating a white biaxially stretched polyester film, particularly IC card substrates, are required to have excellent whiteness, antistatic properties and ink adhesion. However, other than that, durability is required so that the function as a card can be maintained even in the processing process and any usage environment. Specifically, it has high surface strength as a card base material and excellent peeling resistance after bonding two base materials, scratch resistance in the process of laminating printed layers, high temperature and high temperature. It has been demanded that the ink has excellent adhesiveness after being left under humidity. However, at present, it is the actual situation that none satisfying all qualities has been obtained.

[0017]

The object of the present invention is to solve the above-mentioned drawbacks of the prior art and to have high surface strength and excellent whiteness, ink adhesion, water resistance adhesion, antistatic property, and scratch resistance. Another object of the present invention is to provide a white laminated polyester film suitable as a recording material or a printing material, particularly as a base material for an IC card.

[0018]

The present invention has been made in view of the above situation, and the white laminated polyester film capable of solving the above problems is as follows.

That is, the present invention is a white laminated polyester film in which a coating layer (C layer) is provided on at least one surface of a substrate made of a white polyester film having a laminated structure of two or more layers, wherein the substrate is A polyester resin composition layer (A layer) comprising a polyester resin (II) and a white pigment-containing masterbatch polyester resin (III) is laminated on at least one surface of a layer (B layer) mainly comprising the polyester resin (I), The intrinsic viscosity IV of the polyester resins (I) to (III) satisfies the following formula (1), and the C layer is provided directly on the A layer:
It contains a modified resin and a polymeric antistatic agent having at least one sulfonate group or phosphate group, and has a breaking strength of 10 to 100 MPa and a surface specific resistance value of 1 × 10 ⁶ at 25 ° C. and 65% RH. The white laminated polyester film is characterized in that it is 1 × 10 ¹³ Ω / □. IV (II) × a + IV (III) × b> IV (I) × 100 (1) where IV (I), IV (II), and IV (III) are polyester resins (I) and (II), respectively. , (III) intrinsic viscosity (dl / g), and a and b represent the mixing ratio (mass%) of the resin (II) and the resin (III) in the A layer.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION [Substrate] The polyester used for the substrate of the present invention is an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid or an ester thereof and ethylene glycol, diethylene glycol, 1,4- It is a polyester produced by polycondensing glycols such as butanediol and neopentyl glycol. These polyesters include a method of directly reacting an aromatic dicarboxylic acid and a glycol, or an ester exchange reaction of an alkyl ester of an aromatic dicarboxylic acid and a glycol followed by polycondensation, or a diglycol ester of an aromatic dicarboxylic acid. Can be produced by a method such as polycondensing.

Typical examples of such polyesters include polyethylene terephthalate, polyethylene butylene terephthalate and polyethylene-2,6-naphthalate. This polyester may be a homopolymer or a copolymer of a third component. In any case, in the present invention, the ethylene terephthalate unit, the butylene terephthalate unit or the ethylene-2,6-naphthalate unit is 70 mol% or more,
Preferably 80 mol% or more, more preferably 90 mol%
The above polyesters are preferable.

Inorganic particles, heat-resistant organic particles, antioxidants, antistatic agents, white pigments, optical brighteners, crosslinking agents, ultraviolet absorbers, plasticizers, etc. may be contained in the polyester as required. it can.

As the white pigment used in the present invention, at least one kind of titanium oxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate and the like can be used. Also,
The white pigment may be subjected to various organic and inorganic surface treatments for the purpose of improving dispersibility. Among the white pigments, titanium oxide is particularly preferable because it has a high refractive index and can develop high whiteness and hiding power with a small amount. Further, it is preferable to use a fluorescent whitening agent in combination because the whiteness can be further enhanced.

In the present invention, the layer A of the substrate is composed of the polyester resin (II) and the white pigment-containing masterbatch polyester resin (III). Here, the white pigment-containing master batch polyester resin (III) refers to a resin containing a white pigment in a high concentration in the polyester resin, and specifically, the lower limit of the content of the white pigment is preferably 41% by mass. , 45 mass% is particularly preferred. Also,
From the viewpoint of uniform dispersion of the white pigment in the polyester resin and pellet moldability, the upper limit of the content of the white pigment is 70% by mass.
Is preferred, and 65 mass% is particularly preferred.

In the white laminated polyester film of the present invention, the polyester resins (I) and (I
The intrinsic viscosity (dl / g) of I) and (III) and the mixing ratio (mass%) of the resin (II) and resin (III) in the A layer of the surface layer satisfy the relationship of the above formula (1). Thereby, the surface strength of the film can be particularly improved. IV (II) × a + IV (III) × b> IV (I) × 100 (1) where IV (I), IV (II), and IV (III) are polyester resins (I) and (II), respectively. , (III) intrinsic viscosity (dl / g), and a and b represent the mixing ratio (mass%) of the resin (II) and the resin (III) in the A layer.

From the viewpoint of film surface strength, it is preferable that the polyester resin (II), which is one of the constituents of the layer A, has an intrinsic viscosity of 0.70 dl / g or more.

The polyester resins (I) and (I
The intrinsic viscosities of I) and (III) preferably satisfy the following formula (2) from the viewpoint of surface strength. IV (III) <IV (I) <IV (II) (2)

The content of the white pigment in the layer A of the substrate is
From the viewpoint of hiding power, the lower limit is preferably 10% by mass, and particularly preferably 15% by mass. Further, the content of the white pigment has an upper limit of 45 from the viewpoint of film forming stability.
The content is preferably mass%, more preferably 35 mass%, particularly preferably 25 mass%.

When a fluorescent whitening agent is used in combination with a white pigment in the layer A of the substrate in order to further increase the whiteness,
When the amount of the white pigment exceeds 45% by mass, the amount of ultraviolet absorption of the white pigment increases, so that the amount of ultraviolet rays required for the fluorescent whitening agent to exert its effect decreases, which significantly impairs the fluorescent whitening effect and reduces the whiteness. It is not preferable because

In addition to the white pigment, the layer A contains at least one kind of inorganic particles having an average particle size larger than that of the white pigment in order to further improve the film handling property such as slipperiness and winding property. You may let me. The inorganic particles may be white pigments such as titanium oxide, barium sulfate, zinc oxide, zinc sulfide and calcium carbonate, or inorganic particles having a small difference in refractive index from polyester such as silica.

When two types of white pigments having different average particle sizes are used, the white pigments may be the same or different. In short, it is necessary to use two types of inorganic particles having different average particle sizes, and the inorganic particles having a small average particle size are white pigments from the viewpoint of hiding property and handling property. As the inorganic particles having a large average particle diameter, silica is preferable in terms of cost and handleability.

In addition, the layer B of the laminated film may contain a white pigment, inorganic particles, heat-resistant organic particles or the like in order to further improve the hiding property. Further, in order to further improve the whiteness, a fluorescent whitening agent may be contained within a range that does not impair the effects of the present invention.

Further, the base material of the white laminated polyester film of the present invention preferably has an apparent density of 1.3 g / cm ³ or more. The apparent density of the laminated film is 1.
If it is less than 3 g / cm ³ , the stiffness of the film becomes weak and the rigidity is insufficient when used as an information recording material or a printing material, which is not preferable.

A further preferred embodiment is to collect film scraps, which are scraps at the time of film production, in the B layer and reuse them as film raw materials. Such reuse is extremely significant in terms of cost reduction in industrial production. However, since the collected film pieces are re-melted and used, coloring due to heat deterioration of the film raw material and the coating layer and the precipitation of foreign matters such as gels may cause the sharpness of images and characters during printing in the post-processing step to be improved. It tends to decrease. Therefore, in the present invention, the recycled film raw material is not contained in the polyester resin composition layer (A layer) adjacent to the coating layer (C layer) for printing or the like, but the polyester resin layer (B It is preferable to contain it in a layer).

The white laminated polyester film of the present invention comprises C / A / B / A, C / A / B / A / C and C / A /
A layer structure such as B or C / A / B / C can be selected. Moreover, you may combine the polyester resin layer of a composition other than A layer and B layer in the range which does not impair the effect of this invention.

The total thickness of the laminated film may be appropriately adjusted depending on the application, but is generally 25 to 250 μm. When used as a card substrate such as an IC card or a magnetic card, the thickness is usually 100 to 250 μm.

Since the A layer of the base material contains a white pigment, the upper limit of the total thickness of the A layer should be 50% with respect to the total thickness of the laminated film from the viewpoint of maintaining film forming properties. Is preferred. The lower limit of the total thickness of the layer A is preferably 10% from the viewpoint of whiteness and hiding power. A / B /
In the case of the two-kind three-layer laminated structure of A, the thickness of the A layer of the base material may be the same for both outermost layers, or may be different from the viewpoint of curling prevention. The intrinsic viscosity of the laminated film of the base material is preferably 0.50 to 0.70 dl / g.

[Coating Layer] In the white laminated polyester film of the present invention, a compound having at least one functional group of urethane, carbonate, acryl and vinyl is provided on at least one surface of the A layer which is the outermost layer of the substrate. Coating layer C containing a modified resin and a polymeric antistatic agent having at least one sulfonate group or phosphate group
Are formed.

The modified resin, which is a constituent component of the coating layer C of the present invention, has the main purpose of improving adhesion, water-resistant adhesion, antistatic property, and scratch resistance. Further, the polymeric antistatic agent having at least one sulfonate group or phosphate group, which is another constituent, has the main purpose of improving the antistatic property. Hereinafter, the modified resin and the polymer antistatic property will be described in detail.

