KR20150135197A - Laminated polyester film - Google Patents

Abstract

(Adhesive property) under high temperature and high humidity, and a boiling water (water resistance) under a high temperature and a high humidity condition, Which is excellent in adhesiveness (immersion adhesion) when it is immersed in hot water, and is excellent in transparency to hot water when immersed in hot water.
A polyester film having a resin layer (X) on at least one surface of a polyester film, wherein the resin layer (X) comprises an acrylic urethane copolymer resin (a) and a polyester resin having a naphthalene skeleton ), The isocyanate compound (c), and the dicyclohexylmethanecarbodiimide compound (d), and the change amount of the spectral reflectance before and after the mercury treatment test on the resin layer (X) (? R) of from 0% to 2%.

Description

[0001] LAMINATED POLYESTER FILM [0002]

The present invention relates to a laminated polyester film having a resin layer on at least one side of a polyester film. More specifically, the present invention relates to a coating composition which is excellent in transparency and inhibition of an iris pattern (interference pattern) when a hard coating layer is laminated, has excellent initial adhesion with a hard coating layer, adhesiveness under high temperature and high humidity Which is excellent in adhesiveness (immersion adhesion) when immersed in boiling water, and is also excellent in suppressing deterioration (whitening) of transparency (heat resistance water transparency) when immersed in hot water.

As a representative of the display material, there is known a touch panel which is provided on the screen of the image display device and which gives a predetermined support to the information processing apparatus by the position where the screen is pressed. In many image display devices including an image display device provided with a touch panel, a hard coating film for preventing scratches is formed on the outermost surface thereof. 2. Description of the Related Art Recently, image display devices such as a mobile phone, a notebook computer, and a personal digital assistant (PDA) have been used outdoors. The hard coating film used in an outdoor image display device including car navigation requires a property (anti-wet heat adhesion) that does not cause peeling of the hard coat layer and the substrate film even if exposed for a long time under a harsh environment such as high temperature or high humidity.

In recent years, there has been an increase in the use of portable devices in bathrooms and the like, and even in the case of hard coating films used in portable devices such as cellular phones, mobile phones with touch panels, etc., adhesiveness under high temperature and high humidity Is strongly demanded. The hard coating film used for such use is required to have adhesiveness against moisture and heat, which maintains adhesiveness even after holding for 250 hours to 500 hours under an environment of 85 ° C and 85% RH. In recent years, there has been a demand for a self-adhesive property that maintains adhesiveness even after being boiled in boiling water (100 DEG C), which is a more severe condition. There has been a demand for a laminated polyester film which satisfies adhesiveness under such a harsh environment, exhibits no change in appearance, and has excellent suppression (visibility) of an iris pattern (interference fringe) when a hard coating layer is laminated .

Therefore, conventionally, a method of imparting the adhesive property to the surface of a polyester film by various methods has been studied. For example, a method of forming an acrylic-modified polyurethane as a primer layer on the surface of a film (Patent Document 1), a method of forming a copolymerized polyester resin and an isocyanate-based crosslinking agent as a primer layer (Patent Document 2), a polyurethane resin, A method of forming a primer layer composed of an acrylic urethane copolymer resin, an isocyanate compound, an oxazoline compound, and a carbodiimide compound (Patent Document 4), a method of forming a crosslinking agent of a bidentiimide as a primer layer (Patent Document 3) And a method of forming a compound having 30 to 70% of a melamine compound and a naphthalene ring and a urethane resin as a primer layer (Patent Document 5).

Japanese Patent Application Laid-Open No. 2000-229394 Japanese Patent Application Laid-Open No. 2003-49135 Japanese Patent Application Laid-Open No. 2001-79994 WO 2007/032295 Pamphlet Japanese Patent No. 4916339

In Patent Document 1, although the initial adhesion with the ultraviolet curable ink is excellent, the problems such as the adhesion in the moisture-resistant and heat-resistant environment and the lack of adhesion to the ink are liable to occur.

In the method described in Patent Document 2, although the effect of improving anti-wet heat adhesion is observed to be constant, adhesion with ultraviolet rays (hereinafter also referred to as UV) curable resin, especially with a solventless UV curable resin constituting the prism lens layer There is insufficient sex.

In the methods described in Patent Documents 3 and 4, there is a problem that visibility (interference fringes) becomes insufficient because the refractive index of the resin itself is low although the adhesiveness against moisture and heat is improved in addition to the initial adhesion.

In the method described in Patent Document 5, the compound having a naphthalene ring is suppressed from lowering the refractive index to improve the visibility, and the initial adhesion is also improved. However, there has been a problem that the adhesiveness against moisture and heat resistance and the resistance against the self-adhesion are insufficient. In addition, in the method described in Patent Document 5, there is a problem that process contamination due to volatilization of melamine compounds is a problem in the production process due to the presence of a large amount of melamine compounds, or melamine compounds generate formaldehyde which is harmful to the human body through a crosslinking reaction .

As described above, the conventional technique can not satisfy all of the suppression of interference fringe (visibility), anti-wet heat adhesion, and anti-magnetic adhesion. In addition, the conventional technology can not satisfy the heat-resistant water transparency.

It is therefore an object of the present invention to provide a laminated polyester film excellent in not only initial adhesion but also excellent resistance to moisture and heat and adhesion to the interior and of water resistance to heat water by eliminating the aforementioned drawbacks . It is also an object of the present invention to provide a laminated polyester film having excellent properties even in the case where a melamine compound is contained in a small amount or not at all.

The laminated polyester film according to the present invention has the following constitution.

(1) A laminated polyester film having a resin layer (X) on at least one surface of a polyester film, wherein the resin layer (X) comprises an acrylic urethane copolymer resin (a), a polyester resin (b) having a naphthalene skeleton, And a dicyclohexylmethanecarbodiimide compound (d), wherein the amount of change in the spectral reflectance before and after the resistivity treatment on the side of the resin layer (X) ? R) is 0% or more and 2% or less.

(2) The dispersion index of the aggregate containing the acrylic urethane copolymer resin (a) of the resin layer (X) is 5 or less, and the ratio of the acrylic urethane copolymer resin (a) in the coating composition is 3 wt% ≪ / RTI >

(3) The optical recording medium according to (1) or (2), wherein the minimum value of the spectral reflectance in the wavelength range of 450 nm to 650 nm on the side of the resin layer (X) is 4.5% Polyester film.

(4) The dicyclohexylmethanecarbodiimide compound (d) according to any one of (1) to (3), which is characterized by being a dicyclohexylmethanecarbodiimide compound represented by the following formula Laminated polyester film.

In the formula, n represents an integer of 1 or more and 10 or less.

R ¹ and R ² each represent any one of the following formulas (2) to (4).

R ¹ and R ² may be the same or different.

Wherein p is an integer of 4 or more and 30 or less and R < ³ > is an alkyl group of 1 to 5 carbon atoms.

Wherein q is an integer of 1 or more and 3 or less, R ⁴ is an alkyl group having 1 to ⁵ carbon atoms or a phenyl group, and R ⁵ is an alkyl group having 1 to ⁵ carbon atoms.

[Wherein, R ⁶ is an alkyl group having 1 to 5 carbon atoms, R ⁷ represents hydrogen or an alkyl group having 1 to 5 carbon atoms;

(5) The polyester resin (b) according to any one of (1) to (4), wherein the aromatic dicarboxylic acid component containing a sulfonic acid metal base is added to the polyester resin And 30 mol% of the polyester resin.

(6) The laminated polyester film according to any one of (1) to (5), wherein the polyester resin (b) comprises a diol component represented by the following formula (5).

[Wherein, X ^1, X ^2: - it shows a _{(C l H 2l O) m} -H (l = 2 or more than 4, m = 1 or more integer of not more than 15);

(7) The coating composition according to any one of (1) to (6), wherein the solid content ratio of the acrylic urethane copolymer resin (a) and the polyester resin (b) in the coating composition is 40/60 to 5/95 Lt; / RTI >

(8) The coating composition according to the above (7), wherein, when the total weight of the solid content of the acrylic urethane copolymer resin (a) and the polyester resin (b)

Isocyanate compound (c) in an amount of 3 to 20 parts by weight,

Wherein the dicyclohexylmethanecarbodiimide compound (d) is contained in an amount of 10 to 40 parts by weight in terms of solid content.

(9) The laminated polyester film according to (8), wherein the coating composition further comprises 5 to 30 parts by weight of a melamine compound (e).

(Effects of the Invention)

The laminated polyester film of the present invention is excellent in transparency, suppression of iris pattern (interference pattern) when a hard coat layer is laminated, and is excellent in initial adhesion with a hard coat layer and adhesiveness under high temperature and high humidity (Heat resistant adhesive property), excellent adhesion (immersion adhesion) when immersed in boiling water, and suppression of deterioration (whitening) of transparency (heat resistance water transparency) when immersed in hot water .

1 is a cross-sectional view schematically showing a laminated polyester film having a large dispersion index.
2 is a cross-sectional view schematically showing a laminated polyester film having a small dispersion index.
3 is a cross-sectional view schematically showing a laminated polyester film having a small dispersion index.
4 is a diagram schematically showing a surface on which a cross section of the laminated polyester film is observed.

Hereinafter, the laminated polyester film of the present invention will be described in detail.

The laminated polyester film of the present invention has a polyester film to be a substrate and has a resin layer (X) on at least one surface of the polyester film.

The polyester constituting the polyester film to be the base material in the present invention is a general term for polymers having ester bond as a main bonding chain of the main chain. Preferable examples of the polyester include at least one constituent resin selected from the group consisting of ethylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene terephthalate and 1,4-cyclohexanedimethylene terephthalate, . These constituent resins may be used alone or in combination of two or more. The intrinsic viscosity (measured in o-chlorophenol at 25 캜) of the polyester described above is preferably 0.4 to 1.2 dl / g, more preferably 0.5 to 0.8 dl / g in the practice of the present invention Suitable.

In addition, various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic excipients, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents, nucleating agents and crosslinking agents, Or may be added to such an extent that it does not.

It is preferable to use a biaxially oriented polyester film as the polyester film. Here, " biaxial orientation " means a biaxial orientation pattern in wide angle X-ray diffraction. The biaxially oriented polyester film can be generally obtained by stretching a polyester sheet in an unstretched state by 2.5 to 5 times in the sheet longitudinal direction and in the transverse direction, respectively, and then conducting heat treatment.

The polyester film itself may be a laminated structure of two or more layers. As a preferable laminated structure of the polyester film of the present invention, for example, a composite film having an inner layer portion and a surface layer portion, in which a composite film in which a layer containing substantially no particles in the inner layer portion and particles only in the surface layer portion is formed . The polyester constituting the inner layer portion and the surface layer portion may be the same or different.

The thickness of the polyester film is not particularly limited, and is appropriately selected depending on the application and the type. But is usually from 10 to 500 mu m, more preferably from 38 to 250 mu m, and most preferably from 75 to 150 mu m from the viewpoints of mechanical strength and handling properties. The polyester film may be a composite film formed by coextrusion, or a film obtained by bonding the obtained film by various methods.

The laminated polyester film of the present invention is a laminated polyester film having a resin layer (X) on at least one side of a polyester film, wherein the resin layer (X) comprises an acrylic urethane copolymer resin (a) and a poly Is a layer formed by using a coating composition comprising an ester resin (b), an isocyanate compound (c), and a dicyclohexylmethanecarbodiimide compound (d) And the change amount (? R) of the spectral reflectance is 0% or more and 2% or less.

The laminated polyester film of the present invention is excellent in transparency, suppression of iris patterns (interference fringes) when a hard coating layer is laminated, excellent initial adhesion to a hard coating layer, adhesion at high temperature and high humidity (Adhesion resistance) when it is immersed in boiling water (adhesion resistance), and is also excellent in suppressing deterioration (whitening) of transparency (heat resistance water transparency) when immersed in hot water.

The polyester resin (b) is preferably a copolymerized polyester resin containing an aromatic dicarboxylic acid component containing a sulfonic acid metal base in an amount of 1 to 30 mol% based on the total dicarboxylic acid component of the polyester. Further, it is more preferable that the polyester resin (b) includes a diol component represented by the following formula (5).

[Wherein, X ^1, X ^2: - it shows a _{(C l H 2l O) m} -H (l = 2 or more than 4, m = 1 or more integer of not more than 15);

Here, the amount of change (? R) of the spectral reflectance before and after the self-abrasion treatment test in the present invention means the change in the number of laminated polyester films when the laminated polyester film is immersed in boiling water (100 ° C) for 5 hours (%) Of the spectral reflectance before and after the brittleness treatment test when the spectral reflectance is measured from the side of the ground layer (X).

The spectral reflectance (%) before the self-treatment treatment test and the spectral reflectance (%) after the self-treatment treatment test are obtained on the basis of the evaluation method of the variation amount (? R) of the spectral reflectance before and after the self- . ? R is a value obtained by subtracting the average spectral reflectance (%) after the self-bias treatment test from the spectral reflectance (%) before the self-bias test process (? R = average spectral reflectance before the self-bias test process-average spectral reflectance after the self- .

The change amount? R of the spectral reflectance before and after the mercury treatment test needs to be 0% or more and 2% or less, more preferably 0% or more and 1.8% or less, further preferably 0% or more and 1.4% or less, . In addition, although ΔR may take a negative value, it is preferable to use an acrylic urethane copolymer resin (a), a polyester resin (b) having a naphthalene skeleton, an isocyanate compound (c), a dicyclohexylmethanecarbodiimide compound it is difficult to reduce the? R to less than 0% in the laminated polyester film of the present invention having the resin layer (X) formed on at least one surface of the polyester film.

The amount of change (? R) of the spectral reflectance before and after the mercury treatment test as measured from the side of the resin layer (X) is 0% or more and 2% or less, whereby the laminated polyester film of the present invention has transparency, (Viscoelasticity) of an iris image (interference fringe), excellent initial adhesion with a hard coating layer and adhesion resistance to wet heat and heat, and surprisingly, even when immersed in boiling water, Lt; / RTI >

The reason for this is presumed as follows. The change of the spectral reflectance measured from the side of the resin layer (X) is caused by the change of the refractive index due to the change of the composition of the resin layer (X). Therefore, the change of the spectral reflectance before and after the mercury treatment test means that the refractive index of the resin layer (X) is changed by the mercury treatment test. That is, the composition of the resin layer X is changed. As the compositional change of the resin layer (X) by the mercury treatment test, the outflow of the composition component of the resin layer (X) into the self-supporting water and the infiltration of the number of the self-contained resin into the resin layer (X) are considered. When the amount of change (? R) of the spectral reflectance before and after the mercury treatment test is 0% or more and 2% or less, the change in the composition of the resin layer (X) by the mercury treatment test is small. Therefore, even after immersion in hot water or boiling water, Adhesiveness and mastic resistance can be exhibited.

On the other hand, when the amount of change (? R) of the spectral reflectance before and after the mercury treatment test exceeds 2%, the composition change of the resin layer (X) by the mercury treatment test becomes large, .

