JP5720218B2 - Polyester film for insert molding - Google Patents

Description

  The present invention relates to a polyester film for insert molding. In particular, the present invention relates to a polyester film for insert molding that has a good appearance when used as an alternative to plating and has excellent decorating properties.

  Various materials are used for manufacturing molded bodies such as cover members. For example, the exterior surface of a molded body such as an automobile part such as a molding or a pillar is used by being coated with a plating or resin material. By the way, in the manufacture of exterior parts and interior parts of automobiles, a method of performing coating and plating after surface treatment has been generally adopted, but recently, decorative films have been molded as substitutes for painting and plating. A method of applying to the cover has been proposed (Patent Document 1).

  As such a resin sheet material for molding, a polyvinyl chloride film has been conventionally used, but there are problems in terms of environmental suitability such as generation of toxic gas when the film burns and bleed out of a plasticizer. . Thus, unstretched sheets made of polyester, polycarbonate, or acrylic resin have been used in a wide range of fields as materials having excellent environmental suitability. For example, as in Patent Document 2, a molding polyester film having characteristics excellent in moldability has been proposed.

JP 2007-297469 A JP 2008-30475 A

  The plating substitute decorative film made of polyester is provided with an easy-adhesion layer on the film surface in order to exhibit adhesion with various functional layers such as a decorative layer. As the plating substitute decorative film, a relatively thin film is often used, and wrinkles and streaks are likely to occur when the film is rolled up. Then, the slipperiness required for a production process or a process process is provided by adding particle | grains to a film surface, especially an easily bonding layer, and providing a concavo-convex structure on the surface.

  On the other hand, when a mirror-like metallic luster treatment is performed by metal vapor deposition or the like as an alternative to metal plating, it is desirable that the surface be smooth in order to obtain a high-quality appearance. However, the surface feeling may be impaired by having irregularities on the film surface. In particular, a film used as a substitute for plating has a relatively soft waist feeling excellent in moldability, and a film having a relatively thin film thickness is used. Therefore, when it rolls up in roll shape, the film surface tends to deform | transform by press. For example, if a film with a relatively thin film rolled up is used, even if it is a fine uneven structure that cannot be visually recognized by the film itself, reflection due to the fine uneven structure can be achieved by applying a metallic luster treatment. Due to the scattering of light, the mapping onto the mirror surface may be distorted.

  An object of the present invention is to solve the above problems. That is, an object of the present invention is to provide a molding polyester film having a good specular appearance when used as an alternative to plating while having moldability suitable for insert molding. In addition to the above, it is another object of the present invention to provide a polyester film for insert molding that is excellent in adhesiveness even in a humid heat environment.

The molding polyester film of the present invention that can solve the above-described problems has the following configuration.
1st invention has an easily bonding layer in at least one surface of a polyester film, and a polyester film consists of copolyester, or copolyester and homopolyester, The said easily bonding layer is a particle size distribution (d75 / d25). Of 1.1 to 1.5 and an average particle diameter d of 0.04 to 1.2 μm is included as an essential particle, and the average particle diameter d of the particle A and the easy adhesion layer The ratio (d / t) to the thickness t is 5 or more and 100 or less, the thickness of the polyester film is 15 to 100 μm, and the wavelength is 0.1 mm to 0 measured using a wave scanning device on the surface of the easy adhesion layer of the film. This is a polyester film for insert molding having a reflection intensity (Wa) in the region of 3 mm of 4.0 or less.
The second invention, the adhesive layer is a polyester resin, a polyurethane resin, or, which is the polyester film for insert molding comprising at least one binder resins of acrylic resin.
In a third aspect of the invention, the easily adhesive layer includes a polyester resin and a polyurethane resin, and the polyester resin includes a polymerizable unsaturated monomer including an acid anhydride having at least one double bond in the hydrophobic copolyester resin. The polyester film for insert molding, which is a polyester-based graft copolymer grafted with a monomer.
4th invention is the said polyester film for insert molding whose said polyurethane resin is a polycarbonate-type polyurethane resin.
5th invention contains 0.01-3 mass% of said particle | grains A with respect to all resin of the said easily bonding layer , the haze of the said film is 2.0% or less, and the static friction coefficient of easily bonding layer surfaces is 0. .9 or less, the polyester film for insert molding having a coefficient of dynamic friction between the easy-adhesion layer surfaces of 0.8 or less and an air escape index of 200 seconds or less.
6th invention is a decorating film for plating substitute which has a metal vapor deposition layer in one side of the polyester film for insert molding.

  The polyester film for insert molding of the present invention is excellent in good moldability and surface smoothness. Therefore, it is suitable for forming a mirror-like decorative layer excellent in surface feeling. The polyester film for insert molding of the present invention is molded simultaneously with a molding base material in a decorative molding member such as an interior or exterior decoration material for automobiles, a home appliance membrane switch, a base material for a mobile phone, or a construction material member. By doing so, it can be suitably used in a plating alternative treatment method.