(Modified Resin) In the present invention, in the process of evaluating various characteristics, the problem that peeling and scratches are likely to occur particularly when a white film is used is caused by increasing the breaking strength of the resin in the coating layer. It has been found to be improved.

That is, in the coating layer C of the present invention, the base resin is modified by one or more modifying methods to enhance the breaking strength of the base resin, and the white laminated biaxially stretched polyester as the base material. The difference in breaking strength between the surface layer A and the coating layer can be reduced. As a result, the scratch resistance in the film processing step is improved, and
When used as various bonded products, particularly as a base material for a card such as an IC card, it is possible to reduce the print quality due to scratches and suppress peeling. Note that this effect is remarkable in a white film in which the surface layer is brittle because it has a white pigment in the surface layer and in the vicinity of the surface layer.

As a specific method for modifying the polyester resin, urethane modification, carbonate modification, acrylic modification, vinyl modification or the like is carried out to block or graft the base polyester resin. It is also effective to further increase the breaking strength by introducing a functional group reactive with a crosslinking agent into the base resin and causing a crosslinking reaction.

As the base resin to be modified, various resins can be used and are not particularly limited, and examples thereof include acrylic resin, polyester resin, polyurethane resin, polyamide resin, polycarbonate resin, epoxy resin, Examples include polyolefin resins. Since it is desirable to carry out the modification in a state of being dissolved in a solvent, it is desirable that the base resin is soluble in the solvent. Among these, acrylic resin, polyester resin, polyurethane resin and mixtures of these, in terms of adhesion to the polyester film as the base material and adhesion to the printing layer on the coating layer, magnetic recording layer and adhesive layer. Is preferred.

(Modification Method) As a modification method, known methods other than the above-mentioned methods can be used as long as the breaking strength of the base resin can be increased. Examples of methods for increasing the breaking strength of the base resin include (1) a method of introducing a segment having a hard skeleton into the base resin (blocking), and (2) a method of making the molecular chain of the base resin hard to move. Examples of the method (1) include blocking by urethane formation and esterification, and examples of the method (2) include grafting and introduction of a functional group reactive with a crosslinking agent.

Regarding the urethanization in the above method (1), a functional group such as a hydroxyl group or an amino group in the base resin is introduced into a molecule by a polyfunctional isocyanate compound or a polyfunctional isocyanate compound and a chain extender. The breaking strength can be increased depending on the type and amount of the polyfunctional isocyanate compound and the chain extender used.

As the above polyfunctional isocyanate compound, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate and the like are preferable. Examples of the chain extender include neopentyl glycol, cyclohexane dimethylol, cyclohexane diol, tricyclodecane dimethylol, 1,2-propylene glycol, polyhydric hydroxy compounds such as bisphenol A alkylene oxide adduct, neopentyl diamine, A polyvalent amine compound such as ethylenediamine can be used.

Regarding the esterification in the above method (1), a carboxyl group or a hydroxyl group in the base resin is esterified with an epoxy compound or a carbonate compound, and various compounds can be used.

The grafting in the above method (2) means chemically bonding a side chain to the base resin (or using the base resin as a side chain), and a known method can be used. Various methods including copolymerization can be used for introducing the reactive functional group.

Among these methods, from the viewpoint of adhesion to polyester film, adhesion to various inks, magnetic paints and adhesives, water-resistant adhesion, heat resistance and blocking resistance,
Graft modified polyester resins are particularly preferred.

(Graft-Modified Polyester Resin) In general, the graft-modified polyester resin is prepared by reacting a radical initiator and a radical-polymerizable monomer mixture in a state where a hydrophobic copolymerized polyester resin is dissolved in an organic solvent. Can be manufactured by. The reaction product after the completion of the grafting reaction is a graft copolymer of a hydrophobic copolymerized polyester and a radically polymerizable monomer, as well as a non-grafted hydrophobic copolymerized polyester and a hydrophobic copolymerized polyester. It also contains an unmodified radical polymer. The graft copolymer, which is one of the main constituent components in the coating layer of the present invention, includes all of these.

The above-mentioned "graft modification" means that when a trunk polymer is used as a main chain, a branch polymer made of a polymer different from the main chain is introduced into a side chain.

In the present invention, the coating layer is subjected to post-processing such as a printing layer. Therefore, from the viewpoint of the adhesiveness between the coating layer and the post-treatment layer, the acid value of the reaction product obtained by graft-polymerizing the radical-polymerizable monomer onto the hydrophobic copolymerized polyester resin is 600 eq / 10 ⁶ g or more. Is preferred. More preferably, the acid value of the reaction product is 1200 eq / 1
It is 0 ⁶ g or more.

The mass ratio (a / b) of the hydrophobic copolyester resin (a) and the radical-polymerizable monomer (b) is
From the viewpoint of adhesiveness, it is preferably 40/60 or more,
It is more preferably 55/45 or more, and particularly preferably 60/40 or more. Also, the mass ratio (a / b)
From the viewpoint of blocking property, it is preferably 95/5 or less, more preferably 93/7 or less, and particularly preferably 90/10.

The graft modified polyester resin is in the form of a solution or dispersion of an organic solvent or a solution or dispersion of an aqueous solvent. In particular, a dispersion of an aqueous solvent, that is, a form of a water-dispersible resin is preferable in terms of working environment and coatability. To obtain such a water-dispersible resin, usually,
In an organic solvent, to the hydrophobic copolyester resin,
This is achieved by graft-polymerizing a radical-polymerizable monomer containing a hydrophilic radical-polymerizable monomer, then adding water and distilling off an organic solvent.

The above water-dispersible resin is finely dispersed in an aqueous solvent, has an average particle diameter of 500 nm or less as measured by a laser light scattering method, and has a semitransparent or milky white appearance. The water-dispersible resin having various average particle diameters can be obtained by adjusting the polymerization method, but the average particle diameter is 10 to 50.
A range of 0 nm is preferred. Also, in terms of dispersion stability, 4
The thickness is preferably 00 nm or less, more preferably 300 nm or less. If the average particle diameter exceeds 500 nm, the gloss of the surface of the coating layer is reduced, and the transparency of the coating film is likely to be reduced. On the other hand, if the average particle size is less than 10 nm, the adhesiveness and the water-resistant adhesiveness are likely to deteriorate, which is not preferable.

The hydrophilic radical-polymerizable monomer used for the polymerization of the water-dispersible resin means a group having a hydrophilic group or capable of being converted into a hydrophilic group later. The radically polymerizable monomer having a hydrophilic group, a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group, an amide group,
Examples thereof include radically polymerizable monomers containing quaternary ammonium base and the like.

On the other hand, examples of the radical polymerizable monomer that can be converted into a hydrophilic group include radical polymerizable monomers having functional groups such as acid anhydride groups, glycidyl groups and chloro groups. Of these, the radical polymerizable monomer having a carboxyl group is preferable from the viewpoint of water dispersibility. That is, a radical polymerizable monomer having a carboxyl group or a functional group capable of generating a carboxyl group is preferable.

The modified resin containing the graft-modified polyester resin is preferably one having high breaking strength from the viewpoint of scratch resistance. Specifically, the breaking strength when a film is formed from a resin composition containing other components such as a modified resin, a sulfonate group-containing antistatic agent, and a crosslinking agent is 10M.
It is necessary to be Pa or more. For that purpose, the breaking strength when the modified resin alone is formed into a film is preferably 10 MPa or more. The breaking strength can be determined by various measuring methods. However, if the breaking strength is too high, cleavage easily occurs near the surface of the base film on the side of the coating layer, so the upper limit of the breaking strength is 100 M.
It is Pa.

On the other hand, the base resin to be modified preferably has a low glass transition temperature from the viewpoint of adhesiveness to other objects, and from the viewpoint of ink adhesion under high temperature and high humidity environment,
The glass transition temperature of the base resin is preferably in the range of 10 to 100 ° C. Further, the upper limit of the glass transition temperature of the base resin is preferably 80 ° C. By modifying these resins to increase the breaking strength, it becomes possible to satisfy all the properties such as adhesiveness, ink adhesion, scratch resistance and blocking resistance.

(Polyester resin) In the graft-modified polyester resin, the hydrophobic copolyester resin is essentially water-insoluble which does not disperse or dissolve in water by itself. If a polyester resin that disperses in water or dissolves in water is used as a trunk polymer in the graft polymerization, the adhesiveness and the water-resistant adhesiveness deteriorate, which is not preferable.

The hydrophobic copolyester resin contains an aromatic dicarboxylic acid of 60 to 99% as the dicarboxylic acid component.
5 mol%, 0 to 39.5 mol% of aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid, and 0.5 to 10 mol% of dicarboxylic acid containing a polymerizable unsaturated double bond are preferable. . More preferably, the aromatic dicarboxylic acid is 68 to 98 mol%, the aliphatic dicarboxylic acid and / or the alicyclic dicarboxylic acid is 0 to 30 mol%, and the dicarboxylic acid containing a polymerizable unsaturated double bond is 2 to 7%. Mol%.