In the present invention, as a method of forming the resin layer (X) in which the amount of change (? R) of the spectral reflectance before and after the mercury treatment test is 0% or more and 2% or less, the acrylic urethane copolymer resin (a) , The resin layer (X) in which the amount of change (? R) of the spectral reflectance before and after the mercury treatment test is 0% or more and 2% or less can be formed.

The laminated polyester film of the present invention is a laminated polyester film having a resin layer (X) on at least one side of a polyester film, wherein the resin layer (X) comprises an acrylic urethane copolymer resin (a) and a naphthalene skeleton Is a layer formed by using a coating composition comprising a polyester resin (b) having an isocyanate group (b), an isocyanate compound (c) and a dicyclohexylmethanecarbodiimide compound (d) (a) is preferably 10 or less, more preferably 5 or less. The dispersion index in the present invention refers to an aggregate comprising an acrylic urethane copolymer resin (a) having a size of 40 nm or more observed in a specific area when a cross section of the resin layer (X) is observed using a transmission electron microscope (TEM) . ≪ / RTI > The number of agglomerates having a size of 40 nm or more including the acrylic urethane copolymer resin (a) observed at a field of view (Z direction x direction: 500 nm x 1200 nm) at a magnification of 20,000 was measured. The number of aggregates obtained is converted into the number per predetermined area (120000 nm ² ) by the following formula.

(Number of agglomerates having an observed size of 40 nm or more) x 120000 / area occupied by the resin layer (X) in the visual field area

This observation was performed for 10 fields of view, and the average number of aggregates containing the acrylic urethane copolymer resin (a) present per a predetermined area was calculated, and the value obtained by rounding off the number of the first decimal places was used as a dispersion index. Here, the size of the aggregate refers to the maximum diameter of the aggregate (i.e., the longest diameter of the aggregate, which indicates the longest diameter of the aggregate), and also the maximum diameter of the aggregate in the case of aggregates having cavities therein.

The dispersion index represents an integer of 0 or more. The dispersion index in the present invention is preferably 10 or less, more preferably 5 or less, still more preferably 4 or less, particularly preferably 3 or less.

In order to confirm the dispersion index of the resin layer (X), it can be determined by observing the sectional structure of the layer (X) using a transmission electron microscope (TEM).

First, the cross-sectional observation of the resin layer X will be described.

A sample of the cross section of the layer (X) is formed on the laminated polyester film by the RuO ₄ -discriminated ultra thin film cutting method. When the cross section of the obtained sample was observed with respect to a visual field area (Z direction x direction: 500 nm x 1200 nm) at an acceleration voltage of 100 kV and a magnification of 20,000 times, the structure as shown in Figs. 1 to 3 was confirmed have.

Here, the cross-sectional observation of the resin layer X means the cross-sectional observation of the XZ plane in Fig. Here, the dyeing with RuO ₄ is capable of dyeing a portion having an acrylic skeleton.

For example, a laminated polyester film composed of a polyester resin (b) in which the resin layer (X) has a naphthalene skeleton and only an isocyanate compound (c) and a dicyclohexylmethanecarbodiimide compound (d) , The cross section was observed, and no black part was observed because it did not contain the acrylic urethane copolymer resin (a) that was dyed by RuO ₄ . On the other hand, the resin layer (X) is an acrylic-urethane copolymer resin (a) subjected to a sample created similarly for the laminated polyester film comprising only when observing the cross-section, only acryl-urethane copolymer resin (a) to be dyed by RuO ₄ The entire resin layer (X) is blackened. From this result, the black part can be judged as a part including the acrylic urethane copolymer resin (a).

When the layer X has a sea-island structure as shown in Fig. 1, the black part in the thickness direction of the layer X (for example, acrylic urethane Copolymer resin) is large, the dispersion index increases. On the other hand, in the case of the structures of Figs. 2 and 3, the dispersion index is small because the number of black islands is small.

When the dispersion index observed by the above-mentioned method exceeds 10, it was judged that the resin layer (X) does not form a uniform dispersion structure. On the other hand, when the dispersion index was 10 or less, it was judged that the resin layer X formed a uniform dispersion structure.

Wherein the resin layer (X) comprises a coating material comprising an acrylic urethane copolymer resin (a), a polyester resin (b) having a naphthalene skeleton, an isocyanate compound (c), and a dicyclohexylmethanecarbodiimide compound (A) of the layer (X) is preferably 10 or less, more preferably 5 or less, still more preferably 4 or less, Particularly preferably 3 or less. With this range, the laminated polyester film of the present invention is excellent in transparency, suppression of iris images (interference fringes) when the hard coat layer is laminated (visibility), excellent initial adhesion with the hard coat layer, , And moreover, surprisingly, even when immersed in boiling water, it is possible to exhibit more excellent adhesion (anti-magnetic adhesion).

The reason for this is presumed as follows. When the acrylic urethane copolymer resin (a) has a uniform dispersion structure having a dispersion index of 10 or less as shown in FIGS. 2 and 3, an acrylic urethane copolymer resin (a) having excellent adhesiveness to the hard coat layer is formed on the surface of the resin layer . Also, the isocyanate compound (c) and the dicyclohexylmethanecarbodiimide compound (d) which are excellent in adhesion to the hard coat layer are also distributed on the surface of the layer (X). As a result, the interaction between the hard coating layer and the layer (X) increases, and the adhesion with the hard coating layer is greatly improved. In addition, in the case where a force for peeling the stacked hard coat layer is applied in addition to the above, since the adhesive force in the surface is uniform, it is dispersed without locally concentrating the stress, and excellent anti-wet heat adhesion and anti- Lt; / RTI > When the acrylic urethane copolymer resin (a) has a uniform dispersion structure in the resin layer (X), the acrylic / urethane copolymer resin (a) having a low refractive index is not locally agglomerated. The refractive index of the layer X becomes uniform, and the layer X having a uniform refractive index in the thickness direction can be formed. As a result, when the hard coat layer is laminated, the suppression of the iris pattern (interference fringe) is also excellent (visibility), which is preferable.

On the other hand, when the dispersion index exceeds 10, the transparency deteriorates, the anti-wet heat adhesion and the anti-magnetic adhesion decrease due to the dispersion failure of the mutual resin.

In the present invention, as a method for forming a uniform dispersion structure having a dispersion index of not more than 10 in the resin layer (X), for example, a polyester resin (b) having a naphthalene skeleton, A copolymerizable polyester resin containing an aromatic dicarboxylic acid component containing a base in an amount of 1 to 30 mol% based on the total dicarboxylic acid component of the polyester is used, and each resin (a) to (d) To the certain range, the resin layer (X) can form a structure having a dispersion index of 10 or less.

In the laminated polyester film of the present invention, the minimum value of the spectral reflectance in the wavelength range of 450 nm to 650 nm on the side of the resin layer (X) is preferably 4.5% or more and 6.0% or less.

For this reason, when the absorption wavelength of a human photocell is in the range of 450 nm to 650 nm and the minimum value of the spectral reflectance in this wavelength range is 4.5% or more and 6.0% or less, the iris image Pattern) is difficult to see.

In the present invention, as a method for forming a laminated polyester film in which the minimum value of the spectral reflectance in the wavelength range of 450 nm to 650 nm at the resin layer (X) side is 4.5% or more and 6.0% or less, A polyester resin (b) having a naphthalene skeleton is obtained by using a copolymerized polyester resin containing an aromatic dicarboxylic acid component containing a sulfonic acid metal base in an amount of 1 to 30 mol% based on the total dicarboxylic acid component of the polyester, By setting the ratio of each of the resins (a) to (d) in the coating composition to a certain range, the minimum value of the spectral reflectance in the wavelength range of 450 nm or more and 650 nm or less on the side of the layer (X) % Or less of the polyester film.

For this reason, for example, the polyester resin (b) having a naphthalene skeleton may be copolymerized with an aromatic dicarboxylic acid component containing a sulfonic acid metal base in an amount of 1 to 30 mol% based on the total dicarboxylic acid component of the polyester When a polyester resin is used, compatibility with the acrylic urethane copolymer resin (a) and other resins is improved, and a uniform dispersion structure can be formed. As a result, the refractive index in the resin layer (X) is also uniform so that the minimum value of the spectral reflectance in the wavelength range of 450 nm to 650 nm on the side of the resin layer (X) is 4.5% or more and 6.0% Can be formed. When the hard coat layer is laminated, the range of the reflectance is preferable because suppression (visibility) of the iris pattern (interference pattern) is possible from the principle of optical interference.

This reason will be described in detail. The suppression of the shape of the iris image can be achieved by controlling the refractive index and the film thickness of the resin layer (X). The most iris phase can be suppressed when the refractive index of the resin layer X is set to the refractive index of the value of the rising average of the refractive index of the hard coat layer which is laminated with the polyester film of the substrate. For example, when the hard coat layer is made of acrylic resin and the base polyester film is made of polyethylene terephthalate, the refractive index of the hard coat layer is 1.52 and the refractive index of the base polyester film is 1.65. The refractive index of the resin layer X becomes 1.58, which is their rising average. Since there is a correlation between the refractive index of the coating film and the reflectance in the wavelength range of 450 nm to 650 nm, the minimum value of the spectral reflectance in the wavelength range of 450 nm to 650 nm of the resin layer X is 4.5% Or more and 6.0% or less, thereby making it possible to suppress the shape of the iris image.

Further, in the laminated polyester film of the present invention, a coating composition having a solid content ratio of the acrylic urethane copolymer resin (a) and the polyester resin (b) of 40/60 to 5/95 is applied to at least one surface of the polyester film, The laminated polyester film obtained by forming the layer (X) is preferable because adhesion between the laminated polyester film and the hard coat layer becomes good. When the sum of the solid content weight of the acrylic urethane copolymer resin (a) and the polyester resin (b) in the coating composition is 100 parts by weight, 3 to 20 parts by weight of the isocyanate compound (c) (X) is obtained by applying a coating composition containing 10 to 40 parts by weight of a hexylmethanecarbodiimide compound (d) in a solid weight of 10 to 40 parts by weight to form an acrylic urethane copolymer resin a laminated polyester film having a uniform dispersion structure in which the dispersion index of the polyester (a) is 10 or less can be formed, and the laminated polyester film has good anti-wet heat adhesion and mydriatic adhesion.

As a result, the resin layer can exhibit high transparency, adhesion to the hard coating layer, adhesion to moisture and heat, anti-magnetic adhesion, and suppression of interference fringe (visibility) when the hard coating layer is laminated.

In addition, the laminated polyester film of the present invention is also excellent in suppressing deterioration (whitening) of transparency (heat resistance water transparency) when immersed in hot water. The heat-resistant water-transparency can be evaluated by the amount of film haze change (? Hz) before and after the mercury treatment test. The amount of change in film haze (? Hz) before and after the mercury treatment test indicates the amount of change in film haze before and after the mercury treatment test in which the laminated polyester film is immersed in hot water at 100 占 폚. Specifically, the value obtained by subtracting the haze value of the laminated polyester film before the self-bias treatment test from the haze value of the laminated polyester film after the self-leveling treatment test is the film haze change amount (? Hz) before and after the self- Film haze before the mercury treatment test). The detailed measurement method will be described later. In the present invention, a film having a film haze change amount (DELTA Hz) before and after the mercury treatment test of less than 5.0% is made into a film excellent in hot water water transparency.

By setting the film haze change amount (DELTA Hz) before and after the self-extinguishing treatment test to less than 5.0%, it is possible to obtain a laminated polyester film capable of suppressing deterioration of transparency even when used for a long period of time under a harsh environment such as high temperature and high humidity. It is more preferable that the film haze change amount (DELTA Hz) before and after the mercury treatment test is less than 4.5%. As a method for obtaining a laminated polyester film in which the film haze change amount (DELTA Hz) before and after the mercury treatment test is less than 5.0%, for example, a dicyclohexylmethanecarbodiimide compound ( d), a method of setting the ratio of the resin or the compound (a) to (d) in the coating composition to a certain range, and a method of combining these methods.

For this reason, the following mechanism is estimated. From the above examination, it has been confirmed that fine voids are generated on the surface of the resin layer and the haze of the laminated polyester film is increased by performing the self-treatment treatment on the laminated polyester film having the resin layer. It is considered that the unreacted component of the crosslinking component contributing to the adhesion property is leaked out by the self-abrasion treatment test because the haze increases and the adhesiveness is lowered with the increase of the void generation amount. When the dicyclohexylmethanecarbodiimide compound (d) is used, the compatibility with the polyester resin (b) having a naphthalene skeleton and the other resin is improved and a resin layer having a uniform dispersion structure can be formed, In addition, since a resin layer having a high degree of crosslinking can be formed in particular, the dicyclohexylmethanecarbodiimide compound or the unreacted component thereof is difficult to flow out in the mercury treatment test. As a result, generation of voids is suppressed and the amount of haze change is greatly suppressed It is considered to be possible.

Further, the dicyclohexylmethanecarbodiimide compound (d) is more preferably a dicyclohexylmethanecarbodiimide compound represented by the following formula (1).

In the formula, n represents an integer of 1 or more and 10 or less.

R ¹ and R ² each represent any one of the following formulas (2) to (4).

R ¹ and R ² may be the same or different.

Wherein p is an integer of 4 or more and 30 or less and R < ³ > is an alkyl group of 1 to 5 carbon atoms.

Wherein q is an integer of 1 or more and 3 or less, R ⁴ is an alkyl group having 1 to ⁵ carbon atoms or a phenyl group, and R ⁵ is an alkyl group having 1 to ⁵ carbon atoms.

[Wherein, R ⁶ is an alkyl group having 1 to 5 carbon atoms, R ⁷ represents hydrogen or an alkyl group having 1 to 5 carbon atoms;

Hereinafter, the acrylic urethane copolymer resin (a), the polyester resin (b) having a naphthalene skeleton, the isocyanate compound (c), the dicyclohexylmethanecarbodiimide compound (d) and the The melamine compound (e) will be described.

(1) Acrylic urethane copolymer resin (a)

The acrylic urethane copolymer resin (a) in the laminated polyester film of the present invention is not particularly limited as long as it is a copolymer of an acrylic resin and a urethane resin.

The acrylic resin used in the present invention refers to a resin obtained by copolymerizing acrylic monomers described later and monomers of other species, if necessary, by a known polymerization method of acrylic resin such as emulsion polymerization or suspension polymerization.

Examples of the acrylic monomer used for the acrylic urethane copolymer resin (a) include alkyl acrylates (examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, isobutyl, t- (Such as methyl, ethyl, n-propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl etc.), 2-hydroxyethyl acrylate, 2- Hydroxy group-containing monomers such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, monomers containing a hydroxyl group such as acrylamide, methacrylamide, N-methyl methacrylamide, N- Methyl acrylate, N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylol acrylamide, N-methoxymethylacrylamide, N- methoxymethylmethacrylamide, N-butoxymethylacrylamide, Amide group-containing amide group-containing monomers, N, N-diethyl Amino group-containing monomers such as N, N-diethylaminoethyl methacrylate, glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, acrylic acid, methacrylic acid and salts thereof (Sodium salt, potassium salt, ammonium salt, etc.), and the like.

The acrylic resin is obtained by polymerizing one or two or more kinds of acrylic monomers. When the monomers other than acrylic monomers are used in combination, the proportion of the acrylic monomers in the total monomers is 50% by weight or more and 70% by weight or more From the viewpoint of adhesiveness.