It is explanatory drawing which shows the cross section of the apparatus which measures the air escape speed of a film.

(Base polyester film)
The polyester film used as a base material consists of copolymer polyester or copolymer polyester and homopolyester from the viewpoint of moldability.

  Examples of the copolyester include (a) a copolyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol or alicyclic glycol, or (b) terephthalic acid and isophthalic acid. A copolyester composed of an aromatic dicarboxylic acid component containing an acid and a glycol component containing ethylene glycol is preferred. Moreover, it is preferable from the point which improves the moldability that the polyester which comprises a biaxially-oriented polyester film contains a 1, 3- propanediol unit or a 1, 4- butanediol unit as a glycol component further. In the case of (a) above, the copolymerization polyester used in the present invention is preferably added with a copolymerization component so that the proportion of ethylene glycol in the total glycol component is 20 mol% to 95 mol%. The lower limit of the proportion of ethylene glycol in the total glycol component is preferably 30 mol%, more preferably 40 mol%, and the upper limit is preferably 90 mol%, more preferably 80 mol%, still more preferably. Is 70 mol%. In the case of the above (b), the copolymerized polyester used in the present invention is added with a copolymer component such that the proportion of terephthalic acid in the total aromatic dicarboxylic acid component is 50 mol% to 95 mol%. It is preferable. The lower limit of the proportion of terephthalic acid in the total aromatic dicarboxylic acid component is preferably 60 mol%, more preferably 70 mol%, and the upper limit is preferably 90 mol%.

  As the film raw material, any method of copolymerized polyester alone, a blend of one or more types of homopolyester or copolymerized polyester, or a combination of homopolyester and copolymerized polyester is possible. Among these, the blending method is preferable from the viewpoint of suppressing the lowering of the melting point.

  When using a copolymer polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol or alicyclic glycol as the copolymer polyester, the aromatic dicarboxylic acid component is Terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or ester-forming derivatives thereof are suitable, and the amount of terephthalic acid and / or naphthalenedicarboxylic acid component relative to the total dicarboxylic acid component is 70 mol% or more, preferably 85 mol% or more. Particularly preferred is 95 mol% or more, and particularly preferred is 100 mol%.

  Examples of branched aliphatic glycols include neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and the like. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol and tricyclodecane dimethylol.

  Among these, neopentyl glycol and 1,4-cyclohexanedimethanol are particularly preferable. Furthermore, in the present invention, it is a more preferable embodiment that 1,3-propanediol or 1,4-butanediol is used as a copolymerization component in addition to the glycol component. Use of these glycols as a copolymerization component is suitable for imparting the above-mentioned properties, and is also excellent in transparency and heat resistance, and from the viewpoint of improving the adhesion with the adhesion modified layer. Is also preferable.

  When the copolymer polyester is composed of an aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid and a glycol component containing ethylene glycol, the amount of ethylene glycol is based on the total glycol component. It is 70 mol% or more, preferably 85 mol% or more, particularly preferably 95 mol% or more, and particularly preferably 100 mol%. As the glycol component other than ethylene glycol, the above-mentioned branched aliphatic glycol, alicyclic glycol, or diethylene glycol is preferable.

  Examples of the catalyst used for producing the copolymer polyester include alkaline earth metal compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, titanium / silicon composite oxides, and germanium compounds. . Of these, titanium compounds, antimony compounds, germanium compounds, and aluminum compounds are preferred from the viewpoint of catalytic activity.

  When producing the copolymer polyester, it is preferable to add a phosphorus compound as a heat stabilizer. As said phosphorus compound, phosphoric acid, phosphorous acid, etc. are preferable, for example.

  The copolyester preferably has an intrinsic viscosity of 0.50 dl / g or more, more preferably 0.55 dl / g or more, and particularly preferably 0.00 from the viewpoint of moldability, adhesiveness, and film formation stability. 60 dl / g or more. If the intrinsic viscosity is less than 0.50 dl / g, the moldability tends to decrease. In addition, when a filter for removing foreign substances is provided in the melt line, the upper limit of the intrinsic viscosity is preferably 1.0 dl / g from the viewpoint of ejection stability during extrusion of the molten resin.

(Polyester resin used as film raw material)
In the present invention, one or more homopolyesters or copolymerized polyesters are used as film raw materials, and these are blended to form a film, thereby maintaining the same flexibility as when only the copolymerized polyester is used. However, transparency and high melting point (heat resistance) can be realized. In addition, when only a high melting point homopolyester (for example, polyethylene terephthalate) is used, it is possible to realize a melting point (heat resistance) having no flexibility and practical problem while maintaining high transparency.