When the aromatic dicarboxylic acid content is less than 60 mol%, or when the aliphatic dicarboxylic acid content and / or
Alternatively, when the alicyclic dicarboxylic acid exceeds 40 mol%, the adhesive strength tends to decrease. Further, when the dicarboxylic acid containing a polymerizable unsaturated double bond is less than 0.5 mol%, it becomes difficult to efficiently graft the radically polymerizable monomer onto the polyester resin, and conversely 10 If it exceeds mol%, the viscosity remarkably increases in the latter stage of the grafting reaction, which hinders the progress of uniform reaction, which is not preferable.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid and the like. In addition, since a hydrophilic group-containing dicarboxylic acid such as 5-sodium sulfoisophthalic acid has poor water resistance adhesion,
It is preferable not to use.

As the aliphatic dicarboxylic acid, succinic acid,
Examples thereof include adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid and the like. Further, as the alicyclic dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
Examples thereof include 1,2-cyclohexanedicarboxylic acid and its acid anhydride.

Examples of the dicarboxylic acid containing a polymerizable unsaturated double bond include (1) α, β-unsaturated dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid and citraconic acid; ) 2,5-norbornene dicarboxylic acid anhydride, alicyclic dicarboxylic acid containing an unsaturated double bond such as tetrahydrophthalic anhydride, and the like. Among these dicarboxylic acids containing a polymerizable unsaturated double bond, fumaric acid, from the viewpoint of polymerizability,
Maleic acid and 2,5-norbornene dicarboxylic acid are preferred.

On the other hand, the glycol component has 2 carbon atoms.
Examples thereof include an aliphatic glycol having 10 to 10, an alicyclic glycol having 6 to 12 carbon atoms, and an ether group-containing glycol. Two or more of these glycol components may be used in combination.

As the aliphatic glycol having 2 to 10 carbon atoms, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-
Pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol and the like can be mentioned. Further, as the alicyclic glycol having 6 to 12 carbon atoms, 1,
4-cyclohexane dimethanol etc. are mentioned.

As the ether group-containing glycol, glycols obtained by adding ethylene oxide or propylene oxide to two phenolic hydroxyl groups of diethylene glycol, triethylene glycol, dipropylene glycol, and bisphenols, for example, 2,2 -Bis (4-hydroxyethoxyphenyl)
Propane etc. can be mentioned. Polyethylene glycol, polypropylene glycol, polytetramethylene glycol can also be used if necessary.

Among these glycols, 1,2 and 3 are preferable glycols for increasing the breaking strength.
-Propylene glycol, neopentyl glycol, 2
-Methyl-1,3-propanediol, ethylene oxide adduct of bisphenol A, cyclohexane dimethylol, tricyclodecane dimethylol, cyclohexane diol are preferably contained. It is preferable that these glycols are copolymerized in an amount of 5 to 80 mol% based on all glycol components. The copolymer composition ratio can be analyzed by NMR or the like. If the amount of the glycol is less than 5 mol% with respect to the total glycol component, the effect of introduction is small.
On the other hand, when it exceeds 80 mol%, the melt viscosity during polymerization tends to be high. Therefore, it may be difficult to increase the molecular weight, and conversely the resin may become brittle.

In the hydrophobic copolyester resin, 0 to 5 mol% of a trifunctional or higher polycarboxylic acid and / or polyol can be copolymerized.

As the trifunctional or higher polycarboxylic acid,
(Anhydrous) trimellitic acid, (anhydrous) pyromellitic acid,
(Anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) and the like are used.

As the trifunctional or higher functional polyol,
Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like are used.

The trifunctional or higher functional polycarboxylic acid and / or polyol is copolymerized in the range of 0 to 5 mol%, preferably 0 to 3 mol% based on the total acid component or the total glycol component. However, if it exceeds 5 mol%, gelation tends to occur during polymerization, which is not preferable.

The lower limit of the weight average molecular weight of the hydrophobic copolyester resin is preferably 5,000 from the viewpoint of adhesive strength. The upper limit is preferably 50,000 from the viewpoint of gelation during polymerization.

(Polymer-Containing Polymerizable Unsaturated Monomer) Various kinds of polymerizable unsaturated monomers can be used. For example, various (meth) acrylic acid esters, vinyl esters, vinyl ethers, styrene and styrene derivatives,
Examples thereof include maleic acid and its anhydrides and esters, fumaric acid and its esters, itaconic acid and its anhydrides and esters.

Among these, from the viewpoint of increasing the breaking strength of the graft-modified polyester resin, (1) fumaric acid, monoester of fumaric acid such as monoethyl fumarate, diethyl fumarate, dibutyl fumarate, or maleic acid thereof and its anhydride. (2) monoesters or diesters of maleic acid such as monoethyl maleate, diethyl maleate and dibutyl maleate, (3) itaconic acid and its anhydrides, monoesters or diesters of itaconic acid, (4) phenylmaleimide, etc. Maleimide,
(5) Styrene derivatives such as styrene, α-methylstyrene, t-butylstyrene and chloromethylstyrene,
(6) Vinyltoluene, (7) Divinylbenzene and the like are preferable.

Further, in addition to the above components, various (meta)
Acrylic esters can also be used. For example,
(1) Alkyl acrylate, alkyl methacrylate (as the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group,
t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.),
(2) 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, hydroxy-containing acrylic monomer of 2-hydroxypropyl methacrylate, (3) acrylamide, methacrylamide, N-methylmethacrylamide,
Amide group-containing acrylic monomers of N-methylacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-phenylacrylamide,
(4) N, N-diethylaminoethyl acrylate,
Amino group-containing acrylic monomer of N, N-diethylaminoethyl methacrylate, (5) glycidyl acrylate, epoxy group-containing acrylic monomer of glycidyl methacrylate, (6) acrylic acid, methacrylic acid and salts thereof (sodium salt, potassium salt) Examples thereof include acrylic monomers containing a carboxyl group such as salt and ammonium salt) or a salt thereof.

Of these polymerizable unsaturated monomers, maleic anhydride or its ester is preferred in terms of enhancing the breaking strength of the graft-modified polyester. The above monomers can be copolymerized by using one kind or two or more kinds.

(Polymerization Initiator and Other Additives) As the graft polymerization initiator, organic peroxides and organic azo compounds known to those skilled in the art can be used.

The organic peroxide is benzoyl peroxide, t-butyl peroxypivalate, and the organic azo compound is 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-). Dimethylpareronitrile) and the like. The amount of the polymerization initiator used for carrying out the graft polymerization is at least 0.2% by mass, preferably 0.5% by mass or more, based on the polymerizable monomer.

In addition to the polymerization initiator, a chain transfer agent for controlling the chain length of the branch polymer, for example, octyl mercaptan, mercaptoethanol, 3-t-butyl-4-hydroxyanisole, etc. may be used if necessary. it can. In this case, it is preferable to add it in the range of 0 to 5 mass% with respect to the polymerizable monomer.

(Reaction Solvent) The grafting reaction solvent is preferably composed mainly of an aqueous organic solvent having a boiling point of 50 to 250 ° C. Here, the aqueous organic solvent means one having a solubility in water at 20 ° C. of at least 10 g / L or more, preferably 20 g / L or more. Boiling point is 25
If the temperature exceeds 0 ° C, the evaporation rate is too slow and the coating film cannot be sufficiently removed even by heat treatment, which is not preferable. On the other hand, if the boiling point is less than 50 ° C, an initiator that cleaves into radicals at a temperature of less than 50 ° C must be used when carrying out the grafting reaction using it as a solvent, which increases the handling risk. Not preferable.

As the aqueous organic solvent, a hydrophobic copolymerized polyester resin can be dissolved well, and a polymerizable monomer mixture containing a carboxyl group-containing polymerizable monomer and its polymer can be dissolved relatively well. Of the first group of aqueous organic solvents.

As the first group of aqueous organic solvents, (1) esters such as ethyl acetate, (2) ketones such as methyl ethyl ketone, (3) methyl isobutyl ketone,
(4) cyclohexanone, (5) tetrahydrofuran,
Cyclic ethers such as dioxane and 1,3-dioxolane, (6) ethylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol
Glycols such as rupropyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether
Carbitols such as ruthels, (7) methyl carbitol, ethyl carbitol and butyl carbitol,
(8) Glycols such as ethylene glycol diacetate and ethylene glycol ethyl ether acetate, or lower esters of glycol ether, (9) Ketone alcohols such as diacetone alcohol, (1
0) dimethylformamide, dimethylacetamide, N
Examples thereof include N-substituted amides such as -methylpyrrolidone.

Further, as the aqueous organic solvent, the copolymerized polyester resin is hardly dissolved, but the polymerizable monomer mixture containing the carboxyl group-containing polymerizable monomer and the polymer thereof can be dissolved relatively well. It is also possible to use a second group of aqueous organic solvents.

Examples of the second group of aqueous organic solvents include water, lower alcohols, lower carboxylic acids, lower amines and the like. Among these, alcohols and glycols having 1 to 4 carbon atoms are particularly preferable. preferable.

When the grafting reaction is carried out in a single solvent,
Only one of the first group of aqueous organic solvents can be chosen. When the mixed solvent is used, there may be a case where plural kinds are selected only from the first group of aqueous organic solvents, or at least one kind is selected from the first group of aqueous organic solvents and at least one kind is added from the second group of aqueous organic solvents. .

In both cases where the graft polymerization reaction solvent is a single solvent from the first group of aqueous organic solvents, and when it is a mixed solvent consisting of one kind of each of the first group and second group of aqueous organic solvents. A graft polymerization reaction can be performed. However, in the case of the former, there are differences in the progress behavior of the grafting reaction, the appearance and properties of the grafting reaction product and the water dispersion derived therefrom, and thus the latter group of aqueous organic solvents. It is preferable to use a mixed solvent consisting of one of the above.