The urethane resin used in the present invention refers to a resin obtained by reacting a polyhydroxy compound and a polyisocyanate compound by a known urethane resin polymerization method such as emulsion polymerization or suspension polymerization.

Examples of the polyhydroxy compound include polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, poly Polytetramethylene adipate, polytetramethylene sebacate, trimethylol propane, trimethylol ethane, pentaerythritol, polycarbonate diol, glycerin and the like can be mentioned.

Examples of the polyisocyanate compound include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, adducts of tolylene diisocyanate and trimethylene propane, adducts of hexamethylene diisocyanate and trimethylolethane Etc. may be used.

As a method of forming the resin layer (X), when applied to an in-line coating method described later, it is preferable that the acrylic urethane copolymer resin (a) is dissolved or dispersed in water. As a method for enhancing the affinity of the acrylic urethane copolymer resin with water, for example, a polyhydroxy compound containing a carboxylic acid group or a carboxylic acid containing a hydroxyl group is used as one of the polyhydroxy compounds. As the carboxylic acid group-containing polyhydroxy compound, for example, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid, trimellitic acid bis (ethylene glycol) ester and the like can be used. As the hydroxyl group-containing carboxylic acid, for example, 3-hydroxypropionic acid, -hydroxybutyric acid, p- (2-hydroxyethyl) benzoic acid, malic acid and the like can be used.

As another method for enhancing the affinity of the acrylic urethane copolymer resin with water, there is a method of introducing a sulfonic acid base into the urethane resin. For example, a compound in which a prepolymer is produced from a polyhydroxy compound, a polyisocyanate compound and a chain extender and an amino group or a hydroxyl group capable of reacting with a terminal isocyanate group and a sulfonic acid group or a sulfuric acid half ester base in the molecule And finally reacting to obtain a urethane resin having a sulfonic acid group or a sulfuric acid half ester base in the molecule. Examples of the compound having an amino group or a hydroxyl group and a sulfonic acid base capable of reacting with a terminal isocyanate group include aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 2-amino-5-methylbenzene-2-sulfonic acid, Sodium ethanesulfonate, and aliphatic primary amine compounds such as propanesultone, butane sultone adduct, and the like, preferably propane sultone adducts of aliphatic primary amine compounds.

The acryl-urethane copolymer resin (a) is preferable because it is excellent in adhesion with the hard coat layer when the acrylic resin is a skin layer and the urethane resin is an acrylic urethane copolymer resin having a core layer. Among them, it is preferable that the core layer made of the urethane resin is not completely surrounded by the skin layer made of the acrylic resin but the core layer is exposed. When the core layer is completely surrounded by the skin layer, the resin layer (X) becomes a surface state having only characteristics of an acrylic resin, and it becomes difficult to obtain a surface state having characteristics of a urethane resin originating from the core layer, It is not preferable from the viewpoint of adhesion with the coating layer. On the other hand, a state in which the core layer is not surrounded by the skin layer, that is, a state where the core layer is separated from the skin layer, is merely a state in which an acrylic resin and a urethane resin are mixed. Then, in general, acrylic resin having a small surface energy of the resin is selectively coordinated to the air-side surface of the resin layer (X). As a result, the surface of the resin layer (X) is not preferable from the standpoint of adhesion with the hard coat layer because it has only the characteristics of an acrylic resin.

1 shows an example of obtaining an acrylic urethane copolymer resin (a) having a core-skin structure. First, the first-stage emulsion polymerization is carried out using urethane resin monomers, an emulsifier, a polymerization initiator and an aqueous solvent which form the core portion of the polymer resin. Subsequently, after the first stage emulsion polymerization is substantially completed, the second stage emulsion polymerization is carried out by adding the acrylic monomer and the polymerization initiator forming the skin portion. By this two-step reaction, an acrylic urethane copolymer resin having a core-skin structure can be obtained. At this time, in order to make the resulting copolymer resin into a two-layer structure of a core layer and a skin structure, the emulsifier is stopped in an amount not forming a new core in the second-stage emulsion polymerization, and the urethane resin A method of allowing the polymerization to proceed on the surface of the core made of polypropylene is useful.

The acrylic urethane copolymer resin (a) can be prepared by the following method, but the acrylic urethane copolymer resin (a) of the present invention is not limited to those obtained by this method. For example, a small amount of a dispersant and a polymerization initiator are added to an aqueous dispersion of a urethane resin, and the acrylic monomer is slowly added while stirring at a constant temperature. Thereafter, the temperature is elevated as necessary and the reaction is continued for a predetermined time to complete the polymerization of the acrylic monomer to obtain an aqueous dispersion of the acrylic urethane copolymer resin.

The content of the acrylic urethane copolymer resin (a) in the coating composition is preferably 3% by weight or more based on the total weight of the solid content of the resin in the coating composition. When the content of the acrylic urethane copolymer resin (a) is less than 3% by weight, adhesion and suppression of interference fringes may not be compatible at all. Is preferably 3 wt% or more and 25 wt% or less, more preferably 4 wt% or more and 20 wt% or less based on the total weight of the solid content of the resin in the coating composition. Particularly preferably not less than 5% by weight and not more than 10% by weight.

The glass transition temperature (hereinafter referred to as " Tg ") of the acrylic resin in the acrylic urethane copolymer resin (a) is preferably 20 ° C or higher, more preferably 40 ° C or higher. When the Tg of the acrylic resin is 20 DEG C or more, the blocking property at the room temperature storage is improved, which is preferable.

The ratio of the acrylic resin to the urethane resin (acrylic resin / urethane resin) in the acrylic urethane copolymer resin (a) is preferably 10/90 to 70/30, more preferably 20/80 to 50/50 Do. Outside this range, the adhesion between the laminated polyester film and the hard coat layer may deteriorate. The weight ratio of the acrylic resin and the urethane resin can be set to a desired value by adjusting the amount of the raw material in the production of the acrylic urethane copolymer resin (a).

The solid content ratio of the acrylic urethane copolymer resin (a) and the polyester resin (b) in the coating composition is preferably from 40/60 to 5/95, so that the adhesion between the laminated polyester film and the hard coat layer becomes good, Do. More preferably 30/70 to 10/90.

(2) a polyester resin having a naphthalene skeleton (b)

The polyester resin (b) having a naphthalene skeleton in the present invention is a resin having a naphthalene skeleton in a polyester resin having an ester bond as a main bonding chain of the main chain.

Examples of the method for obtaining a polyester resin having a naphthalene skeleton include a method in which a diol component or a polyhydric hydroxyl group component in which two or more hydroxyl groups are introduced as a substituent in a naphthalene ring or a polyhydric hydroxyl group component in which a carboxylic acid group or an ester- There is a method of using a dicarboxylic acid component or a polycarboxylic acid component in which two or more derivatives are introduced as a polyester resin raw material. From the viewpoint of the stability of the polyester resin, it is preferable to obtain a polyester resin having a naphthalene skeleton by using a dicarboxylic acid component in which two carboxylic acid groups are introduced into a naphthalene ring as a polyester resin raw material. Examples of the naphthalene skeleton having two carboxylic acid groups include 2,6-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene Aromatic dicarboxylic acids such as dicarboxylic acid and 2,7-naphthalenedicarboxylic acid, and aromatic dicarboxylic acids such as dimethyl 2,6-naphthalenedicarboxylate, diethyl 2,6-naphthalenedicarboxylate, 1,4- Ester-forming derivatives of aromatic dicarboxylic acids such as dimethyl naphthalenedicarboxylate and diethyl 1,4-naphthalenedicarboxylate. Of these, ester-forming derivatives of 2,6-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid are particularly preferable in view of the refractive index and dispersibility with other resins.

It is preferable to use a polyester in which the dicarboxylic acid component having a naphthalene skeleton accounts for at least 30 mol%, more preferably at least 35 mol%, and even more preferably at least 40 mol%, of the total dicarboxylic acid component It is preferable because it can be improved.

Further, as the constituent component of the polyester resin (b) containing a naphthalene skeleton, for example, a polyvalent carboxylic acid and a polyhydric hydroxy compound having no naphthalene skeleton may be used in combination. That is, examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenylcarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, There may be mentioned phthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, , Trimellitic acid monopotassium salt, and ester-forming derivatives thereof. Examples of the polyhydric hydroxy compound include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, Hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol , Polyethylene glycol, polypropylene glycol, polytetramethylene glycol Call, there may be mentioned a polytetramethylene oxide glycol, dimethylol propionic acid, glycerin, trimethylolpropane, sodium dimethylol ethyl sulfonate, such as dimethylol propionic acid potassium.

The polyester resin (b) in the present invention is a copolymerized polyester resin having an aromatic dicarboxylic acid component containing a sulfonic acid metal base in an amount of 1 to 30 mol% based on the total dicarboxylic acid component of the polyester desirable. If the content is less than 1 mol%, the polyester resin may not exhibit water solubility, and the compatibility with the acrylic urethane copolymer resin (a), the isocyanate compound (c) and the dicyclohexylmethanecarbodiimide compound (d) The uniformity and transparency of the resin layer X may be lowered. On the other hand, if it exceeds 30 mol%, the dispersibility with other resins decreases, and transparency, anti-wet heat adhesion and anti-magnetic adhesion tend to be inferior.

Examples of the aromatic dicarboxylic acid component containing a sulfonic acid metal base include alkali metal salts of sulfophthalic acid, alkali metal salts of sulfoisophthalic acid, alkali metal salts of sulfoterephthalic acid, alkaline earth metal salts of sulfophthalic acid, Alkaline earth metal salts of sulfoterephthalic acid, alkali metal salts of sulfo-2,6-naphthalenedicarboxylic acid, alkali metal salts of sulfo-2,3-naphthalenedicarboxylic acid, sulfo-1,4-naphthalenedicarboxylic acid Alkaline earth metal salts of sulfo-2,6-naphthalene dicarboxylic acid, alkaline earth metal salts of sulfo-2,3-naphthalene dicarboxylic acid, alkaline earth metal salts of sulfo-1,4-naphthalene dicarboxylic acid And a compound having a sulfonic acid base such as an earth metal salt.

Examples of the aromatic dicarboxylic acid component containing a sulfonic acid metal base other than the above include alkali metal salts of dimethyl sulfophthalate, alkali metal salts of dimethyl sulfoisophthalate, alkali metal salts of dimethyl sulfoterephthalate, Alkaline earth metal salts of sodium sulfoisophthalic acid, alkaline earth metal salts of dimethyl sulfoterephthalic acid, alkali metal salts of dimethyl sulfo-2,6-naphthalenedicarboxylic acid, salts of dimethyl sulfo-2,3-naphthalenedicarboxylate An alkali metal salt of dimethyl sulfo-2,4-naphthalenedicarboxylate, an alkali metal salt of dimethyl sulfo-1,4-naphthalenedicarboxylate, an alkaline earth metal salt of dimethyl sulfo-2,6-naphthalenedicarboxylate, An aromatic dicarboxylic acid having a sulfonic acid base such as an alkaline earth metal salt of dimethyl sulfo-1,4-naphthalenedicarboxylate And salts of ester-forming derivatives of carboxylic acids.

Of these, alkali metal salts of sulfoisophthalic acid, alkaline earth metal salts of sulfoisophthalic acid, alkali metal salts and alkaline earth metal salts of ester forming derivatives of sulfoisophthalic acid are particularly preferable.

Specific examples of the alkali metal salt of dimethyl sulfophthalate include dimethyl sulfoxide 5-sulfophthalate, dimethyl sodium 5-sulfophthalate, dimethyl potassium 5-sulfophthalate and dimethyl cesium 5-sulfophthalate, and the alkaline earth metal salt of dimethyl sulfophthalate (5-sulfophthalic acid dimethyl) magnesium, bis (5-sulfophthalic acid dimethyl) calcium, bis (5-sulfophthalic acid dimethyl) barium and the like. Although concrete examples are omitted, the same applies to alkali metal salts and alkaline earth metal salts of dimethyl dimethyl sulfo isophthalate and dimethyl sulfoterephthalate.

In addition, the polyester resin (b) of the present invention may contain a diol component represented by the following formula (5) as a diol component of the polyester resin, thereby improving the dispersibility with other resins and improving the visibility desirable. Since the following formula (5) has a bisphenol S skeleton having an S element having a high refractive index, the refractive index of the polyester resin (b) can be increased. On the other hand, when a bisphenol compound including bisphenol A having a structure similar to that of the formula (5) is used as a diol component, the dispersibility improving effect and visibility improving effect with other resins are improved compared with the use of the diol component represented by the formula It is lagging.

Here, X ¹ and X ² : - (C ₁ H _{2 1} O) _m -H 1 = 2 or more and 4 or less, and m = 1 or more and 15 or less.

The oxyalkylene units constituting X ¹ and X ² are those having 2 to 4 carbon atoms and include oxyethylene units, oxypropylene units, oxybutylene units and / or oxytetramethylene units, Oxyethylene unit and / or oxypropylene unit (l = 2 or 3). The repeating number (m) of the oxyalkylene group is preferably 1 or more and 15 or less, more preferably 1 or more and 4 or less, still more preferably 1 or 2.

The polyester resin (b) in the present invention is preferably a copolymer polyester resin containing the diol component represented by the formula (5) in an amount of 5 mol% to 50 mol% with respect to the total diol component of the polyester. And more preferably 10 mol% or more and 40 mol% or less.

The polyester resin (b) preferably contains at least one diol compound represented by the following formula (6) as a diol component other than the formula (5).

(Wherein X ^{3 represents} - (C _x H _2x O) _y -, x represents an integer of 2 or more and 10 or less, y is an integer of 1 or more and 4 or less)

Examples of the alkane diol having 2 to 10 carbon atoms (x = 2 to 10) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6- hexanediol, neopentyl glycol, 1,6-octanediol, 1,8-octanediol, and 1,10-decanediol. Of these, 1,3-propanediol and 1,4-butanediol (x = 2 or 3) are preferred. The repeating number y of the oxyalkylene group is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less. The polyester resin (b) in the present invention is preferably a copolymerized polyester resin containing the diol component represented by the formula (6) in an amount of 5 mol% to 50 mol% with respect to the total diol component of the polyester. And more preferably 10 mol% or more and 40 mol% or less. Having such an oxyalkylene group is more preferable because the hydrophilicity of the polyester resin (b) can be improved and the dispersibility with the other resin can be improved.

The intrinsic viscosity of the polyester resin (b) used in the present invention is not particularly limited, but is preferably from 0.3 dl / g to 2.0 dl / g, more preferably from 0.4 dl / g to 1.0 dl / g, Is more preferable. The intrinsic viscosity in the present invention was obtained by dissolving 0.3 g of a polyester resin in 25 ml of a mixed solvent of phenol / tetrachloroethane = 40/60 (weight ratio), and measuring the viscosity of the solution by using a Cannon-Fenske viscometer Lt; 0 > C.

The polyester resin (b) according to the present invention preferably has a refractive index of 1.58 or more, preferably 1.61 or more and 1.65 or less. In the present invention, the refractive index is a value measured at 25 占 폚 using an Abbe's refractometer by molding a polyester resin into a resin plate having a thickness of 0.5 mm using a mini hot press. For the measurement, monobromonaphthalene is used as the intermediate liquid.

In the laminated polyester film of the present invention, the polyester resin (b) can be produced by the following production method. For example, a mixture of dimethyl naphthalenedicarboxylate as a dicarboxylic acid component having a naphthalene skeleton and sodium 5-sulfoisophthalate as an aromatic dicarboxylic acid component containing a sulfonic acid metal base and (5) A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S as a diol component to be represented and a diol component represented by formula (6) in the presence of a known polymerization catalyst, A polycondensation reaction in which a low molecular weight compound is distilled off and subjected to a polycondensation reaction. Further, it is also possible to use dimethyl naphthalenedicarboxylate as a dicarboxylic acid component having a naphthalene skeleton, dimethyl sodium 5-sulfoisophthalate as an aromatic dicarboxylic acid component containing a sulfonic acid metal base, A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S as a diol component and ethylene glycol as a diol component represented by formula (6) are transesterified in the presence of a known polymerization catalyst, Polycondensation-depolymerization reaction in which a compound is distilled off and a polycondensation reaction and a depolymerization reaction are carried out. Further, it is also possible to use dimethyl naphthalenedicarboxylate as a dicarboxylic acid component having a naphthalene skeleton, dimethyl sodium 5-sulfoisophthalate as an aromatic dicarboxylic acid component containing a sulfonic acid metal base, A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S as a diol component and ethylene glycol as a diol component represented by formula (6) are reacted in the presence of a known polymerization catalyst while distilling off low molecular weight compounds under high temperature and high vacuum, And a method of preparing by the sum reaction.

At this time, for example, alkali metals, alkaline earth metals, manganese, cobalt, zinc, antimony, germanium, titanium compounds and the like can be used as a reaction catalyst.

The Tg of the polyester resin (b) is preferably 0 deg. C or more and 130 deg. C or less, and more preferably 10 to 85 deg. When the Tg is in the range of 0 占 폚 or more and 130 占 폚 or less, anti-wet heat adhesion and anti-magnetic adhesion are improved. In addition, it is possible to suppress the occurrence of a blocking phenomenon in which the resin layers X are fixed to each other, and to improve the stability of the resin and the water dispersibility of the coating composition.

(3) Isocyanate Compound (c)

The isocyanate compound (c) in the present invention means a compound containing a structure derived from the following isocyanate compound (c) or the subsequently described isocyanate compound (c).

Examples of the isocyanate compound (c) include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, meta-xylylene diisocyanate, hexamethylene-1,6-diisocyanate, 1,6-diisocyanate hexane, Adducts of tolylene diisocyanate and hexanetriol, adducts of tolylene diisocyanate and trimethylol propane, polyol-modified diphenylmethane-4,4'-diisocyanate, carbodiimide-modified diphenylmethane-4,4'-di Isocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-bitolylene-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, Isocyanate and the like can be used. Particularly, when a polymeric isocyanate compound having a plurality of isocyanate groups at the terminals or side chains of a polymer such as polyester resin or acrylic resin is used, the toughness of the layer (X) becomes high, and therefore it can be preferably used.

When applied to an in-line coating method described later as a method for forming the resin layer (X), the isocyanate compound (c) is preferably water-dispersed. Particularly, a block isocyanate compound in which an isocyanate group is masked with a block agent or the like is particularly preferable in view of the pot life of the coating composition. As a crosslinking reaction of a block agent, a system is known in which the block agent is volatilized by the heat of the drying step after application and the isocyanate group is exposed to cause a crosslinking reaction. The isocyanate group may be a monofunctional or multifunctional type, but the cross-linking density of the layer (X) is improved by the polyfunctional type block polyisocyanate compound, and the cross-linking density with the hard coat layer, It is preferable because it has excellent properties.

Examples of the low molecular weight or high molecular compound having two or more block isocyanate groups include tolylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate 3 moles adduct of trimethylol propane, polyvinyl isocyanate, vinyl isocyanate copolymer, Methyl ethyl ketone oxime block of isocyanate, tolylene diisocyanate, sodium hypochlorite block of hexamethylene diisocyanate, methyl ethyl ketone oxime block of polyisocyanate diisocyanate, and tolylene diisocyanate trimethyl adipate of trimethylol propane Phenol block bodies and the like can be used.

When the total amount of the acrylic urethane copolymer resin (a) and the polyester resin (b) in the coating composition is 100 parts by weight, the coating composition used in the present invention contains not less than 3 parts by weight and not more than 20 parts by weight of the isocyanate compound (c) . More preferably 4 parts by weight or more and 18 parts by weight or less, and still more preferably 5 parts by weight or more and 16 parts by weight or less.

When the content of the isocyanate compound (c) is within the above range and the total content of the dicyclohexylmethanecarbodiimide compound (d) is within a predetermined range, the resin layer (X) exhibits high transparency, Adhesiveness and excellent visibility can be exhibited. When the content of the isocyanate compound (c) in the coating composition is less than 3 parts by weight, the adhesion with the hard coat layer may be poor. On the other hand, when the amount exceeds 20 parts by weight, the transparency of the laminated polyester film is deteriorated. In addition, the refractive index of the resin layer is lowered and the visibility when the hard coat layer is laminated may be poor.

(4) Dicyclohexylmethanecarbodiimide compound (d)

The dicyclohexylmethanecarbodiimide compound (d) in the present invention may have an alkyl group having 1 to 5 carbon atoms or a phenyl group as a substituent on a cyclohexyl ring or methane. Above all, the dicyclohexylmethanecarbodiimide compound represented by the following formula (1) is particularly preferable because it is excellent in suppressing interference fringes of the resin layer (X), anti-wet heat adhesion and heat-resistant water transparency.

For this reason, it is necessary to form a uniform dispersion structure of the resin layer (X) for the suppression of the iris phase shape (interference half). When the dicyclohexylmethanecarbodiimide compound represented by the formula (1) is used, And the uniform dispersion structure can be formed. Therefore, it is considered that the suppression (visibility) of the iris pattern (interference half) is improved. In addition, when the dicyclohexylmethanecarbodiimide compound represented by the formula (1) is used as described above, a resin layer having a high degree of crosslinking can be formed. Therefore, fine void generation on the surface of the resin layer It is considered that the amount of change in haze can be largely suppressed.

The preparation of the dicyclohexylmethanecarbodiimide compound represented by the above formula (1) can be carried out, for example, by reacting isocyanate-terminated dicyclohexyl (2-ethylhexyl) dicyclohexylmethane diisocyanate obtained from 4,4'-dicyclohexylmethane diisocyanate represented by the following formula Methanecarbodiimide and an organic compound having at least one hydroxyl group capable of reacting with an isocyanate group represented by the following formulas (8) to (10).

More specifically, isocyanate-terminated dicyclohexylmethanecarbodiimide is synthesized by a condensation reaction involving the carbon disulfide of the 4,4'-dicyclohexylmethane diisocyanate, and the isocyanate-terminated dicyclohexylmethane carbodiimide And a mixture of an organic compound having at least one hydroxyl group capable of reacting with an isocyanate group represented by the formulas (8) to (10).

The above-mentioned isocyanate-terminated dicyclohexylmethanecarbodiimide can be produced by a known method for producing a polycarbodiimide (US Pat. No. 2,941,956 or Japanese Patent Publication No. 47-33279, J. Org. Chem., 28, 2076 (1963), Chemical Review 1981, vol. 81, No. 4, 619-621).

The condensation reaction involving the carbon dioxide of the dicyclohexylmethane diisocyanate proceeds in the presence of a carbodiimidization catalyst. Examples of the catalyst include 1-phenyl-2-phosphorene-1-oxide, 3-methyl 1-oxide, 1-ethyl-2-phosphorene-1-oxide, 1-ethyl- Phosphorane-1-oxide. Of these, 3-methyl-1-phenyl-2-phosphorene-1-oxide is particularly preferred.

The reaction temperature in the condensation reaction is preferably in the range of 80 占 폚 to 180 占 폚. If the reaction temperature is below this range, the reaction time becomes very long. If the reaction temperature exceeds the above range, side reactions may occur and the carbodiimide compound having high purity may not be obtained.

The condensation degree of the dicyclohexylmethanecarbodiimide compound represented by the formula (1) is preferably 1 or more and 10 or less (n is preferably 1 or more and 10 or less in the formula (1)). When the degree of condensation exceeds 10, the dispersibility when the dicyclohexylmethanecarbodiimide compound (d) is dispersed in a water-based resin is lowered, and the dicyclohexylmethanecarbodiimide compound is previously dispersed in an aqueous solution or an aqueous dispersion , A good aqueous solution or aqueous dispersion may not be obtained because the dispersibility is low. Further, in order to complete the reaction quickly, the reaction of the 4,4'-dicyclohexylmethane diisocyanate is preferably carried out under an inert gas such as nitrogen.

Examples of the organic compound having at least one hydroxyl group capable of reacting with the isocyanate group include compounds represented by the following general formula (8).

Wherein p is an integer of 4 or more and 30 or less and R < ³ > is an alkyl group of 1 to 5 carbon atoms.

Further, examples of the organic compound having at least one hydroxyl group capable of reacting with the isocyanate group include compounds represented by the general formula (9).

Wherein q is an integer of 1 or more and 3 or less, R ⁴ is an alkyl group having 1 to ⁵ carbon atoms or a phenyl group, and R ⁵ is an alkyl group having 1 to ⁵ carbon atoms.

Further, examples of the organic compound having at least one hydroxyl group capable of reacting with the isocyanate group include compounds represented by the general formula (10).

[Wherein, R ⁶ is an alkyl group of 5 or less one or more carbon atoms, R ⁷ represents an alkyl group of five or fewer carbon atoms or at least one hydrogen;

Examples of the compound represented by the general formula (10) include dialkylaminoalcohols, specifically, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 1- Especially preferred is 1-diethylamino-2-propanol.

In the present invention, an organic compound having at least one hydroxyl group capable of reacting with an isocyanate group represented by the formula (8) and an organic compound having at least one hydroxyl group capable of reacting with an isocyanate group represented by the formula (9) It is preferable to use the mixture of the organic compounds in a molar ratio of 1: 1 to 1:19. When the ratio is outside the above range, for example, when the proportion of the organic compound represented by the formula (9) is decreased, the protection of the carbodiimide group by the organic compound represented by the formula (9) The reaction between the carbodiimide group and the functional group (for example, carboxyl group) in the aqueous resin progresses, which may lower the storage stability of the mixed solution or deteriorate the adhesion of the resin layer (X).

When the organic compound represented by the formula (9) is all added, the dispersibility when the aqueous dicyclohexylmethanecarbodiimide compound is added to the aqueous resin may be lowered.

An isocyanate-terminated dicyclohexylmethanecarbodiimide, an organic compound having at least one hydroxyl group capable of reacting with an isocyanate group represented by the formula (8), and an isocyanate group capable of reacting with an isocyanate group represented by the formula (9) The addition reaction of the mixture of the organic compounds having at least one hydroxyl group does not interfere with the use of the catalyst, but is easily proceeded only by heating.

The reaction temperature of the reaction is preferably in the range of 60 占 폚 to 160 占 폚, and more preferably in the range of 100 占 폚 to 150 占 폚. If the reaction temperature is below this range, the reaction time becomes very long. On the other hand, if the reaction temperature exceeds the above range, side reactions may occur and the carbodiimide compound having high purity may not be obtained.

The dicyclohexylmethanecarbodiimide compound of the present invention can be isolated from the reaction system according to a conventional method. Whether the carbodiimide compound is a dicyclohexylmethanecarbodiimide compound represented by the formula (1) can be judged by infrared absorption (IR) spectrum and nuclear magnetic resonance absorption (NMR) spectrum analysis.

The dicyclohexylmethanecarbodiimide compound obtained by the above production method can be used in various forms. When it is added to an aqueous resin or the like, it can be mixed as it is. However, it can be easily mixed with an aqueous solution or an aqueous dispersion beforehand .

In addition, the dicyclohexylmethanecarbodiimide compound (d) used in the present invention preferably has an aqueous solution. In the present invention, the term " aqueous " means that the compound has a property of uniformly affinity with water, such as water-soluble or self-emulsifiable. In order to improve the water-solubility and water-dispersibility of the carbodiimide compound in the range not to lose the effect of the present invention, addition of a surfactant, and addition of a polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, hydroxyalkylsulfonic acid A hydrophilic monomer such as a salt may be added and used.

The content of the dicyclohexylmethanecarbodiimide compound (d) in the coating composition is preferably 10 to 40 parts by weight based on 100 parts by weight of the total weight of solid components (a) and (b) in the coating composition. When the resin layer (X) of the present invention is formed on the polyester film in the range of 10 to 40 parts by weight, a laminated polyester film can impart a high resistance to moisture and heat and adhesion to the laminated polyester film .

When the isocyanate compound (c) and the dicyclohexylmethanecarbodiimide compound (d) are contained in the resin layer (X), it is possible to achieve a very good anti- Can be imparted to an ester film.

(5) Melamine compound (e)

The resin layer (X) of the present invention may be a layer formed using a coating composition further containing a melamine compound (e).

The melamine compound (e) is not particularly limited, but methylol, ethyl alcohol, isopropyl alcohol and the like are subjected to a dehydration condensation reaction as a lower alcohol to a methylol melamine derivative obtained by condensing melamine and formaldehyde in view of hydrophilization, And one compound.

Examples of the methylolated melamine derivatives include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine.

The layer formed by using the coating composition containing the melamine compound (e) in the resin layer (X) of the present invention is preferable because adhesion can be improved, but if the coating composition contains a large amount of melamine compound, There is a problem that process contamination due to the volatilization of the melamine compound becomes a problem or that the melamine compound generates formaldehyde which is harmful to the human body by the crosslinking reaction. Therefore, the content of the melamine compound (e) is preferably 30 parts by weight or less based on 100 parts by weight of the total weight of solid components (a) and (b) in the coating composition. More preferably 5 parts by weight or more and 30 parts by weight or less, and particularly preferably 10 parts by weight or more and 25 parts by weight or less.

When the melamine compound (e) is used in an amount of 5 parts by weight or more and 30 parts by weight or less, when the layer (X) of the present invention is formed on a polyester film to form a laminated polyester film, the adhesion between the laminated polyester film and the hard coat layer It can be made better.

(6) Method of forming the resin layer (X)

The resin layer (X) in the present invention is a polyester film which is the base material of the above-mentioned polyester film. The acrylic urethane copolymer resin (a), the polyester resin (b), the isocyanate compound (c), the dicyclohexyl Methanecarbodiimide compound (d). Here, the acrylic urethane copolymer resin (a), the polyester resin (b), the isocyanate compound (c), the dicyclohexylmethanecarbodiimide compound (d ) And, if necessary, a melamine compound (e) is formed into a layer shape on the base film and cured or crosslinked as required. For example, the acrylic urethane copolymer resin (a), the polyester resin (b), the isocyanate compound (c), the dicyclohexylmethanecarbodiimide compound (d) and, if necessary, the melamine compound , A coating liquid containing a solvent or a surfactant is coated on the polyester film, and if necessary, the solvent is dried and, if necessary, cured or crosslinked to form a resin layer (X) on the polyester film .