From the viscosity measurement of the copolyester in the solution, in the solvent of the first group, the molecular chain of the copolyester was in a state in which the chain having a large spread was extended, and the mixed solvent of the first group / second group It was confirmed that they were entangled in a thread-like shape with a small spread.

It is effective to prevent gelation by adjusting the dissolved state of the copolyester to prevent intermolecular crosslinking. The compatibility of highly efficient grafting and suppression of gelation is achieved in the latter mixed solvent system.

The mixing ratio (mass ratio) of the mixed solvent of the first group / second group is preferably 95/5 to 10/90, more preferably 90/10 to 20/80, and particularly preferably. The range is 85/15 to 30/70. The optimum mixing ratio is determined according to the solubility of the polyester used and the like.

(Water Dispersion) The grafting reaction product is preferably neutralized with a basic compound, and can be easily water-dispersed by neutralization. As the basic compound, a compound that volatilizes during the formation of a coating film or during thermal curing by blending with a curing agent is desirable, and ammonia, organic amines and the like are preferable.

Preferred compounds are triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-
Methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyl Examples thereof include iminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine and triethanolamine.

The basic compound has a PH value of 5.0 to 9.0 depending on the content of the carboxyl group contained in the graft reaction product by at least partial neutralization or complete neutralization. It is preferable to adjust it to fall within the range.

When a basic compound having a boiling point of 100 ° C. or lower is used, the amount of residual basic compound in the coating film after drying is small, and the adhesiveness of a metal or an inorganic vapor-deposited film or when laminated with another material is small. Excellent water and heat resistant adhesion.

Further, by using a basic compound at 100 ° C. or higher, or by controlling the drying conditions so that 500 ppm or more of the basic compound remains in the coating film after drying,
The transferability of printing ink can be improved.

In the aqueous dispersion, the weight average molecular weight of the polymer of the radically polymerizable monomer is preferably 500 to 50,000. It is generally difficult to control the weight average molecular weight to be less than 500, the grafting efficiency tends to be low, and the hydrophilic group may not be sufficiently imparted to the copolymerized polyester.

Further, the graft polymer of the radically polymerizable monomer forms a hydrated layer of dispersed particles. Therefore, in order to have a hydrated layer with a sufficient thickness and obtain a stable dispersion,
The weight average molecular weight of the graft-polymerized product of the radical-polymerizable monomer is preferably 500 or more. The upper limit of the weight average molecular weight is preferably 50,000 from the viewpoint of polymerizability in solution polymerization. The control of the molecular weight within this range can be controlled by appropriately combining an initiator amount, a monomer dropping time, a polymerization time, a reaction solvent, a monomer composition, or a chain transfer agent or a polymerization inhibitor if necessary.

The graft-modified polyester resin obtained by modification as described above has a carboxyl group in the molecule and an ester of a lower alcohol, and these functional groups are easily esterified with the polyester resin which is the main chain by heating. Since it causes an exchange reaction, it exhibits self-crosslinking properties and exhibits high solvent resistance. When an unsaturated monomer having a plurality of carboxyl groups in the molecule such as maleic acid or itaconic acid or a half ester thereof has a side chain, dehydration or dealcoholization reaction is caused by heating to form an anhydride, and the main chain The reaction with the polyester is preferable because the efficiency of self-crosslinking is further increased.

The crosslinkability of the coating layer can be evaluated by various methods. For example, it can be examined by the insoluble content in a chloroform solvent which dissolves both the hydrophobic copolyester resin and the radical polymer. The insoluble matter content of the coating film obtained by drying at 80 ° C. or lower and heat treatment at 120 ° C. for 5 minutes is preferably 50% or more, more preferably 70% or more from the viewpoint of adhesiveness, water-resistant adhesion and blocking property. Is.

(Polymeric Antistatic Agent) In the present invention,
As another constituent component of the coating layer C, a polymer antistatic agent having at least one sulfonate group or phosphate group in the molecule is used. The characteristic feature of this polymer type antistatic agent is the structure having a large number of highly hydrophilic sulfonic acid components and phosphoric acid components. These polymeric antistatic agents may be used alone or in combination of two or more.

As the resin containing a sulfonic acid group component in the molecule, a sodium salt of polystyrenesulfonic acid,
Homopolymers such as potassium salts, lithium salts, ammonium salts and phosphonium salts, copolymers of acrylic monomers such as acrylic acid esters or methacrylic acid esters with styrene sulfonic acid monomers, and acrylamide methyl propane sulfonic acid Examples thereof include copolymers of saturated monomers. In the present invention, the sulfonate may be a mixture of metal salt and amine salt.

Examples of the resin containing a phosphate group in the molecule include resins obtained by polymerizing or copolymerizing various phosmers (manufactured by Unichemical) which are unsaturated monomers having a phosphate group.

The weight average molecular weight of the antistatic agent is preferably in the range of 1,000 to 1,000,000, more preferably 5,000 to 1,000,000. When the weight average molecular weight is less than 1,000, the coating film is excellent in gloss, but it becomes difficult to obtain water-resistant adhesion of the coating film. On the other hand, if it exceeds 1 million, the water-resistant adhesion will be high, but it will be difficult to uniformly mix it with the modified resin.
The coating film gloss tends to decrease.

The white laminated polyester film of the present invention has further improved sharpness at the time of printing.
The color tone b value measured from the coating layer side is preferably -5.0 to 2.0. Further, the upper limit value of b value is preferably 1.5, and particularly preferably 0.0. On the other hand, in applications where the substrate is not bluish, the lower limit of the color tone b value measured from the coating layer side is preferably -2.0. The color tone b value is a scale representing the degree of yellowness, and b
It means that the larger the value is, the stronger the yellowness is, and the more negative the b value is, the stronger the bluishness is.

In order to adjust the color tone b value measured from the coating layer side to 2.0 or less, sodium salt, potassium salt and lithium salt are used as the basic component of the polymer compound containing polystyrene sulfonate as a main component. It is preferable to use.
When the color tone b value exceeds 2.0, the apparent whiteness of the coating layer becomes insufficient, and yellowness tends to stand out.

Further, the white laminated polyester film of the present invention has a surface specific resistance of 1 × 10 ⁶ to 1 at 65% RH at 25 ° C. from the viewpoint of antistatic property in the film forming step and the processing step. It is necessary to be × 10 ¹³ Ω / □. Since the surface resistivity is low, it is possible to prevent foreign matter from adhering due to static electricity when the film roll is unwound and the print layer is provided, and therefore defects such as print defects can be eliminated.

In order to make the surface specific resistance value of the coating layer surface at 25 ° C. and 65% RH to be 1 × 10 ¹³ Ω / □ or less, the content of the sulfonate group-containing antistatic agent is set to the resin composition of the coating layer. It is preferably 5% by mass or more with respect to the product. However, if the content exceeds 60% by mass, the performance of adhesion to the base film, film strength, and solvent resistance may become insufficient. Further, the suitability for dampening water (water loss) is deteriorated during offset printing, and problems such as fading and bleeding are likely to occur. Further, even if the surface specific resistance value of the coating layer surface is less than 1 × 10 ⁶ Ω / □, there is no difference in practical effect.

Further, in the white laminated polyester film of the present invention, the contact angle of the surface of the coating layer with water is preferably 60 to 80 degrees from the viewpoint of water-resistant adhesion. If the contact angle with water is less than 60 degrees, dampening water suitability (water loss) may be deteriorated during offset printing, and problems such as blurring and bleeding may occur. On the other hand, even if the contact angle with water exceeds 80 degrees, there is practically no difference in effect.

In the present invention, in order to further improve the water-resistant adhesion, various crosslinking agents may be used in combination with the resin composition forming the coating layer. As a cross-linking agent,
Examples thereof include melamine-based, epoxy-based, isocyanate-based, amine-based, amide-based, aziridine-based and the like. The type and blending amount of the crosslinking agent may be appropriately determined according to the mixing ratio of the modified resin and the sulfonate group-containing antistatic agent and the type and content of those functional groups. For example, when a melamine-based crosslinking agent or an isocyanate-based crosslinking agent is used, usually 2 to 30 parts by mass is suitable for 100 parts by mass of the resin component.

When an isocyanate compound is used as a crosslinking agent, it is also possible to use a block type isocyanate compound. As a method for producing a white laminated polyester film, a coating layer is provided on the surface of the base material film and then stretched in at least one direction, and then heat setting treatment is performed.
When the so-called in-line coating method is adopted, it is preferable to select a block type isocyanate compound having a blocking agent satisfying the following conditions as the block type isocyanate compound.

That is, the deblocking temperature at which the blocking agent at the terminal of the isocyanate compound is desorbed by heat energy must have an upper limit not higher than the heat setting temperature, and a lower limit is the heat setting temperature from the latter stage of the stretching temperature. It is preferable that the period is up to. As such an isocyanate blocking agent, bisulfites are preferable.

When the aqueous coating solution is applied to the surface of the substrate film, in order to improve the wettability to the film and coat the coating solution uniformly, a known anionic surfactant,
It is preferable to add at least one nonionic surfactant in a necessary amount.

The thickness of the coating layer is not particularly limited, but in the present invention, the dry coating thickness after biaxial stretching is preferably 0.05 to 1.0 μm, more preferably from the viewpoint of adhesion and blocking resistance. The thickness is 0.07 to 0.5 μm, particularly preferably 0.09 to 0.3 μm.

The thickness of the coating layer after biaxial stretching is, for example, obtained by embedding a white laminated polyester film in an epoxy resin, cutting the cross section of the film with a microtome at right angles to the film surface, and taking a photograph with a transmission electron microscope (TEM). It can be obtained by shooting. In TEM observation, 10 points are photographed at different places, and the average value of the coating layer thickness read from the scale is used as the coating layer thickness of the white laminated polyester film.

In addition, a white pigment may be contained in the coating liquid for forming the coating layer in order to further improve the hiding property. Further, within the range that does not impair the effects of the present invention, known additives such as surfactants, antioxidants,
Heat resistance stabilizer, weather resistance stabilizer, UV absorber, organic lubricant,
Pigments, dyes, inorganic particles, heat resistant organic particles, nucleating agents, antibacterial agents and the like may be added.

[Manufacturing Method] The method for manufacturing the white laminated polyester film of the present invention is arbitrary and is not particularly limited. For example, it can be manufactured as follows.

The film raw materials used for the A layer and the B layer are sufficiently vacuum dried, then melted by an extruder and extruded into a sheet form while applying static electricity to a rotating cooling metal roll from a T-die to obtain an unstretched film. .

At this time, the white pigment and other additives are not added to the extruder by powdering and kneading, but a masterbatch polymer in which the white pigment and the like are separately contained in a polyester resin at a high concentration in advance is prepared. However, the method of diluting them with a polyester resin is preferable from the viewpoint of uniform mixing. As the extruder, it is preferable to use a twin-screw extruder in order to further sufficiently uniformly mix various film raw materials. Further, it is preferable to add an alkaline earth metal salt and / or an alkali metal salt and phosphoric acid or a salt thereof when polymerizing the polyester in order to improve electrostatic adhesion. Further, addition of phosphoric acid or a salt thereof also has an effect of improving color tone (particularly, b value).

The lamination of A layer and B layer constituting the base material is A
It is most preferable to employ a co-extrusion method in which the resin for the layer and the resin for the other layer are supplied to separate extruders, then laminated in a molten state and extruded from the same die.

The above-mentioned unstretched film is further stretched between rolls having a speed difference (roll stretching), stretched by gripping with a clip and expanded (tenter stretch) or stretched by expanding by air pressure (inflation). Biaxial orientation treatment is performed by, for example, stretching.

The conditions for stretching and orienting the unstretched film are closely related to the physical properties of the film. As the biaxial stretching method, a sequential biaxial stretching method (vertical-horizontal, horizontal-vertical, vertical-vertical-horizontal,
Longitudinal-horizontal-longitudinal) and simultaneous biaxial stretching methods (methods driven by a linear motor) are well known.
The stretching / orientation conditions will be described by taking the most common sequential biaxial stretching method, particularly a method of stretching an unstretched sheet in the longitudinal direction and then in the width direction.

First, in the first stage of the longitudinal stretching step, the crystallization temperature (Tc1) of polyester (glass transition temperature (Tg) -10 ° C.) or more is raised between two or a large number of rolls having different peripheral speeds. It is stretched 2.5 to 5 times at a temperature of less than. As a heating means at this time, a method using a heating roll or a non-contact heating method may be used, or they may be used in combination.

Then, the end of the longitudinally uniaxially stretched film is guided to a tenter while gripping the end portion with a clip, and after preheating, it is heated in the width direction at a temperature not lower than the glass transition temperature (Tg) of the polyester and lower than the temperature rising crystallization temperature (Tc1). Stretch 5 to 5 times.

The biaxially stretched film thus obtained is subjected to a heat treatment in order to improve dimensional stability. The heat treatment is preferably performed in a tenter, and is preferably performed in the range of the melting point Tm of the polyester, Tm-50 ° C to Tm. Further, depending on the application, in order to further improve the dimensional stability, 1 to 10% in the width direction and / or the longitudinal direction.
May be subjected to relaxation treatment. The temperature for relaxation treatment is
It is appropriately set according to the heat treatment temperature at the time of post-processing for the purpose of using the film of the present invention.

As the step of providing the coating layer, any method such as a method of coating before stretching the film, a method of coating after longitudinal stretching, a method of coating on the film surface after the biaxial orientation treatment and the like can be used. Among these, the in-line coating method, in which the base polyester film is applied before the crystal orientation is completed and then stretched in at least one direction, the crystal orientation of the polyester film is completed, is more remarkable in the effect of the present invention. It is a preferred method because it can be expressed. The coating layer may be provided on only one side or both sides of the film depending on the application.

Since the modified resin and the polymeric antistatic agent have a large difference in hydrophilicity and are easily separated into layers, it is preferable to adopt special coating conditions. Immediately before application, apply 1
Immediately after applying a shear rate of 000 (1 / sec) or more, 2
Apply to the substrate film within 2 seconds, and 70 seconds within 2 seconds after application.
Pre-drying is performed at a wind speed of 10 to 20 m / sec for 1 to 3 seconds and then at 90 ° C. or higher. As a result, the modified resin, the polymeric antistatic agent and other components are uniformly dispersed, and a good surface resistance value is obtained.

The conditions of heat treatment after coating and drying are not particularly limited, but in order to exhibit the self-crosslinking property of the graft copolymer, it is preferable to increase the amount of heat within the range where thermal deterioration does not occur. Specifically, it is 90 ° C to 250 ° C, more preferably 150 ° C to 220 ° C. However, by extending the drying time, sufficient self-crosslinking property is exhibited even at a relatively low temperature, and therefore it is not necessarily limited to the above conditions. However, in order to lengthen the drying time, it is necessary to slow the film feed rate or lengthen the drying zone. The former is less productive,
The latter is also not a suitable method for industrial implementation, due to equipment restrictions.

As a method for providing the coating layer, a commonly used method such as a gravure coating method, a kiss coating method, a dipping method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method is applied. it can.

Further, a magnetic recording layer is provided on a predetermined surface of the obtained white laminated polyester film, and a magnetic card is produced through processes such as printing and punching. Also, I
An IC card is prepared by embedding a C chip and an antenna in an adhesive and sandwiching them with the white laminated polyester film provided with two or more printing ink layers punched to a predetermined size.

In the process of making a card such as the magnetic card or IC card, the film is easily scratched by being rubbed. When the coating layer of the film is scratched,
Microscopic voids are generated at the interface between the ink or adhesive and the white polyester film due to the entrainment of bubbles during high-speed transfer of ink or high-speed coating of adhesive, which reduces the characteristics and quality of printed matter. Occur. However, the above problem can be solved by increasing the breaking strength of the coating layer made of the modified resin or the like so that the surface is not easily scratched. Further, the durability of the ink and the adhesive after the immersion in the solvent and the treatment in the moist heat atmosphere are also improved.

The scratches have a length of 500 μm or more and a width of 10 μm or more in the major axis direction as observed by a microscope. Scratches with a length of 500 μm or more in the long axis direction
When it exceeds 10 lines per cm ² , it may cause peeling of the ink or the adhesive. The length along the major axis observed by a microscope is 500 μm or more and the width is 10 μm.
Preferably m above the wound is less than ten per 1 cm ^2, more preferably the length 300μm following flaws in the axial direction of the can 1 cm ² per 10 or less, particularly preferably a length in the long axis direction There are 10 or less scratches of 200 μm or less per 1 cm ² .

As the adhesive, an epoxy adhesive,
Examples thereof include polyester adhesives, polyester hot melt adhesives, olefin hot melt adhesives, and the like. The thickness of the adhesive layer is preferably in the range of 10 to 500 μm, but it is preferable to appropriately adjust it in consideration of the thickness of the white laminated polyester film of the present invention.

When a hot melt adhesive is used,
The laminating temperature is preferably 200 ° C. or lower.
When the laminating temperature is 200 ° C. or higher, the white laminated polyester film is likely to be wrinkled or distorted due to shrinkage. Further, curling or the like is likely to occur in the pasted state. Therefore, it is preferable to perform molding in a short time of 1 minute or less using a method such as an injection molding method.

When a printing layer is provided on the surface of the coating layer of the white laminated polyester film of the present invention, the printing ink applied to the surface of the coating layer is not particularly limited, but ultraviolet curable ink, oxidation polymerization type ink, general dry type ink. Etc. can be used. For example, in the case of UV curable ink,
Polyester, urethane, acrylic resin and modified products thereof as the resin component, compounds having a plurality of unsaturated bonds such as esterification products of polyols such as ethylene glycol, glycerin, pentaerythritol and acrylic acid as the crosslinking component, and carbon as the pigment component. black,
Examples thereof include aluminum hydroxide or aluminum powder as a main constituent component, to which a polymerization initiator such as diethylaminobenzophenone is added.
The method for providing these printing layers is not particularly limited, and a letterpress,
It can be performed by a method such as planographic printing, letterpress printing, screen printing, flat printing, rotary printing, and transfer.

Specific examples of printing ink include Best Cure 161, VP, VNL, STP (T & K TOKA
), FD-O, FD-O-G, FD-O-new KR
In addition to offset inks such as No. 2 (manufactured by Toyo Ink Co., Ltd.), any commonly known one can be used.
Further, in terms of durability of the printed layer, use of OP varnish is desirable. A desirable OP varnish is video OP varnish Y.
(Made by T & K TOKA) or the like can be used.