In the present invention, it is preferable to use an aqueous solvent (f) as a solvent. The use of an aqueous solvent can suppress the rapid evaporation of the solvent in the drying step, so that a uniform resin layer (X) can be formed, and is excellent in environmental load.

Here, the water-based solvent (f) is water or an alcohol such as methanol, ethanol, isopropyl alcohol or butanol, ketones such as acetone or methyl ethyl ketone, glycols such as ethylene glycol, diethylene glycol or propylene glycol And that organic solvent soluble in water is mixed at an arbitrary ratio. By using an aqueous solvent, rapid evaporation of the solvent in the drying step can be suppressed, and a uniform resin layer can be formed. It is also excellent in terms of environmental load.

The coating method of the coating composition onto the polyester film may be any of an in-line coating method and an off-coating method, but is preferably an in-line coating method.

The in-line coating method is a method of performing coating in a process of producing a polyester film. Specifically, this refers to a method in which polyester resin is melt-extruded, biaxially stretched, thermally treated, and wound up in an optional step. Normally, it is applied to a film of the following steps.

(Substantially unoriented) non-oriented (non-oriented) polyester film (hereinafter referred to as "A film") obtained by melt-extruding a polyester resin and quenching it,

A uniaxially stretched (uniaxially oriented) polyester film (hereinafter referred to as "B film") obtained by stretching "A film" in the longitudinal direction or width direction,

Biaxially oriented (biaxially oriented) polyester film (hereinafter referred to as "C film") before heat treatment in which the "B film" is stretched in the width direction or the longitudinal direction.

In the present invention, the coating composition is applied to any one of the A film, the B film or the C film before the crystal orientation is completed, and thereafter the polyester film is uniaxially or biaxially stretched, It is preferable to adopt a method of completing the crystal orientation of the polyester film by performing heat treatment at a temperature higher than the boiling point and forming the resin layer (X). According to this method, since the film formation of the polyester film and the application and drying of the coating composition (that is, the formation of the resin layer (X)) can be carried out at the same time, there is merit in production cost. Further, since stretching is performed after coating, it is easy to make the thickness of the resin layer X thinner. The thickness of the resin layer X is preferably such that optical interference can be removed from the viewpoint of visibility, and is preferably 50 nm or more and 200 nm or less, more preferably 60 nm or more and 150 nm or less, further preferably 70 nm or more 130 nm or less.

Among them, a method of applying a coating composition to a uniaxially stretched film (B film) in the longitudinal direction or the width direction and then stretching in the width direction or the longitudinal direction to perform heat treatment is excellent. Compared with the biaxial stretching method after coating on an unstretched film, since the stretching process is performed only once, defects and cracks of the resin layer (X) due to stretching are less likely to occur, so that a resin layer (X) having excellent transparency and smoothness is formed I can do it. It is also preferable to apply the coating composition to a film (B film) uniaxially stretched in the longitudinal direction from the width direction. This is because the uniaxially stretched film (B film) in the longitudinal direction can be uniformly applied because the coating width of the coating composition is narrow, and as a result, the thickness of the coating film can be strictly controlled. Since it is necessary to control the film thickness in the nano order to suppress the interference layer, it is preferable that the coating composition is applied to the uniaxially stretched film (B film) in the longitudinal direction.

On the other hand, the offline coating method is a method in which the film A is uniaxially or biaxially stretched and subjected to a heat treatment to complete the crystal orientation of the polyester film, or to a film A in a process different from the film- And then applying the composition.

In the present invention, it is preferable that the resin layer (X) is formed by the in-line coating method from the above-mentioned various advantages.

Therefore, a preferred method of forming the resin layer (X) in the present invention is a method in which a water-based coating composition using an aqueous solvent (f) is applied on a polyester film using an inline coating method and dried. More preferably, the coating composition is in-line coated on the B film after uniaxial stretching. The solid content concentration of the coating composition in the coating liquid is preferably 5% by weight or less. By setting the solid content concentration to 5% or less, a good coating property can be imparted to the coating composition, and a laminated polyester film having a transparent and homogeneous resin layer can be produced.

(7) Method for preparing a coating liquid containing a coating composition using an aqueous solvent (f)

The coating composition using the water-based solvent (f) may contain a water-soluble or water-permeable acrylic urethane copolymer resin (a), a polyester resin (b), an isocyanate compound (c), a dicyclohexylmethanecarbodiimide compound d) and the water-based solvent (f) in any desired order at a desired solid content weight ratio and stirring.

Then, the melamine compound (e) may be added to the coating composition as desired in any order in a desired solid content weight ratio and stirred. For mixing and stirring, the container may be shaken by hand, or a magnetic stirrer, a stirring blade, ultrasonic wave irradiation, vibration dispersion, or the like may be performed.

If necessary, various additives such as lubricants, inorganic particles, organic particles, surfactants, and antioxidants may be added to the extent that the properties of the resin layer formed by the coating composition are not deteriorated.

(8) Coating method

As a method of applying the coating composition to the polyester film, any known coating method such as a bar coating method, a reverse coating method, a gravure coating method, a die coating method, and a blade coating method can be used.

(9) Method for producing laminated polyester film

Next, the production method of the laminated polyester film of the present invention will be described by taking as an example the case where a polyethylene terephthalate (hereinafter abbreviated as PET) film is used for the polyester film, but the invention is not limited thereto. First, the pellets of PET are sufficiently vacuum-dried and then fed to an extruder and melt-extruded into a sheet form at about 280 DEG C, followed by cooling and solidification to produce an unstretched (unoriented) PET film (A film). The film is stretched 2.5 to 5.0 times in the longitudinal direction by a roll heated to 80 to 120 占 폚 to obtain a uniaxially oriented PET film (B film). The coating composition of the present invention prepared at a predetermined concentration is applied to one side of the B film. At this time, a surface treatment such as a corona discharge treatment may be performed on the coated surface of the PET film before coating. It is possible to improve the wettability of the coating composition to the PET film by performing the surface treatment such as corona discharge treatment, thereby preventing the coating composition from being crawled and achieving a uniform coating thickness.

After the application, the end of the PET film is gripped with a clip and is led to a heat treatment zone (preheating zone) at 80 to 130 캜 to dry the solvent of the coating composition. After drying, it is stretched by 1.1 to 5.0 times in the width direction. Then, it is led to a heat treatment zone (heat fixing zone) at 160 to 240 占 폚 and heat treatment is performed for 1 to 30 seconds to complete crystal orientation.

In this heat treatment step (heat fixing step), 3 to 15% relaxation treatment may be carried out in the width direction or the longitudinal direction as necessary. The thus-obtained laminated polyester film is transparent, and becomes a laminated polyester film excellent in adhesion to a hard coat layer, anti-wet heat adhesion, anti-magnetic adhesion, heat-resistant water resistance, and visibility when a hard coating layer is laminated.

[Method of measuring characteristics and evaluation method of effect]

(1) Evaluation method of transparency

The transparency was evaluated by the initial haze (%). The haze was measured using a turbidimeter "NDH5000" manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD. After leaving the laminated polyester film for 1 hour in a state (temperature 23 ° C., relative humidity 65%). The average value measured three times was taken as the initial haze of the laminated polyester film. Transparency was evaluated in four steps according to the value of haze. C is a level with practical problems, B is a practical level, and S and A are good.

S: Less than 1.0%

A: 1.0% or more and less than 2.0%

B: 2.0% or more and less than 3.0%

C: More than 3.0%.

(2) Evaluation method of adhesion to hard coat layer

(2-1) Evaluation method of initial adhesion property

The UV cured resin mixed in the following ratio on the surface of the resin layer (X) of the laminated polyester film was uniformly coated using a bar coater so that the cured UV cured resin layer had a thickness of 2 탆.

Dipentaerythritol hexaacrylate: 60 parts by weight

("KAYARAD" (registered trademark) DPHA manufactured by NIPPON KAYAKU CO., LTD.)

Pentaerythritol triacrylate: 40 parts by weight

("KAYARAD" (registered trademark) PETA manufactured by NIPPON KAYAKU CO., LTD.)

Photopolymerization initiator ("IRGACURE" (registered trademark) 184 manufactured by NAGASE & CO., LTD.): 3 parts by weight

Methyl ethyl ketone: 100 parts by weight

Subsequently, a light-collecting type high-pressure mercury lamp (H03-L31 manufactured by EYE GRAPHICS CO., LTD.) Having an irradiation intensity of 120 W / cm set at a height of 9 cm from the surface of the UV cured resin layer was irradiated with ultraviolet light having an integrated irradiation intensity of 300 mJ / Ultraviolet rays were irradiated so as to be cured, and a hard coat laminated polyester film in which a hard coat layer was laminated on a laminated polyester film was obtained. 100 cross-cuts of 1 mm < 2 > were put on the hard coat laminated surface of the obtained hard-coated laminated polyester film, and a cellophane tape (registered trademark) (CT405AP manufactured by NICHIBAN CO., LTD.) Was attached. After pressing with a load, the hard-coated laminated polyester film was rapidly peeled in the direction of 90 °. Adhesiveness was evaluated in four steps by the number of remaining crosscuts. The number of remaining crosscuts was a value obtained by rounding off the number of first decimal places of the average value obtained three times. C is a level with practical problems, B is a practical level, and S and A are good.

S: 100 remaining

A: 80 to 99 remaining

B: 50 to 79 remaining

C: Only 0 ~ 50 ants remain.

(2-2) Evaluation method of adhesion resistance in wet heat

A hard-coated laminated polyester film was obtained in the same manner as in (2-1). The resultant hard-coated laminated polyester film was allowed to stand for a predetermined time (240 hours, 500 hours) in a constant-temperature and constant-humidity bath at a temperature of 85 ° C and a relative humidity of 85%, and then dried in a state (23 ° C, relative humidity 65% A hard-coated laminate sample for wet heat adhesion test was obtained. The obtained hard-coating laminate sample for wet adhesion test was subjected to adhesion evaluation in the same manner as in (2-1), and evaluated in four steps. The number of remaining crosscuts was a value obtained by rounding off the number of first decimal places of the average value obtained three times. C is a level with practical problems, B is a practical level, and S and A are good.

(2-3) Evaluation method of self-adhesive property

The UV cured resin was applied to the surface of the resin layer of the laminated polyester film in the same manner as in the evaluation of (2-1) and cured to obtain an evaluation sample for adhesion of masticity. Then, the samples for evaluation of adhesion resistance were cut into a size of 10 cm x 10 cm, fixed to the respective clips to form a bundle state, and then the entire surface of the laminated polyester film was immersed in boiling hot water (100 DEG C) Immersed for 18 hours. Thereafter, a sample for evaluation of mabi adhesion was taken out and dried in a state (23 ° C, relative humidity 65%) for 1 hour to obtain a hardcoat laminated sample for mabi adhesion test. The obtained hard-coating laminate sample for self-adhesive adhesion test was evaluated for adhesion in the same manner as in (2-1) and evaluated in four steps. The number of remaining crosscuts was a value obtained by rounding off the number of first decimal places of the average value obtained three times. C is a level with practical problems, B is a practical level, and S and A are good.

(3) Evaluation method of thermal water resistance

The heat-resistant water-transparency was evaluated by the haze change (? Hz) (%) before and after immersing the laminated polyester film in the hot water furnace. The laminated polyester film was cut into a size of 10 cm x 10 cm and fixed on a clip to be in a state of being put in a state of being put in a state of being immersed in the boiled hot water (100 DEG C) Time. Thereafter, the laminated polyester film was taken out and dried in a state (23 캜, relative humidity 65%) for 1 hour to obtain a sample for heat water resistance transparency test. Here, in the case of a sample having only the resin layer (X) on one side of the polyester film, the side of the polyester film opposite to the resin layer was wiped with a nonwoven fabric containing acetone (OZU CORPORATION, , And left standing for one hour in the state to remove the oligomer precipitated from the surface of the polyester film opposite to the resin layer to obtain a sample for heat water resistance transparency test.

Transparency was evaluated by the same method as in (1) for the obtained hot water water resistance test sample, and the obtained value was defined as haze (%) after the mercury-free test. The value obtained by subtracting the haze (%) (initial haze) before the mercury-free testing process from this value is used as the film haze change amount (? Hz) before and after the mercury-free testing process (? Hz = haze after mercury- Evaluation was carried out, and a four-step evaluation was carried out. C is a level with practical problems, B is a practical level, and S and A are good.

S: less than 3.0%

A: 3.0% or more and less than 5.0%

B: 5.0% or more and less than 6.0%

C: 6.0% or more.

(4) Evaluation method of visibility (interference pattern)

(2-1), a hard coating film having a hard coat layer of 2 탆 in thickness laminated on the laminated polyester film was obtained. Subsequently, a sample having a size of 8 cm (in the hard coating film width direction) × 10 cm (in the hard coating film length direction) was cut out from the obtained hard coating film, and a black glossy tape (YAMATO CO., LTD. Tape No. 200-50-21: black) were bonded so as to prevent air bubbles from entering.

The sample was placed in a dark room at 30 cm directly below a 3-wavelength fluorescent lamp (MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD., 3rd wavelength type main white (F · L 15EX-N 15W)), And the following evaluation was made. A or better.

S: Interference half hardly visible

A: I see a little interference

B: We see a weak interferometer.

C: The interference half is strong.

(5) Evaluation method of film thickness of resin layer (X)

On the laminated polyester film, RuO ₄ A sample was prepared by a dyed ultra-thin slice method. The cross section of the obtained sample was observed using a transmission electron microscope (TEM) to measure the thickness of the resin layer (X) on the laminated polyester film. The thickness of the resin layer X was read from the image taken at a magnification of 200,000 times by TEM. The thickness of the resin layer was measured at 20 points, and the average value thereof was taken as the film thickness (nm) of the resin layer (X).

· Measuring device: transmission electron microscope (H-7100FA type from HITACHI CO., LTD.).

(6) Evaluation method of spectral reflectance

The film sheet cut in the A4 cut size was divided into three in the vertical and horizontal directions, and nine points in total were used as measurement samples. And the longer side was the longitudinal direction. The measurement of the spectral reflectance was carried out as follows. A black glossy tape (YAMATO CO., LTD. Vinyl tape No. 200-50-21: black) having a width of 50 mm was bubbled into the back surface of the measurement surface The sample and the tape were bonded together in the longitudinal direction, and then cut into 4 cm x 4 cm sample pieces, and the spectral reflectance was measured on a spectrophotometer (UV2450 manufactured by SHIMADZU CORPORATION) at an incident angle of 5 deg. The direction in which the sample is set in the measuring device is the longitudinal direction of the sample in the forward and backward directions toward the front of the measuring device. In addition, we used a part of the Al ₂ O ₃ plate as standard reflection plate to screen based on the reflectance. The spectral reflectance of the surface side having the resin layer X is measured for a wavelength range of 450 nm to 650 nm and the minimum value of the spectral reflectance in the wavelength range of 450 nm to 650 nm %). The measurement was carried out on 9 pieces of sample pieces cut into 4 cm x 4 cm and the average value of 9 points was obtained.

(7) Evaluation method of dispersion index (determination by cross-sectional photograph of transmission electron microscope (TEM))

On the laminated polyester film, RuO ₄ A sample on the surface of the resin layer (X) is prepared by a dyed ultra thin film slice method. A cross-section of the obtained sample was taken using a transmission electron microscope (TEM) under the following conditions. The number of agglomerates including the acrylic urethane copolymer resin (a) having a size of 40 nm or more observed in the view area (Z direction x direction: 500 nm x 1200 nm) in the obtained cross-sectional photograph was observed, The number is converted into the number per a predetermined area (120000 nm ² ) by the following formula.

(Number of agglomerates having an observed size of 40 nm or more) x 120000 / area occupied by the resin layer (X) in the visual field area

The observation was performed for 10 fields and the number of first decimal places of the average number of aggregates observed per a predetermined area was rounded off to obtain a dispersion index.

· Measuring device: transmission electron microscope (H-7100FA type, HITACHI CO., LTD.)

Measurement conditions: Acceleration voltage 100 kV

· Magnification: 20,000 times.

(8) Analysis of dicyclohexylmethanecarbodiimide compound (d)

The dicyclohexylmethanecarbodiimide compound (d) was analyzed by proton nuclear magnetic resonance (1H-NMR), carbon nuclear magnetic resonance spectroscopy (13C-NMR) and Fourier infrared spectroscopy (FT- ). ≪ / RTI >

(9) Evaluation method of the change amount (? R) of the spectral reflectance before and after the mercury treatment test

The spectral reflectance (%) before the mercury treatment test was measured in the same manner as described in the evaluation method of reflectance (6), and the spectral reflectance was measured for the wavelength range of 400 nm to 800 nm on the side of the resin layer (X) I got it.

The spectral reflectance (%) after the mercury treatment test was obtained by the following method. Namely, the laminated polyester film was cut into nine samples at a size of 10 cm x 10 cm and fixed on a clip to form a bundle state. Thereafter, the entire surface of the laminated polyester film in the boiled hot water (100 ° C) Was immersed in water for 5 hours (mercury treatment test). Thereafter, the laminated polyester film was taken out and dried in a state (23 ° C, relative humidity 65%) for 1 hour to obtain a sample for measurement of spectral reflectance after the self-treatment treatment test.

A 50 mm wide black glossy tape (YAMATO CO., LTD. Vinyl Tape No. 200-50-21: manufactured by YAMATO CO., LTD.) Was applied to the back surface of the measurement surface (the resin layer (X) Black) was bonded so as not to enter the bubbles. The sample was cut into 4 cm x 4 cm sample pieces, and the spectral reflectance was measured at a wavelength of 400 nm to 800 nm at an incident angle of 5 DEG from a spectrophotometer (SHIMADZU CORPORATION made by UV2450) did. An average value in a wavelength range of 400 nm or more and 800 nm or less in wavelength was taken as an average value of 9 pieces of sample pieces cut into 4 cm x 4 cm with the spectral reflectance (%) after the self treatment test.

The value obtained by subtracting the average spectral reflectance (%) after the self-bias treatment test obtained above from the average value (%) of the spectral reflectance before the self-bias test treatment is referred to as a change amount (? R) of the spectral reflectance before and after the self- (Reflectance-spectral reflectance after the self-examination) (%).

Example

The present invention will be described in more detail based on examples. However, the present invention is not limited to the following examples.

A reference example also shows a method of synthesizing an acrylic urethane copolymer resin and a polyester resin having a naphthalene skeleton.

(Reference Example 1)

Preparation of an aqueous dispersion of the acrylic urethane copolymer resin (a-1)

66 parts by weight of a polyester-based urethane resin (DIC CORPORATION "HYDRAN" (registered trademark) AP-40 (F)) and 35 parts by weight of methyl methacrylate were placed in a vessel 1 under a nitrogen gas atmosphere at room temperature (25 ° C.) 29 parts by weight of ethyl acrylate, and 2 parts by weight of N-methylolacrylamide were injected to obtain Solution 1. Subsequently, 7 parts by weight of an emulsifier ("REASOAP" ER-30 manufactured by ADEKA CORPORATION) was added, and water was further added so that the solid content of the solution became 50% by weight to obtain Solution 2. 30 parts by weight of water was added to vessel 2 at room temperature (25 占 폚), and the temperature was raised to 60 占 폚. Thereafter, the solution 2 was continuously added dropwise to the vessel 2 over 3 hours while stirring. Simultaneously, 3 parts by weight of a 5 wt% aqueous solution of potassium persulfate was continuously added dropwise to the vessel 2. After completion of the dropwise addition, the mixture was further stirred for 2 hours and then cooled to 25 캜 to complete the reaction to obtain an acrylic urethane copolymer resin (a-1) water dispersion. The solid content concentration of the obtained acrylic urethane copolymer resin (a-1) water dispersion was 30% by weight.

In the following Reference Examples 2 to 13, the composition ratio of the dicarboxylic acid component and the diol component is a value obtained by taking the entire dicarboxylic acid component and the entire diol component as 100 mol%. In Reference Examples 2 to 13, the molar ratio of the total dicarboxylic acid component to the total diol component was 1: 1.

(Reference Example 2)

Preparation of a water dispersion of a polyester resin (b-1) having a naphthalene skeleton

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Dimethyl 2,6-naphthalenedicarboxylate: 88 mol%

Dimethyl sodium 5-sulfoisophthalate: 12 mol%

(Diol component)

A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S: 86 mole%

1,3-propanediol: 14 mol%.

(Reference Example 3)

Preparation of a water dispersion of a polyester resin (b-2) having a naphthalene skeleton and an aromatic dicarboxylic acid component containing a sulfonic acid metal base

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Dimethyl 2,6-naphthalenedicarboxylate: 99 mol%

Dimethyl sodium 5-sulfoisophthalate: 1 mol%

(Diol component)

A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S: 86 mole%

1,3-propanediol: 14 mol%.

(Reference Example 4)

Preparation of an aqueous dispersion of a polyester resin (b-3) having a naphthalene skeleton and an aromatic dicarboxylic acid component containing a sulfonic acid metal base

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Dimethyl 2,6-naphthalenedicarboxylate: 85 mol%

Dimethyl sodium 5-sulfoisophthalate: 15 mol%

(Diol component)

A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S: 86 mole%

1,3-propanediol: 14 mol%.

(Reference Example 5)

Preparation of an aqueous dispersion of a polyester resin (b-4) having a naphthalene skeleton and an aromatic dicarboxylic acid component containing a sulfonic acid metal base

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

2,6-naphthalene dicarboxylic acid: 85 mol%

Dimethyl sodium 5-sulfoisophthalate: 15 mol%

(Diol component)

A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S: 86 mole%

1,3-propanediol: 14 mol%.

(Reference Example 6)

Preparation of a water dispersion of a polyester resin (b-5) having a naphthalene skeleton and an aromatic dicarboxylic acid component containing a sulfonic acid metal base

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Dimethyl 2,6-naphthalenedicarboxylate: 65 mol%

5 mol% sodium dimethylsulfoisophthalate: 35 mol%

(Diol component)

A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S: 86 mole%

1,8-octanediol: 14 mol%.

(Reference Example 7)

Preparation of a water dispersion of a polyester resin (b-6) having a naphthalene skeleton and no aromatic dicarboxylic acid component containing a sulfonic acid metal base

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Dimethyl 2,6-naphthalenedicarboxylate: 88 mol%

Trimellitic acid: 12 mol%

(Diol component)

A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S: 86 mole%

Ethylene glycol: 14 mol%.

(Reference Example 8)

Preparation of a water dispersion of a polyester resin (b-7) having a naphthalene skeleton and further having a bisphenol S skeleton

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Dimethyl 2,6-naphthalenedicarboxylate: 88 mol%

Dimethyl sodium 5-sulfoisophthalate: 12 mol%

(Diol component)

A compound obtained by adding 2 mol of propylene oxide to 1 mol of bisphenol S: 86 mol%

Ethylene glycol: 14 mol%.

(Reference Example 9)

Preparation of an aqueous dispersion of an ester resin (b-8) having a naphthalene skeleton and further having a bisphenol S skeleton

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Dimethyl 2,6-naphthalenedicarboxylate: 88 mol%

Dimethyl sodium 5-sulfoisophthalate: 12 mol%

(Diol component)

A compound obtained by adding 10 mol of propylene oxide to 1 mol of bisphenol S: 50 mol%

Ethylene glycol: 50 mol%.

(Reference Example 10)

Preparation of a water dispersion of a polyester resin (b-9) having a naphthalene skeleton and further having a bisphenol A skeleton

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Dimethyl 2,6-naphthalenedicarboxylate: 85 mol%

5-sulfoisophthalic acid dimethyl lithium: 15 mol%

(Diol component)

A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol A: 86 mole%

Ethylene glycol: 14 mol%.

(Reference Example 11)

Preparation of a water dispersion of a polyester resin (b-10) having a naphthalene skeleton and having a bisphenol A skeleton

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Dimethyl 2,6-naphthalenedicarboxylate: 85 mol%

Dimethyl sodium 5-sulfoisophthalate: 15 mol%

(Diol component)

A compound obtained by adding 10 moles of propylene oxide to 1 mole of bisphenol A: 86 mole%

Ethylene glycol: 14 mol%.

(Reference Example 12)

Preparation of a water dispersion of a polyester resin (b-11) having no naphthalene skeleton

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Isophthalic acid: 88 mol%

Dimethyl sodium 5-sulfoisophthalate: 12 mol%

(Diol component)

A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S: 86 mole%

Ethylene glycol: 14 mol%.

(Reference Example 13)

Preparation of a water dispersion of a polyester resin (b-12) having no naphthalene skeleton

A polyester resin aqueous dispersion comprising the following copolymerization composition

≪ Copolymerization component &

(Dicarboxylic acid component)

Terephthalic acid: 88 mol%

Dimethyl sodium 5-sulfoisophthalate: 12 mol%

(Diol component)

A compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S: 86 mole%

Ethylene glycol: 14 mol%.

(Reference Example 14)

The water dispersion of the carbodiimide compound (d-1)

The dicyclohexylmethanecarbodiimide compound represented by the formulas (11) to (13) was obtained by the following synthesis method.

578 g of 4,4'-dicyclohexylmethane diisocyanate and 2.9 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 ° C. for 15 hours to obtain an isocyanate- Hexylmethanecarbodiimide (polymerization degree = 4) was obtained. Then, a mixture (mixing molar ratio = 1: 1) of 242.5 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 and 39.7 g of propylene glycol monomethyl ether was added to the resulting isocyanate-terminated dicyclohexylmethanecarbodiimide And the mixture was reacted at 150 DEG C for 5 hours. After the reaction, the solution was cooled to 80 ° C, and 1173 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of light yellow transparent carbodiimide compound (d-1).

(Reference Example 15)

The water dispersion of the carbodiimide compound (d-2)

The dicyclohexylmethanecarbodiimide compound represented by the formula (11), the formula (12) and the formula (14) was obtained by the following synthesis method.

578 g of 4,4'-dicyclohexylmethane diisocyanate and 2.9 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 ° C. for 15 hours to obtain an isocyanate- Hexylmethanecarbodiimide (polymerization degree = 4) was obtained. Then, a mixture of 242.5 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 and 57.8 g of N, N-diethyl isopropanolamine (mixing molar ratio = 1: 1) was added to the obtained isocyanate-terminated dicyclohexylmethanecarbodiimide. 1) was added and reacted at 150 ° C for 5 hours. After the reaction, the mixture was cooled to 80 ° C, and 1200 g of distilled water was slowly added to obtain an aqueous dispersion (solid concentration: 40% by weight) of light yellow transparent carbodiimide compound (d-2).

(Reference Example 16)

The water dispersion of the carbodiimide compound (d-3)

The dicyclohexylmethanecarbodiimide compound represented by the formula (15), the formula (12) and the formula (13) was obtained by the following synthesis method.

584 g of 4,4'-dicyclohexylmethane diisocyanate and 2.9 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 DEG C for 17 hours to obtain an isocyanate- Hexylmethanecarbodiimide (polymerization degree = 6) was obtained. Then, a mixture (mixing molar ratio = 1: 1) of 242.5 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 and 39.7 g of propylene glycol monomethyl ether was added to the resulting isocyanate-terminated dicyclohexylmethanecarbodiimide And the mixture was reacted at 150 DEG C for 5 hours. After the reaction, the solution was cooled to 80 ° C, and 1173 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of light yellow transparent carbodiimide compound (d-3).

(Reference Example 17)

The water dispersion of the carbodiimide compound (d-4)

The dicyclohexylmethanecarbodiimide compound represented by the formula (16), the formula (12) and the formula (13) was obtained by the following synthesis method.

589 g of 4,4'-dicyclohexylmethane diisocyanate and 3.0 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 DEG C for 21 hours to obtain an isocyanate- Hexylmethanecarbodiimide (polymerization degree = 9) was obtained. Then, a mixture (mixing molar ratio = 1: 1) of 242.5 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 and 39.7 g of propylene glycol monomethyl ether was added to the resulting isocyanate-terminated dicyclohexylmethanecarbodiimide And the mixture was reacted at 150 DEG C for 5 hours. After the reaction, the mixture was cooled to 80 deg. C and 1200 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of light yellow transparent carbodiimide compound (d-4).

(Reference Example 18)

The water dispersion of the carbodiimide compound (d-5)

The dicyclohexylmethanecarbodiimide compound represented by the formula (11) and the formula (17) was obtained by the following synthesis method.

578 g of 4,4'-dicyclohexylmethane diisocyanate and 2.9 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 ° C. for 15 hours to obtain an isocyanate- Hexylmethanecarbodiimide (polymerization degree = 4) was obtained. 485.0 g of poly (ethylene oxide) monomethyl ether having a polymerization degree (p) = 12 was added to the resulting isocyanate-terminated dicyclohexylmethanecarbodiimide, and the mixture was reacted at 150 ° C for 5 hours. After the reaction, the mixture was cooled to 50 캜, and 1478 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of light yellow transparent carbodiimide compound (d-5).

(Reference Example 19)

The water dispersion of the carbodiimide compound (d-6)

The dicyclohexylmethanecarbodiimide compound represented by the formula (11) and the formula (18) was obtained by the following synthesis method.

578 g of 4,4'-dicyclohexylmethane diisocyanate and 2.9 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 ° C. for 15 hours to obtain an isocyanate- Hexylmethanecarbodiimide (polymerization degree = 4) was obtained. Then, a mixture (mixing molar ratio = 1: 9) of 48.5 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 and 71.4 g of propylene glycol monomethyl ether was added to the resulting isocyanate-terminated dicyclohexylmethanecarbodiimide And the mixture was reacted at 150 DEG C for 5 hours. After the reaction, the mixture was cooled to 80 ° C and 930 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of a milky white colored carbodiimide compound (d-6).

(Reference Example 20)

The water dispersion of the carbodiimide compound (d-7)

The dicyclohexylmethanecarbodiimide compound represented by the formula (11) and the formula (19) was obtained by the following synthesis method.