When a magnetic recording layer is provided on the surface of the coating layer of the white laminated polyester film of the present invention to prepare a magnetic card, the constituent components of the magnetic recording layer are not particularly limited. It is mentioned as a component of a layer. That is, as magnetic powder, γ-Fe
₂ O ₃ , CrO ₂ , Co-γ-Fe ₂ O ₃ , metal powder,
As the binder, vinyl acetate, vinyl resin such as PVC, rubber resin such as acrylonitrile / butadiene copolymer, fibrin such as acetyl cellulose and nitrocellulose, epoxy resin, phenol resin, monomer isocyanate, Modified isocyanate urethane prepolymer, polyurethane resin used in the form of blocked isocyanate, etc., and a dispersant added if necessary,
Examples thereof include lubricants, antistatic agents such as carbon, stabilizers, and plasticizers. The method for providing these magnetic recording layers is not particularly limited, and a known method can be used.

[0138]

EXAMPLES Next, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to the methods described in the examples. Various properties of the white laminated polyester film in the present invention were evaluated by the following evaluation methods.

(1) Average particle size The coating layer provided on the white laminated polyester film is
Scrape with Bencotton or gauze impregnated with organic solvent. The sample was dried overnight in a vacuum dryer to remove the organic solvent. The dried sample was subjected to ion plasma etching treatment to expose the white pigment and inorganic particles contained in the layer A of the substrate. Then, using a scanning electron microscope (SEM), the magnification was appropriately changed according to the size of the particles, and a photograph was taken. The equivalent circle diameter of particles of at least 100 points was determined by an image processing apparatus and divided by the number of particles to determine the number-based average particle diameter (μm). When the contrast of the photographed particles is weak, the contours of the particles may be traced on the OHP film with an extra-fine magic pen, and the trace image may be obtained by an image processing device to obtain the equivalent circle diameter of the particles.

For the particles in the powder state before adding the particles to the polyester, double-sided tape was attached to the SEM sample stand,
A powder was thinly placed on the powder, and after vapor deposition of carbon, a magnification was appropriately changed according to the size of the particles by using a scanning electron microscope (SEM), and a photograph was taken. The equivalent circle diameter of particles of at least 100 points was determined by an image processing apparatus and divided by the number of particles to determine the number-based average particle diameter (μm).

(2) Intrinsic viscosity of polyester resin The polyester raw material was dissolved in a mixed solvent of 60% by mass of phenol and 40% by mass of 1,1,2,2-tetrachloroethane, and the solid content was filtered with a glass filter, then 30 It was measured at ° C.

(3) Compositional analysis of resin for coating layer Deuterated chloroform / trifluoroacetic acid = 90
It melt | dissolved in the mixed solvent of / 10 (volume ratio), and performed it using the NMR spectroscope (Varian, Unity-500).

(4) Glass transition temperature and melting point Differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-5)
0), 10 mg of a sample was filled in an aluminum pan, heated to 290 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere, held at the same temperature for 3 minutes, and then the aluminum pan was thrown into liquid nitrogen. Quenched. The rapidly cooled aluminum pan was set again in the differential scanning calorimeter, and the glass transition temperature and melting point (peak temperature of endothermic peak) were determined from the chart when the temperature was raised at a temperature rising rate of 20 ° C./min.

(5) Breaking strength A resin composition or a resin corresponding to the coating layer of each Example and Comparative Example was dried on a biaxially oriented polypropylene film (Toyobo Co., Ltd., P2161, thickness 50 μm). Apply so that the thickness of the coating film is 80 μm,
It was dried for 2 hours. Then, the coating film was peeled off from the biaxially oriented polypropylene film to obtain a film sample. This sample was cut out to a width of 1 cm with a single-edged razor, the sample length was 4 cm, and the crosshead speed was 100 mm.
/ Min It evaluated by the tensile tester.

(6) Apparent Density of Film Four films were cut into squares of 5.00 cm square to obtain samples. 4 pieces of this are piled up, and the thickness is changed by a micrometer.
It was measured by a digit and the average value of the overlapping thickness was obtained. This average value was divided by 4 and rounded to three significant figures to obtain the average thickness (t: μm) per sheet. The weight (w: g) of four sheets of the same sample was measured with an effective precision balance with four significant digits, and the apparent density was obtained from the following formula. The apparent density was rounded to three significant figures. Apparent density (g / cm ³ ) = (w × 10 ⁴ ) / (5.00
X5.00xt)

(7) Color tone b value The color tone b value measured from the coating layer side of the coating film was used using a color difference meter (Z-1001DP manufactured by Nippon Denshoku Industries Co., Ltd.).

(8) Contact angle with water After leaving the sample in an atmosphere of 23 ° C. and 65% RH for 24 hours, a contact angle meter (Kyowa Interface Science Co., Ltd., C
A-X) was used to measure the contact angle between the surface of the coating layer of the sample and water using distilled water stored under the same conditions. The measurement was performed at 10 points, and the average value thereof was used as the contact angle data.

(9) Adhesion with Oxidative Polymerization Ink Oxidation polymerization type ink (Jujo Kako Co., Ltd., black) diluted solvent (Jujo Kabushiki Kaisha, Tetron) ink: diluted solvent = 4: 1 (volume) Ratio) and print on the film surface (the surface of the coating layer, if a coating layer is provided) with a Tetoron screen (# 250 mesh), then 2
It was left for 4 hours.

Then, a 100 mm cross cut surface of 2 mm square was put on the printing surface with a cutter knife, and an adhesive tape (Cellotape CT-made by Nichiban Co., Ltd.) was placed on it.
24) is affixed so that air bubbles do not enter, and further rubbed on it so that it adheres sufficiently. After that, both the front and rear ends of the ink surface where the adhesive tape was not adhered were pressed by hand to rapidly peel off the crosscut surface in the 90 ° direction.

The ink surface after peeling was observed, and the adhesiveness was evaluated based on the following four-stage criteria with respect to the ink residual rate in 100 squares (treating the number of peeled pieces even in a part of the squares). , ◎ and ○ were passed. ⊚: Residual rate 100% (no peeling at all) ◯: Residual rate 90% or more and less than 100% (can be used without problems in practice) Δ: Residual rate 70% or more and less than 90% (adhesion is slightly weak,
Practical problems may occur) x: Residual ratio less than 70% (adhesion problem)

(10) Adhesiveness with ultraviolet (UV) curable ink UV curable ink (U manufactured by Seiko Advance Co., Ltd., U
After printing VA710 black) on the film surface (the surface of the coating layer when the coating layer is provided) with a Tetoron screen (# 300 mesh), 500
UV exposure was performed at mJ / cm ² .

A cross-cut surface of 100 squares of 2 mm square was put into the cured ink layer with a cutter knife,
An adhesive tape (Cellotape CT-24, manufactured by Nichiban Co., Ltd.) is attached on top of it so that no air bubbles enter, and it is rubbed evenly over it so that no air bubbles remain. After that, both the front and rear ends of the ink surface on which the adhesive tape was not adhered were pressed by hand and rapidly peeled in the 90 ° direction.

The ink surface after peeling was observed, and the adhesiveness was evaluated based on the following four-stage criteria based on the ink residual ratio (treating the number of peeled pieces even in a part of the squares) in 100 squares. , ◎ and ○ were passed. ⊚: Residual rate 100% (no peeling at all) ◯: Residual rate 90% or more and less than 100% (can be used without problems in practice) Δ: Residual rate 70% or more and less than 90% (adhesion is slightly weak,
(Practical problems may occur) x: Residual ratio less than 70% (adhesiveness is poor)

(11) Water-resistant adhesion UV curable ink (manufactured by Seiko Advance Co., U
After printing VA710 black) on the film surface (the surface of the coating layer when the coating layer is provided) with a Tetoron screen (# 300 mesh), 500
UV exposure was performed at mJ / cm ² .

The above film was boiled in boiling water at 100 ° C. for 2 hours, wiped off water, and then dried in an oven at 40 ° C.
C., and dried for 30 minutes.

A cross-cut surface of 100 squares of 2 mm square was put into the cured ink layer with a cutter knife,
An adhesive tape (Cellotape CT-24, manufactured by Nichiban Co., Ltd.) is attached on top of it so that no air bubbles enter, and it is rubbed evenly over it so that no air bubbles remain. After that, both the front and rear ends of the ink surface on which the adhesive tape was not adhered were pressed by hand and rapidly peeled in the 90 ° direction.

The ink surface after peeling was observed, and the adhesiveness was evaluated by the following four-level criteria with respect to the ink residual rate in 100 squares (treating the number of peeled pieces even in a part of the squares). , ◎ and ○ were passed. ⊚: Residual rate 100% (no peeling at all) ◯: Residual rate 90% or more and less than 100% (can be used without problems in practice) Δ: Residual rate 70% or more and less than 90% (adhesion is slightly weak,
(Practical problems may occur) x: Residual ratio less than 70% (adhesiveness is poor)

(12) Surface specific resistance value After leaving the film in an atmosphere of 23 ° C. and 65% RH for 24 hours, a surface resistance measuring device (HIRESTA-IP, manufactured by Mitsubishi Petrochemical Co., Ltd.) was used in the atmosphere. , Applied voltage 500
The film surface at V (if a coating layer is provided,
The surface specific resistance value (Ω / □) of the coating layer surface) was measured.
The case where the surface resistivity was less than 1 × 10 ¹² Ω / □ was regarded as good.