578 g of 4,4'-dicyclohexylmethane diisocyanate and 2.9 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 ° C. for 15 hours to obtain an isocyanate- Hexylmethanecarbodiimide (polymerization degree = 4) was obtained. Then, a mixture (mixing molar ratio = 1: 9) of 48.5 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 and 117.5 g of dipropylene glycol monomethyl ether was added to the resulting isocyanate-terminated dicyclohexylmethanecarbodiimide. And the mixture was reacted at 150 ° C for 5 hours. After the reaction, the mixture was cooled to 80 ° C and 999 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of a milky white carbodiimide compound (d-7).

(Reference Example 21)

The water dispersion of the carbodiimide compound (d-8)

The dicyclohexylmethanecarbodiimide compound represented by the formula (11) and the formula (20) was obtained by the following synthesis method.

578 g of 4,4'-dicyclohexylmethane diisocyanate and 2.9 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 ° C. for 15 hours to obtain an isocyanate- Hexylmethanecarbodiimide (polymerization degree = 4) was obtained. Then, a mixture (mixing molar ratio = 1: 9) of 48.5 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 and 163.5 g of tripropylene glycol monomethyl ether was added to the resulting isocyanate-terminated dicyclohexylmethanecarbodiimide. And the mixture was reacted at 150 ° C for 5 hours. After the reaction, the mixture was cooled to 80 ° C and 1068 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of a milky white carbodiimide compound (d-8).

(Reference Example 22)

The water dispersion of the carbodiimide compound (d-9)

The dicyclohexylmethanecarbodiimide compound represented by the formula (11) and the formula (21) was obtained by the following synthesis method.

578 g of 4,4'-dicyclohexylmethane diisocyanate and 2.9 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 ° C. for 15 hours to obtain an isocyanate- Hexylmethanecarbodiimide (polymerization degree = 4) was obtained. Then, a mixture (mixing molar ratio = 1: 9) of 48.5 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 and 120.6 g of propylene glycol monophenyl ether was added to the resulting isocyanate-terminated dicyclohexylmethanecarbodiimide And the mixture was reacted at 150 DEG C for 5 hours. After the reaction, the mixture was cooled to 80 ° C and 1004 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of a milky white carbodiimide compound (d-9).

(Reference Example 23)

The water dispersion of the carbodiimide compound (d-10)

The dicyclohexylmethanecarbodiimide compound represented by the formula (11) and the formula (22) was obtained by the following synthesis method.

578 g of 4,4'-dicyclohexylmethane diisocyanate and 2.9 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 ° C. for 15 hours to obtain an isocyanate- Hexylmethanecarbodiimide (polymerization degree = 4) was obtained. Then, a mixture of 48.5 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 and 104.0 g of N-N 'diethyl isopropanolamine (mixing molar ratio = 1: 1) was added to the obtained isocyanate-terminated dicyclohexylmethanecarbodiimide. 9) was added and reacted at 150 ° C for 5 hours. After the reaction, the mixture was cooled to 80 DEG C and 979 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of a milky white colored carbodiimide compound (d-10).

(Reference Example 24)

The water dispersion of the carbodiimide compound (d-11)

As a carbodiimide compound other than dicyclohexylmethanecarbodiimide compound, NISSHINBO CHEMICAL INC. "CARBODILITE" (registered trademark) V04 (solid content concentration: 40% by weight) was used.

(Reference Example 25)

The water dispersion of the carbodiimide compound (d-12)

An isophorone carbodiimide compound represented by the formula (23) and the formula (17) which does not contain a dicyclohexylmethanecarbodiimide compound was obtained by the following synthesis method.

594 g of isophorone diisocyanate and 2.9 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 ° C for 10 hours to obtain an isocyanate-terminated isophorone carbodiimide ). Then 588.8 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 was added to the obtained isocyanate-terminated isophorone carbodiimide, and the mixture was reacted at 150 DEG C for about 5 hours. After the reaction, the mixture was cooled to 50 캜, and 1633 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of light yellow transparent carbodiimide compound (d-12).

(Reference Example 26)

The water dispersion of the carbodiimide compound (d-13)

A tetramethylxsilylene carbodiimide compound represented by the formula (24) and the formula (17) not containing the dicyclohexylmethanecarbodiimide compound was obtained by the following synthesis method.

584 g of m-tetramethyl xylylene diisocyanate and 11.7 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were reacted at 180 DEG C for 20 hours to obtain an isocyanate-terminated tetramethyl xylylene Carbodiimide (polymerization degree = 4) was obtained. Subsequently, 526.8 g of poly (ethylene oxide) monomethyl ether having a degree of polymerization (p) = 12 was added to the obtained isocyanate-terminated tetramethyl xylylene carbodiimide, and the mixture was reacted at 150 ° C for 6 hours. After the reaction, the solution was cooled to 50 ° C and 1558 g of distilled water was gradually added to obtain an aqueous dispersion (solid concentration: 40% by weight) of a yellowish brown transparent carbodiimide compound (d-13).

(Example 1)

The coating composition was prepared as follows.

Water dispersion of acrylic urethane copolymer resin (a): "Sanaron" WG-658 (solid content concentration: 30% by weight) manufactured by SANANOGO SEIKA KAGAKU Co.,

Water dispersion of polyester resin (b): polyester resin (b-1) (solid concentration: 15% by weight)

ELASTRON 占 E-37 (solid concentration: 28% by weight) manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD., An aqueous dispersion of isocyanate compound (c)

An aqueous dispersion of dicyclohexylmethanecarbodiimide compound (d): dicyclohexylmethanecarbodiimide compound (d-1) (solid concentration: 40% by weight)

Aqueous solvent (f): pure water

(A) / (d) = 15/85/10/30, and the solid content concentration of the coating composition is 8.5% by weight (F) were mixed to adjust the concentration. The resin composition in the coating composition at this time is shown in Table 1-1.

Subsequently, the PET pellets (intrinsic viscosity: 0.63 dl / g) substantially free from particles were thoroughly vacuum-dried and then fed to an extruder and melted at 285 DEG C, compressed into a sheet form from a tee- Was wound around a mirror casting drum having a surface temperature of 25 占 폚 to be cooled and solidified. The unstretched film was heated to 90 DEG C and stretched 3.4 times in the machine direction to obtain a uniaxially stretched film (B film). This film was subjected to a corona discharge treatment in air.

Subsequently, a coating composition whose concentration was adjusted in an aqueous solvent was applied to the corona discharge treated surface of the uniaxially stretched film using a bar coating. Both ends in the width direction of the uniaxially stretched film coated with the coating composition adjusted to the concentration in the aqueous solvent were gripped with clips and guided to a preheating zone, and the atmosphere temperature was set to 75 캜. Subsequently, the atmosphere temperature was elevated to 110 캜 , And then the coating composition was adjusted to an ambient temperature of 90 占 폚 and adjusted to an aqueous solvent to form a resin layer (X). Subsequently, the laminate was stretched 3.5 times in the width direction continuously in a heating zone (stretching zone) at 120 ° C, followed by heat treatment in a heat treatment zone (heat fixing zone) at 230 ° C for 20 seconds to complete crystal orientation A film was obtained. The thickness of the PET film in the obtained laminated polyester film was 100 탆.

Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. Low haze, excellent transparency, excellent initial adhesion with the hard coat layer and adhesion to anti-wet heat, and a small change in reflectance (? R) before and after the self-toughening test showed good resistance to mastic adhesion, heat resistance, transparency and visibility .

(Examples 2 to 3)

A laminated polyester film was obtained in the same manner as in Example 1 except that the following melamine compound (e) was used and the solid content ratio of (e) was changed to the values shown in Table 1-1. Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. The content of the melamine compound as compared with Example 1 decreased the reflectance change amount? R before and after the mercury-free treatment test, and thus showed excellent resistance to intrinsic coercive force and excellent equivalent transparency, initial adhesive property, anti- Visibility.

NIKALAC (registered trademark) MW12LF (solid content concentration: 71% by weight) manufactured by SANWA CHEMICAL CO., LTD., An aqueous dispersion of the melamine compound (e)

(Example 4)

A laminated polyester film was obtained in the same manner as in Example 3 except that the weight ratio of solids of the melamine compound (e) was changed to the values shown in Table 1-1. Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. The initial haze was slightly higher, the reflectance change amount (? R) before and after the mercury treatment test, the dispersion index slightly increased, and the transparency and the adhesion resistance were slightly lowered, although the content of the melamine compound (e) And exhibited equivalent initial adhesion, anti-wet heat adhesion, heat-resistant water transparency, and visibility.

(Example 5)

A laminated polyester film was obtained in the same manner as in Example 3 except that the polyester resin (b-2) was used as the polyester compound (b). Properties and other properties of the obtained laminated polyester film are shown in Table 2-1.

(B-2) having a small content of aromatic dicarboxylic acid component containing a sulfonic acid metal base was used as compared with Example 3, the initial haze was slightly higher, and the reflectance change amount (? R) before and after the self- The dispersion index slightly increased and the transparency, the mastic adhesion and the water resistance to water resistance were slightly lowered. However, the initial dispersibility, the initial adhesion, the anti-wet heat adhesion and the visibility were the same.

(Examples 6 to 7)

A polyester film was produced in the same manner as in Example 3 except that the polyester resin (b-3) (Example 6) and the polyester resin (b-4) (Example 7) were used as the polyester compound (b) ≪ / RTI > Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. By using a polyester resin having a large content of an aromatic dicarboxylic acid component containing a sulfonic acid metal base as compared with Example 3, the initial haze was slightly lower and the reflectance change amount? R before and after the blackening treatment test was equivalent, Heat-resistant adhesive property, mastic adhesion, heat-resistant water transparency, and visibility, which are equivalent to each other.

(Example 8)

A laminated polyester film was obtained in the same manner as in Example 3 except that the polyester resin (b-5) was used as the polyester compound (b). Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. The use of a polyester resin containing a large amount of an aromatic dicarboxylic acid component containing a sulfonic acid metal base as compared with Example 3 resulted in a slight increase in initial haze, a change in reflectance (? R) before and after the self- Transparency, visibility, initial adhesion, mastic adhesion, and heat resistance water transparency were somewhat inferior, but they were good.

(Example 9)

A laminated polyester film was obtained in the same manner as in Example 3 except that the polyester resin (b-6) was used as the polyester compound (b). Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. Using a polyester resin containing no aromatic dicarboxylic acid component containing a sulfonic acid metal base as compared with Example 3, the initial haze was slightly higher, the reflectance change amount (? R) before and after the blackening treatment test, and the dispersion index became larger Transparency, visibility, initial adhesion, mastic adhesion, and heat resistance water transparency were somewhat inferior, but they were good.

(Examples 10 to 11)

A polyester film was produced in the same manner as in Example 3 except that the polyester resin (b-7) (Example 10) and the polyester resin (b-8) (Example 11) were used as the polyester compound (b) ≪ / RTI >

Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. Even when a polyester resin having a different skeleton of bisphenol S was used as compared with Example 3, the reflectance change amount? R before and after the blush treatment test was small and excellent equivalent initial adhesion, anti-wet heat adhesion, Heat water transparency, and visibility.

(Example 12)

A laminated polyester film was obtained in the same manner as in Example 3 except that the solid content ratio of the isocyanate compound (c) was changed to the values shown in the table. Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. Reduction of the content of the isocyanate compound (c) in Example 3 slightly increased the reflectance change amount? R before and after the self-abrasion treatment test, resulting in a slight decrease in initial adhesion, anti-wet heat bonding property, , The same transparency and visibility.

(Examples 13 to 14)

A laminated polyester film was obtained in the same manner as in Example 3 except that the solid content ratio of the isocyanate compound (c) was changed to the values shown in the table. Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. By increasing the content of the isocyanate compound (c) as compared with Example 3, the same transparency, excellent initial adhesion, anti-wet heat adhesion, anti-magnetic adhesion, heat water transparency and visibility were exhibited.

(Examples 15 to 16)

A laminated polyester film was obtained in the same manner as in Example 3, except that the solid content ratio by weight of the dicyclohexylmethanecarbodiimide compound (d) was changed to the values shown in the table. Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. By reducing the content of the dicyclohexylmethanecarbodiimide compound (d) as compared with Example 3, the reflectance change amount? R slightly increased before and after the mercury treatment test, and the initial adhesion, anti-wet heat adhesion and anti- Although slightly deteriorated, it was satisfactory and exhibited the same transparency, visibility, and heat-resistant water transparency.

(Example 17)

A laminated polyester film was obtained in the same manner as in Example 3 except that the solid content ratio of the dicyclohexylmethanecarbodiimide compound (d) was changed to the values shown in Table 1-1. Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. The initial adhesion, the anti-wet heat adhesion, the anti-magnetic adhesion, the visibility, and the heat resistance water transparency were shown by increasing the content of the dicyclohexylmethanecarbodiimide compound (d) as compared with Example 3.

(Examples 18 to 26)

(Example 18), dicyclohexylmethanecarbodiimide compound (d-3) (Example 19), dicyclohexylmethanecarbodiimide compound (d-2) (Example 20), dicyclohexylmethanecarbodiimide compound (d-5) (Example 21), dicyclohexylmethanecarbodiimide compound (d-4) (Example 22), dicyclohexylmethanecarbodiimide compound (d-7) (Example 23), dicyclohexylmethanecarbodiimide compound (d-8) (Example 24), dicyclohexylmethanecarboxylic acid A laminated polyester film was obtained in the same manner as in Example 3 except that the dodecylhexylmethane carbodiimide compound (d-10) (Example 26) was used instead of the dodecylhexylmethane carbodiimide compound (d-9) (Example 25) . Properties and other properties of the obtained laminated polyester film are shown in Table 2-1. The dicyclohexylmethanecarbodiimide compound (d-2 to d-10) having a terminal structure and a different degree of polymerization as compared with Example 3 has the same transparency, initial adhesion, anti-wet heat adhesion, Visibility, and water resistance.

(Examples 27 to 28)

A laminated polyester film was obtained in the same manner as in Example 3, except that the solid content ratio of the acrylic urethane copolymer resin (a) and the polyester resin (b) was changed to the values shown in Table 1-2. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. (A) / polyester resin (b) = 40/60 (Example 27), acrylic urethane copolymer resin (a) / polyester resin (b) = 30/70 (Example 28), the reflectance change amount (? R) before and after the self-abrasion treatment test, the dispersion index slightly increased, the reflectivity slightly decreased, and the haze slightly increased. In addition, the resistance to mabi adhesion and the visibility were slightly lowered, but it was satisfactory and exhibited the same initial adhesion, anti-wet heat adhesion, and heat resistance water transparency.

(Example 29)

A laminated polyester film was obtained in the same manner as in Example 3, except that the solid content ratio of the acrylic urethane copolymer resin (a) and the polyester resin (b) was changed to the values shown in Table 1-2. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. Even when the acrylic urethane copolymer resin (a) / the polyester resin (b) = 20/80 as compared with Example 3, the reflectance change amount? R slightly increased before and after the mercury treatment test, Adhesiveness, anti-wet heat adhesion, anti-self-adhesive property, heat resistance water transparency, and visibility.

(Example 30)

A laminated polyester film was obtained in the same manner as in Example 3, except that the solid content ratio of the acrylic urethane copolymer resin (a) and the polyester resin (b) was changed to the values shown in Table 1-2. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. Compared with Example 3, the dispersibility of the acrylic urethane copolymer resin (a) / polyester resin (b) = 5/95 was slightly reduced, resulting in a slight decrease in haze, a slight increase in reflectivity, and good transparency. In addition, since the reflectance change amount? R slightly increased before and after the self-abrasion treatment test, the initial adhesion, anti-wet heat adhesion, anti-magnetic adhesion, heat resistance water transparency and visibility decreased slightly.

(Example 31)

A laminated polyester film was obtained in the same manner as in Example 3, except that the solid content ratio of the isocyanate compound (c) was adjusted to the values shown in Table 1-2. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. Since the content of the isocyanate compound (c) was reduced as compared with Example 3, the transparency and visibility were excellent, and the reflectance change amount? R slightly increased before and after the self-abrasion treatment test. Although the transparency of the water resistance and water resistance was slightly lowered, it was good.

(Example 32)

A laminated polyester film was obtained in the same manner as in Example 3, except that the solid content ratio of the isocyanate compound (c) was adjusted to the values shown in Table 1-2. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. Compared with Example 3, the haze was slightly increased by increasing the content of the isocyanate compound (c), and the transparency was slightly lowered. In addition, since the reflectance change amounts? R before and after the self-extinguishing treatment test were equivalent, the same initial adhesion, anti-wet heat adhesion, anti-magnetic adhesion and heat resistance water transparency were exhibited.

(Example 33)

A laminated polyester film was obtained in the same manner as in Example 3, except that the solid content ratio of the dicyclohexylmethanecarbodiimide compound (d) was adjusted to the values shown in Table 1-2. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. Since the content of the dicyclohexylmethanecarbodiimide compound (d) was decreased as compared with Example 3, the reflectance change amount? R slightly increased before and after the self-abrasion treatment test, so that the initial adhesion, wet heat resistance, , The water resistance of the water of heat resistance was slightly lowered, but it was good.

(Example 34)

A laminated polyester film was obtained in the same manner as in Example 3, except that the solid content ratio of the dicyclohexylmethanecarbodiimide compound (d) was adjusted to the values shown in Table 1-2. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. Compared with Example 3, the haze was slightly increased by increasing the content of the dicyclohexylmethanecarbodiimide compound (d), and the transparency was slightly lowered, but it was good. In addition, since the reflectance change amounts? R before and after the self-extinguishing treatment test were equivalent, the same initial adhesion, anti-wet heat adhesion, anti-magnetic adhesion and heat resistance water transparency were exhibited.

(Example 35)

A laminated polyester film was obtained in the same manner as in Example 3 except that the weight ratio of solids of the melamine compound (e) was adjusted to the values shown in Table 1-2. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. The content of the melamine compound (e) was smaller than that of Example 3, and the same excellent transparency, initial adhesion and anti-wet heat adhesion were exhibited. In addition, since the reflectance change amount? R slightly increased before and after the self-abrasion treatment test, the mabi adhesion and the heat resistance water transparency were slightly lowered, but were good.

(Example 36)

A laminated polyester film was obtained in the same manner as in Example 3 except that the weight ratio of solids of the melamine compound (e) was adjusted to the values shown in Table 1-2. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. Compared with Example 3, the content of the melamine compound (e) was increased, so that the dispersion index was slightly increased and the haze was slightly increased. Further, the reflectance change amount? R before and after the self-abrasion treatment test was slightly increased and the self-adhesive strength was slightly lowered, but this was good.

(Example 37)

A laminated polyester film was obtained in the same manner as in Example 3 except that the polyester resin (b-9) was used as the polyester compound (b). Properties and the like of the obtained laminated polyester film are shown in Table 2-2. By using a polyester resin having a skeleton of bisphenol A in comparison with Example 3, the initial haze was slightly higher, the reflectance change amount (? R) before and after the mercury treatment test, the dispersion index was slightly and the reflectance was small, and transparency, visibility, The adhesive properties were slightly lowered, but the initial adhesive properties and the anti-wet heat adhesion properties were equivalent.

(Example 38)

A laminated polyester film was obtained in the same manner as in Example 3 except that the polyester resin (b-10) was used as the polyester compound (b). Properties and the like of the obtained laminated polyester film are shown in Table 2-2. By using a polyester resin having a skeleton of bisphenol A in comparison with Example 3, the initial haze was slightly higher, the reflectance change amount (? R) before and after the mercury treatment test, and the dispersion index were slightly higher and the reflectance was lowered, and transparency, visibility, The adhesive properties were slightly lowered, but the initial adhesive properties and the anti-wet heat adhesion properties were equivalent.

(Example 39)

A laminated polyester film was obtained in the same manner as in Example 1 except that the polyester resin (b-2) was used as the polyester compound (b). Properties and the like of the obtained laminated polyester film are shown in Table 2-2.

By using the polyester resin (b-2) having a small content of the aromatic dicarboxylic acid component containing a sulfonic acid metal base as compared with Example 1, the initial haze was slightly higher and the dispersion index slightly increased, , The heat resistance water transparency was slightly lowered, but it was good, and the reflectance change amount (? R) before and after the blush treatment test was excellent, showing the same initial adhesion, anti-wet heat adhesion and visibility.

(Examples 40 to 42)

Except for using the polyester resin (b-2) as the polyester compound (b) and changing the solid content ratio of the acrylic urethane copolymer resin (a) and the polyester resin (b) to the values shown in Table 1-2 A laminated polyester film was obtained in the same manner as in Example 3. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. (A) / polyester resin (b) was used in place of the polyester resin (b-2) having a small content of the aromatic dicarboxylic acid component containing a sulfonic acid metal base, (A) / polyester resin (b) = 40/60 (Example 40), acrylic urethane copolymer resin (a) / polyester resin (b) = 30/70 = 20/80 (Example 42), the dispersion index slightly increased, the reflectance slightly decreased, and the haze slightly increased, but this was good. Further, the reflectance change amount? R before and after the self-abrasion treatment test was slightly increased, and the self-bonding strength and visibility were slightly lowered, but it was satisfactory and exhibited equivalent initial adhesion, anti-wet heat adhesion and heat resistance water resistance.

(Example 43)

A laminated polyester film was obtained in the same manner as in Example 3 except that the film thickness of the resin layer (X) was changed. Properties and the like of the obtained laminated polyester film are shown in Table 2-2. By reducing the film thickness of the resin layer (X) as compared with Example 3, the reflectance was lowered and the visibility was slightly lowered. However, the initial adhesiveness, the anti-wet heat adhesion, the anti- Respectively.

(Comparative Example 1)

A laminated polyester film was obtained in the same manner as in Example 1 except that the weight ratio of solids in (a) to (e) was adjusted to the values shown in Table 1-3. Properties and the like of the obtained laminated polyester film are shown in Table 2-3. The laminated polyester film of Comparative Example 1 did not contain an acryl-urethane copolymer resin and exhibited the same excellent transparency as in Example 1, but the reflectance change amount (ΔR) before and after the self-abrasion treatment test, the initial adhesive property, And the performance was poor in terms of adhesion, mastic adhesion, and visibility.

(Comparative Examples 2 to 3)

A laminated polyester film was obtained in the same manner as in Example 3 except that the weight ratio of solids in (a) to (e) was adjusted to the values shown in Table 1-3. Properties and the like of the obtained laminated polyester film are shown in Table 2-3. The laminated polyester films of Comparative Examples 2 and 3 did not contain the polyester resin (b) having a naphthalene skeleton, and thus the reflectance change amount (DELTA R) before and after the excellent masticatory treatment test as compared with Example 3, transparency, Heat resistance, anti-wet heat adhesion, and anti-magnetic adhesion, but the performance was poor in visibility.

(Comparative Examples 4 to 5)

A laminated polyester film was obtained in the same manner as in Example 3 except that the weight ratio of solids in (a) to (e) was adjusted to the values shown in the table. Properties and the like of the obtained laminated polyester film are shown in Table 2-3.

Since the laminated polyester film of Comparative Example 4 did not contain the isocyanate compound (c), it exhibited the same excellent transparency and good visibility as compared with Example 3, but the reflectance change amount (? R) before and after the self- And the performance was poor in terms of adhesion and resistance to abrasion.

In addition, since the laminated polyester film of Comparative Example 5 did not contain the dicyclohexylmethanecarbodiimide compound (d), it showed the same excellent transparency and good visibility as in Example 3, but the reflectance before and after the mercury treatment test The performance was inferior in the change amount? R, initial adhesion, anti-wet heat adhesion, anti-magnetic adhesion, and heat resistance water transparency.

(Comparative Examples 6 to 9)

A laminated polyester film was obtained in the same manner as in Example 3 except that the solid content ratio of the acrylic urethane copolymer resin (a) and the polyester resin (b) was changed to the values shown in the table. Properties and the like of the obtained laminated polyester film are shown in Table 2-3.

The laminated polyester film of Comparative Example 6 had a dispersion index of 7 and a slight increase in haze as a result of the acrylic urethane copolymer resin (a) / polyester resin (b) = 50/50 as compared with Example 3, It became smaller. In addition, it exhibited excellent initial adhesion and anti-wet heat adhesion properties of the same, but the reflectance change amount (? R) before and after the self-toughening treatment test, the self-adhesive adhesion, the heat resistance water transparency and the visibility were poor.

When the acryl-urethane copolymer resin (a) / polyester resin (b) = 60/40 as compared with Example 3, the dispersion index of the laminated polyester film of Comparative Example 7 was increased to 10, the reflectance was decreased and the haze was increased And the transparency became poor. In addition, while showing the same initial adhesion and anti-wet heat adhesion properties, the reflectance change amount (? R) before and after the self-toughening treatment test, mabi adhesion, heat-resistant water transparency, and visibility were poor.

Compared with Example 3, the laminated polyester film of Comparative Example 8 had a dispersion index of 15 as the acrylic urethane copolymer resin (a) / polyester resin (b) = 80/20, lowering the reflectance and increasing the haze And the transparency became poor. In addition, while showing the same initial adhesion and anti-wet heat adhesion properties, the reflectance change amount (? R) before and after the self-toughening treatment test, the resistance to magnetic resistance, the heat resistance water transparency and the visibility were poor.

When the acryl-urethane copolymer resin (a) / the polyester resin (b) = 90/10, the dispersion index of the laminated polyester film of Comparative Example 9 was increased to 20, the reflectance was lowered, the haze was increased, . In addition, while showing the same initial adhesion and anti-wet heat adhesion properties, the reflectance change amount (? R) before and after the self-toughening treatment test, mabi adhesion, heat-resistant water transparency, and visibility were poor.

(Comparative Examples 10 to 12)

(Comparative Example 10), a carbodiimide compound (d-12) (Comparative Example 11), a carbodiimide compound (d-13) as a dicyclohexylmethanecarbodiimide compound (d) ) (Comparative Example 12) was used in place of the polyester film obtained in Example 1, a laminated polyester film was obtained. Properties and the like of the obtained laminated polyester film are shown in Table 2-3. The laminated polyester films of Comparative Examples 10 to 12 were obtained by using the carbodiimide compounds (d-11 to d-13) other than the dicyclohexylmethanecarbodiimide compound so that the film haze change amount (DELTA Hz) before and after the self- (Comparative example 10) and 6.4% (comparative examples 11 and 12), the transparency of the hot water was inferior and the transparency, the initial adhesion, the anti-wet heat adhesion and the visibility were comparable to those of Example 3. However, The reflectance change amount (? R) before and after the self-extinguishing treatment test, and the self-adhesive property were inferior in performance.

The present invention relates to a laminated polyester film having a resin layer which is excellent not only in initial adhesion but also excellent in anti-wet heat adhesion, anti-magnetic adhesion and heat resistance water transparency and excellent in suppression of interference fringes when a hard coating layer is laminated And can be used as an adhesive film for optical applications for various display applications, an adhesive film for hard coating films used for industrial and construction materials such as window glass for automobiles and buildings, and adhesiveness to various laminates such as inks This excellent adhesive film can be used.

1: Resin layer (X) 2: Polyester film
3: X direction 4: Y direction
5: Z direction

Claims (9)

On at least one side of the polyester film
As a laminated polyester film having a resin layer (X)
The resin layer (X)
The acrylic urethane copolymer resin (a)
A polyester resin (b) having a naphthalene skeleton,
The isocyanate compound (c)
And a dicyclohexylmethanecarbodiimide compound (d), wherein the dicyclohexylmethanecarbodiimide compound (d)
Wherein a change amount (? R) of the spectral reflectance before and after the resistivity treatment on the side of the resin layer (X) is 0% or more and 2% or less. The method according to claim 1,
The dispersion index of the agglomerate containing the acrylic-urethane copolymer resin (a) of the resin layer (X) is 5 or less,
Also, the ratio of the acrylic urethane copolymer resin (a) in the coating composition is 3% by weight or more. 3. The method according to claim 1 or 2,
And the minimum value of the spectral reflectance in the wavelength range of 450 nm or more and 650 nm or less on the side of the resin layer (X) is 4.5% or more and 6.0% or less. 4. The method according to any one of claims 1 to 3,
The dicyclohexylmethanecarbodiimide compound (d) is a dicyclohexylmethanecarbodiimide compound represented by the following formula (1).

Wherein n represents an integer of 1 or more and 10 or less.
R ¹ and R ² each represent any one of the following formulas (2) to (4).
R ¹ and R ² may be the same or different,

Wherein p is an integer of 4 or more and 30 or less and R < ³ > is an alkyl group of 1 to 5 carbon atoms.

Wherein q is an integer of 1 or more and 3 or less, R ⁴ is an alkyl group having 1 to ⁵ carbon atoms or a phenyl group, and R ⁵ is an alkyl group having 1 to ⁵ carbon atoms.

[Wherein, R ⁶ is an alkyl group having 1 to 5 carbon atoms, R ⁷ represents hydrogen or an alkyl group having 1 to 5 carbon atoms; 5. The method according to any one of claims 1 to 4,
Wherein the polyester resin (b) is a copolymerized polyester resin containing an aromatic dicarboxylic acid component containing a sulfonic acid metal base in an amount of 1 to 30 mol% based on the total dicarboxylic acid component of the polyester. Ester film. 6. The method according to any one of claims 1 to 5,
The polyester resin (b) comprises a diol component represented by the following formula (5).

[Wherein, X ^1, X ^2: - it shows a _{(C l H 2l O) m} -H (l = 2 or more than 4, m = 1 or more integer of not more than 15); 7. The method according to any one of claims 1 to 6,
Wherein the solid content weight ratio of the acrylic urethane copolymer resin (a) and the polyester resin (b) in the coating composition is 40/60 to 5/95. 8. The method of claim 7,
When the total weight of the solid content of the acrylic urethane copolymer resin (a) and the polyester resin (b) in the coating composition is 100 parts by weight,
Isocyanate compound (c) in an amount of 3 to 20 parts by weight,
Wherein the dicyclohexylmethanecarbodiimide compound (d) is contained in an amount of 10 to 40 parts by weight in terms of solid content. 9. The method of claim 8,
Wherein the coating composition further comprises 5 to 30 parts by weight of a melamine compound (e).

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