(13) Film surface strength Two sample films were prepared, and a polyester hot melt adhesive (Vylon GM920, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm was sandwiched between them, and the film was sandwiched at 150 ° C. Heat fusion was performed for 5 minutes at a pressure of 30 MPa, the heat fusion film was cut into a width of 20 mm, and the sample film was rapidly peeled off. The state after peeling was visually judged on the basis of three levels, and ◯ was passed. ◯: Peeling is not possible or the material of the film is destroyed. Δ: Peeling is possible, but the film is not damaged. X: Peeled at the interface between the A layer and the B layer.

(14) Printability A pattern is printed by ordinary screen printing to improve finishability.
Visual evaluation was made at each stage, and ◯ was passed. ◯: Good printability Δ: Slight print missing ×: Large print missing

Example 1 [Film Raw Material] As a film raw material, 49.9% by mass of polyethylene terephthalate resin having an intrinsic viscosity of 0.62 dl / g and anatase type titanium dioxide particles having an average particle diameter of 0.3 μm obtained by a conventional method. (Fujititanium Co., Ltd., TA-300) 50.0% by mass and a fluorescent whitening agent (Eastman Chemical Co., Ltd., OB1) 0.1% by mass were mixed and supplied to a vent type twin-screw extruder. And kneaded in advance. Next, this molten resin is continuously supplied to a vent-type single-screw kneader, kneaded and extruded, and the obtained strand is cooled and cut to give titanium dioxide-containing master pellets having an intrinsic viscosity of 0.49 dl / g. (III) was produced.

Next, an intrinsic viscosity of 0.7% by mass of silica particles having an average particle diameter of 1.8 μm (manufactured by Fuji Silysia Chemical Ltd., Silysia) added by a conventional addition method during polymerization was added.
A 62 dl / g polyethylene terephthalate resin pellet was produced, and further solid phase polymerization (SSP) was performed to obtain a polyester resin (II) having an intrinsic viscosity of 0.75 dl / g.

Master pellets (II) containing 75% by mass of polyethylene terephthalate resin (I) having an intrinsic viscosity of 0.62 dl / g, and the above titanium dioxide particles (white pigment)
I) 25% by mass of pellets were mixed and vacuum-dried at 140 ° C. for 8 hours to obtain a film raw material (α) for layer B. Further, 30% by mass of titanium dioxide-containing master pellets (III) and 70% by mass of silica particles (inorganic particles) -containing solid-state polymerized polyester resin pellets (II) were pellet-mixed and vacuum dried at 140 ° C. for 8 hours, It was used as the film raw material (β) for the A layer.

[Preparation of Aqueous Coating Agent] (Preparation of Copolymerized Polyester) In a stainless steel autoclave equipped with a stirrer, a thermometer, and a partial reflux type cooler, 747 parts by mass of terephthalic acid and 664 parts by mass of isophthalic acid. Parts, 202 parts by mass of sebacic acid, 58 parts by mass of fumaric acid, 744 parts by mass of ethylene glycol, 720 parts by mass of neopentyl glycol.
The esterification reaction was carried out for 3 hours while raising the temperature from 60 ° C to 220 ° C. Next, 0.7 parts by mass of tetra-N-butyl titanate was added, and the temperature was raised from 200 ° C. to 220 ° C. over 1 hour to perform an esterification reaction. Next, after raising the temperature to 255 ° C. and gradually reducing the pressure of the reaction system,
The mixture was reacted under a reduced pressure of 0.22 mmHg for 1 hour and 30 minutes to obtain a copolyester. The obtained copolyester was pale yellow and transparent, and had a glass transition temperature of 40 ° C. and a weight average molecular weight of 20,000.

(Graft-modified polyester resin) In a reactor equipped with a stirrer, a thermometer, a reflux device and a metering dropping device, 75 parts by mass of the above copolymerized polyester resin, 56 parts by mass of methyl ethyl ketone, and 19 parts by mass of isopropyl alcohol. Part of the mixture was stirred under heating at 65 ° C. to dissolve the resin. After the resin is completely dissolved, maleic anhydride 15
Parts by weight were added to the polyester solution. Then, a solution prepared by dissolving 10 parts by mass of styrene and 1.5 parts by mass of azobisdimethylvaleronitrile in 12 parts by mass of methyl ethyl ketone was added dropwise to the polyester solution at 0.1 mL / min, and stirring was continued for another 2 hours. After sampling for analysis from the reaction solution, 5 parts by mass of methanol was added. Next, 300 parts by mass of ion-exchanged water and 15 parts by mass of triethylamine were added to the reaction solution and stirred for 1 hour. Then, the internal temperature of the reactor was raised to 100 ° C., methyl ethyl ketone, isopropyl alcohol, and excess triethylamine were distilled off to obtain a water-dispersion graft-modified polyester resin. The water-dispersion graft-modified polyester resin fat was light yellow and transparent, and had a glass transition temperature of 40 ° C. and a breaking strength of 30 MPa.

(Coating liquid) The graft-modified polyester resin and polystyrene sulfonate ammonium salt (manufactured by Japan NSC Co., Ltd., molecular weight 70,000) obtained above were mixed at a solid content mass ratio of 70/30 to obtain a total resin solid. Concentration is 5% by mass, solvent is water / isopropyl alcohol = 60 /
The mass ratio was adjusted to 40 to prepare an aqueous coating solution. The breaking strength of the film prepared from the resin composition of the coating liquid for coating layer by the method described in the above "(5) Breaking strength" was 30 MPa.

[Production of Laminated Film] The film raw materials were fed to different extruders, and a feed block was used to form a layer (B layer) made of the raw material (α) and a layer (A layer) made of the raw material (β). Was laminated in the molten state in the order of A layer / B layer / A layer, and the discharge rate of each extruder was adjusted so that the thickness ratio of each layer was 10:80:10. This molten resin is coextruded from a T die onto a rotating cooling metal roll whose temperature is adjusted to 25 ° C.,
An unstretched film having a thickness of 920 μm was prepared by adhering and solidifying by an electrostatic application method.

The obtained unstretched film was uniformly heated to 66 ° C. using a heating roll, and two pairs of nip rolls (low speed roll: 2 m / min, high speed roll: 6.2 m) having different peripheral speeds were used.
/ Min) and stretched 3.1 times. At this time, as an auxiliary heating device for the film, an infrared heating heater (rated output: 74 W / cm) equipped with a gold reflecting film in the middle of the nip roll was installed at a position 1 cm from the film surface facing both sides of the film. Heated at 30%. The uniaxially stretched film thus obtained was subjected to corona discharge treatment on both sides, and the water-based coating agent shown above was applied to both treated surfaces by the reverse coating method.

When the coating liquid was applied to both sides of the film, the following method was used. 1 between roll gaps
After applying a shear rate of 000 (1 / sec) or more to the substrate within 2 seconds, and drying for 2 seconds in an atmosphere of a temperature of 65 ° C and a wind speed of 15 m / sec, an atmosphere of a temperature of 130 ° C and a wind speed of 20 m / sec. Water was removed by drying under 3 seconds.

Then, while continuously holding the edges of the film with clips, the film was guided to a tenter, heated to 120 ° C., laterally stretched 3.7 times, fixed in the width direction, and heat treated at 230 ° C. for 5 seconds. The film was applied and further relaxed by 4% in the width direction at 200 ° C. to obtain a 100 μm-thick white laminated polyester film having a coating layer of 0.20 g / m ^{2 on} both sides. The average particle diameter of the particles in the layer A of the base material was 0.32 μm for the titanium oxide particles, which are white pigments, and 1.9 μm for the silica particles.

In this Example 1, the intrinsic viscosity (dl) of the polyester resins (I), (II) and (III) used as the substrate was determined.
/ G) is IV (I) = 0.62, IV (II) = 0.75, IV, respectively.
(III) = 0.49. The mixing ratio (mass%) of the resin (II) and the resin (III) in the layer A is 70 mass% (a = 70) and 30
It is mass% (b = 30). Substituting these numerical values into “IV (II) × a + IV (III) × b” on the left side of equation (1) yields 67.2.
Becomes Further, when substituting into the right side “IV (I) × 100” of the equation (1), it becomes 62.0. That is, it can be seen that the first embodiment satisfies the following relational expression (1) defined in claim 1 of the present invention. IV (II) × a + IV (III) × b> IV (I) × 100 (1)

Example 2 In Example 1, the polystyrene sulfonic acid ammonium salt of the coating solution (manufactured by Japan NSC Co., molecular weight 70,0) was used.
00) is a polystyrene sulfonic acid lithium salt (Japan NS
C Co., Ltd., molecular weight 10,000), in the same manner as in Example 1 to obtain a 100 μm thick white laminated polyester film having 0.20 g / m ² coating layers on both sides. The breaking strength of the film prepared from the resin composition of the coating liquid for coating layer by the method described in the above "(5) Breaking strength" was 30 MPa.

Example 3 In Example 1, the drying condition immediately after coating was 90 ° C.
A 100 μm thick white laminated polyester film having a coating layer of 0.20 g / m ^{2 on} both sides was obtained in the same manner as in Example 1 except that the wind speed was 15 m / sec and 2 seconds. The breaking strength of the film prepared from the resin composition of the coating liquid for coating layer by the method described in the above "(5) Breaking strength" was 30 MPa.

Comparative Example 1 In Example 1, as the layer B film raw material (α),
The mixing ratio of the polyethylene terephthalate resin (I) having an intrinsic viscosity of 0.62 dl / g and the titanium dioxide-containing master pellet (III) was changed to 70% by mass and 30% by mass.

Further, as the film raw material (β) for the layer A, the average particle size of the polyethylene terephthalate resin (II) before solid phase polymerization was used instead of the polyethylene terephthalate resin (II) having an intrinsic viscosity of 0.75 dl / g. Diameter 1.
8 μm silica particles (Fuji Silysia, Sylysia)
A polyethylene terephthalate resin (II ′) containing 0.7% by mass and having an intrinsic viscosity of 0.62 dl / g was used. That is, the film raw material (β) for the A layer was changed to a pellet mixture of 70% by mass of polyethylene terephthalate resin (II ′) having an intrinsic viscosity of 0.62 dl / g and 30% by mass of titanium dioxide-containing master pellet (III). .

Except for these changes, the same procedure as in Example 1 was carried out to obtain a thickness of 10 with a coating layer of 0.20 g / m ^{2 on} both sides.
A 0 μm white laminated polyester film was obtained. In addition,
The average particle size of the particles in the layer A of the base material was 0.32 μm for the titanium oxide particles, which are white pigments, and 1.9 μm for the silica particles. Further, the breaking strength of the film prepared from the resin composition of the coating liquid for coating layer by the method described in the above “(5) Breaking strength” was 30 MPa.

In Comparative Example 1, the intrinsic viscosity (dl) of the polyester resins (I), (II) and (III) used as the substrate
/ G) is IV (I) = 0.62, IV (II) = 0.62, IV
(III) = 0.49. The mixing ratio (mass%) of the resin (II) and the resin (III) in the layer A is 70 mass% (a = 70) and 30
It is mass% (b = 30). Substituting these numerical values into “IV (II) × a + IV (III) × b” on the left side of equation (1) gives 58.1
Becomes Further, when substituting into the right side “IV (I) × 100” of the equation (1), it becomes 62.0. That is, Comparative Example 1 is an example that does not satisfy the following relational expression (1) defined in claim 1 of the present invention. IV (II) × a + IV (III) × b> IV
(I) × 100 (1)

Comparative Example 2 A white laminated polyester film having a thickness of 100 μm was obtained in the same manner as in Example 1 except that the coating layer was not provided. The white laminated polyester film obtained in this Comparative Example 2 does not satisfy the requirement of "white laminated polyester film in which the coating layer (C layer) is provided on at least one surface of the base material" defined in claim 1 of the present invention. Here is an example.

Comparative Example 3 The same method as in Example 1 was carried out except that a copolymerized polyester resin (Vylonal MD-1200 manufactured by Toyobo Co., Ltd.) was used in place of the above graft modified polyester resin. 0.20g / on both sides
A 100 μm thick white laminated polyester film having a m ² coating layer was obtained. The breaking strength of the film prepared from the resin composition of the coating liquid for coating layer by the method described in the above "(5) Breaking strength" was 5 MPa.

The white laminated polyester film obtained in Comparative Example 3 does not use a modified resin as a resin constituting the coating layer (C layer), and the "the C layer is defined in claim 1 of the present invention. ,, modified resin, and has a breaking strength of 10
It is an example that does not satisfy ".

Example 4 After confirming with a microscope that the surface of the white laminated polyester film obtained in Example 1 was not scratched, a UV curable ink (UVA7 manufactured by Seiko Advance Co., Ltd.) was coated on one side.
10 Black) on the surface of the film (the surface of the coating layer if a coating layer is provided) on a Tetoron screen (#
After printing with 300 mesh), 500mJ /
UV exposure was carried out at cm ² . This was cut into a size and shape described in JIS-X6311 to obtain a card-shaped sample.
According to the method described in JIS-X6311,
After being immersed in an aqueous acetic acid solution at 25 ° C. for 24 hours, the sample was taken out and left at 25 ° C. for 1 hour. After leaving, the printed surface was rubbed with a nail to confirm the presence or absence of peeling, but peeling of the printing layer was not observed, and a good card was obtained.

Comparative Example 4 Using the white laminated polyester film having no coating layer obtained in Comparative Example 3, a card-shaped sample was prepared in the same manner as in Example 4. This sample is JI
According to the method described in S-X6311, in an aqueous solution of acetic acid at 25 ° C.
After soaking for 24 hours at 25 ° C, remove the sample.
Left for 1 hour. When the printed surface was rubbed with a nail after standing, the printed layer was peeled off, which was not suitable as a card.

Comparative Example 5 The white laminated polyester film obtained in Example 1 was used in which 10 or more scratches each having a length of 500 μm or more were preliminarily scratched with a metal brush before printing with UV ink. A card-like sample was obtained in the same manner as in 1. In this case, peeling of the ink layer was observed from around the scratched area by rubbing with a nail, which was not suitable as a card.

The results of measuring the physical properties of the white laminated polyester films obtained in the above Examples and Comparative Examples are shown in Table 1.

[0185]

[Table 1]

[0186]

As described above, the white laminated polyester film of the present invention is a masterbatch polyester resin containing a polyester resin (II) and a white pigment on at least one surface of a layer (B layer) mainly composed of the polyester resin (I). A polyester resin composition layer (A layer) composed of (III) is laminated, and a laminated film base material having the intrinsic viscosity of the polyester resins (I), (II) and (III) in a specific range is modified. Since it has a coating layer mainly composed of resin and a specific polymer antistatic agent, it has high surface strength and is excellent in whiteness, ink adhesion, water resistance adhesion, antistatic property, and scratch resistance. . In addition, since film pieces that have been scraps during film production can be reused as film raw materials, they are of great industrial value in terms of cost reduction. It is also industrially valuable in terms of cost reduction. Therefore, the white laminated polyester film having high-quality printability of the present invention is suitable as various information recording materials such as IC cards and magnetic cards, and printing materials. Further, since it has a high surface strength as a card base material and is excellent in peel resistance after bonding two base materials, it is particularly suitable as a base material for an IC card which is a bonding application.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinya Higashiura             2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo             Film Development Laboratory, Katata Phil             Inside the center (72) Inventor Yasushi Sasaki             Toyobo Co., Ltd. 10-24 Toyocho, Tsuruga City, Fukui Prefecture             Film Development Laboratory Tsuruga Film Center             In the center (72) Inventor Katsufumi Kumano             Toyobo Co., Ltd. 10-24 Toyocho, Tsuruga City, Fukui Prefecture             Film Development Laboratory Tsuruga Film Center             In the center (72) Inventor Mutsuo Nishi             Toyobo Co., Ltd. 10-24 Toyocho, Tsuruga City, Fukui Prefecture             Film Development Laboratory Tsuruga Film Center             In the center (72) Inventor Toshiyuki Shimizu             2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo             Film Development Laboratory, Katata Phil             Inside the center F-term (reference) 2C005 MA11 MA40 PA04 PA15 PA21                       PA29                 4F100 AA20 AA21 AK01D AK25D                       AK41A AK41B AK41C AK41D                       AK42 AK51D AL01 AL03                       AL04D AL05A AL05C AL06D                       AL07 AL07D AT00B BA03                       BA04 BA10A BA10D BA15                       BA16 CA13A CA13C CA22D                       EH20 EH46 EJ05D EJ38                       EJ55 GB71 GB90 JA05D                       JA06A JA06B JA06C JB06D                       JG03 JG04D JK03D JK06                       JK14 JL11 JN30 YY00 YY00A                       YY00B YY00C YY00D

Claims (8)

[Claims] 1. A white laminated polyester film in which a coating layer (C layer) is provided on at least one surface of a base material made of a white polyester film having a laminated structure of two or more layers, wherein the base material is a polyester resin (I A polyester resin composition layer (A) composed of a polyester resin (II) and a white pigment-containing masterbatch polyester resin (III) on at least one side of a layer (B layer) mainly composed of
Layers), and the polyester resin (I)
The intrinsic viscosity IV of (III) satisfies the following formula (1), and the C layer is provided directly on the A layer, and has a modified resin and at least one sulfonate group or phosphate group. Contains an inhibitor and has a breaking strength of 10 to 10
A white laminated polyester film having a surface specific resistance of 1 × 10 ⁶ to 1 × 10 ¹³ Ω / □ at 0 MPa and 65% RH at 25 ° C. IV (II) × a + IV (III) × b> IV (I) × 100 (1) where IV (I), IV (II), and IV (III) are polyester resins (I) and (II), respectively. , (III) intrinsic viscosity (dl / g), and a and b represent the mixing ratio (mass%) of the resin (II) and the resin (III) in the A layer. 2. The intrinsic viscosity of the polyester resin (II)
IV (II) is 0.70 dl / g or more, The white laminated polyester film of Claim 1 characterized by the above-mentioned. 3. The white laminated polyester film according to claim 1, wherein the modified resin has a glass transition temperature of 10 to 100 ° C. 4. The modified resin is a modified polyester resin,
It is at least 1 sort (s) of modified acrylic resin and modified polyurethane resin, The white laminated polyester film in any one of Claims 1-3 characterized by the above-mentioned. 5. The white laminated polyester film according to claim 1, wherein the modified resin is a graft modified resin. 6. The self-crosslinking polyester in which the graft-modified resin is a hydrophobic polyester resin in which a polymerizable unsaturated monomer containing at least one monomer containing an acid anhydride having a double bond is grafted. The white laminated polyester film according to claim 5, which is a system-based graft copolymer. 7. The tone b value measured from the C layer side is −
It is 5.0-2.0, The white laminated polyester film in any one of Claims 1-6 characterized by the above-mentioned. 8. The white laminated polyester film according to claim 1, which is used as a base material for an IC card.