  In addition, blending at least one or more of the above copolyester and a homopolyester other than polyethylene terephthalate (for example, polytetramethylene terephthalate or polybutylene terephthalate) and using it as a raw material for the polyester-based resin film roll of the present invention Further, it is further preferable from the viewpoint of moldability.

  In the present invention, the film raw material is a polyester resin obtained by blending a copolyester alone or one or more homopolyesters or copolyesters. It is preferable that the polyester-type resin used for this invention contains 5-50 mass% of copolymerization components.

  The melting point of the polyester resin composition constituting the film is preferably 180 to 250 ° C. from the viewpoint of heat resistance and moldability. By controlling the type and composition of the polymer to be used and the film forming conditions within the range of the melting point, a balance between moldability and finish can be achieved, and a high-quality molded product can be produced economically. Here, the melting point is an endothermic peak temperature at the time of melting, which is detected at the time of primary temperature rise in so-called differential scanning calorimetry (DSC). The melting point was determined by measuring at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.). The lower limit of the melting point is more preferably 190 ° C., further preferably 200 ° C., still more preferably 210 ° C., and particularly preferably 220 ° C. If the melting point is less than 180 ° C, the heat resistance tends to deteriorate. Therefore, it may become a problem when exposed to high temperature during molding or use of a molded product.

  The upper limit of the melting point is preferably higher from the viewpoint of heat resistance, but when the polyethylene terephthalate unit is the main component, the film having a melting point exceeding 250 ° C. tends to deteriorate moldability. In addition, transparency tends to deteriorate. Furthermore, in order to obtain high moldability and transparency, it is preferable to control the upper limit of the melting point to 250 ° C.

  The polyester film of the present invention is preferably a biaxially stretched film. In the present invention, solvent resistance and dimensional stability, which are disadvantages of an unstretched sheet, are improved by molecular orientation by biaxial stretching. That is, it is possible to improve the solvent resistance and heat resistance, which are disadvantages of the unstretched sheet, while maintaining good moldability of the unstretched sheet.

  As a preferred embodiment of the present invention, in order to obtain good transparency and stable workability (especially surface friction characteristics), a film having a multilayer structure and using a polyester layer containing fine particles only in the surface layer is used. You can also. Such a base film has a multilayer structure (a / b / a) in which a surface layer (a layer) containing inert particles is laminated on both sides of a central layer (b layer) by a coextrusion method. It is preferable to use a polyester film. The layers constituting the front and back surface layers may be the same or different, but in order to maintain the flatness of the base film, the polyester resin of the front and back surface layers should have the same configuration. Is desirable. Moreover, for the use which has high transparency, the aspect which does not contain particle | grains in the polyester film used as a base material but has particles only in the easy adhesion layer is preferable. According to this aspect, since the design can be visually recognized even from the opposite surface of the decorative layer, it can be suitably used as a decorative application.

  In the case of integral molding with a molding substrate by insert molding, it is preferable that the film thickness is thinner. The thickness of the film of the present invention is preferably 15 to 100 μm, more preferably 80 μm or less, further preferably 75 μm or less, and still more preferably 60 μm or less. Moreover, the minimum of film thickness is 15 micrometers or more from the point of the intensity | strength as a film, More preferably, it is 20 micrometers or more, More preferably, it is 25 micrometers or more.

  As a scale for evaluating the moldability of the film, there is a stress at 100% elongation (F100). As a reason why F100 is closely related to the moldability of the film, for example, in insert molding, the film may locally expand to 100% or more near the corner of the mold. In a film having a high F100, extremely high stress is partially generated in such a locally stretched portion, and it is considered that the film breaks due to the stress concentration and the formability is lowered. On the other hand, a film having an F100 that is too small has good moldability, but only a very weak tension is generated in a portion that is uniformly stretched, such as a flat portion of a mold. It is thought that proper elongation cannot be obtained.

In the present invention, 100% elongation stress at 100 ° C. (F100 ₁₀₀ ) is used as a physical property related to the moldability corresponding to the temperature at the time of insert molding. In addition, when insert molding is performed using a mold having irregularities and depressions, as a physical property related to moldability when insert molding is performed by lightly following the mold before molding, 100% elongation stress (F100 ₂₅ ) is used.

Regarding the above physical properties, the film of the present invention preferably has a stress at 100% elongation (F100 ₂₅ ) at 25 ° C. of 40 to 300 MPa. The lower limit is preferably 50 MPa, more preferably 60 MPa, and even more preferably more than 70 MPa. The upper limit is preferably 250 MPa, more preferably 200 MPa, and even more preferably 150 MPa. When F100 ₂₅ is less than 40 MPa, when the roll-shaped film is pulled and unwound, the film is stretched or torn, resulting in poor workability. On the other hand, when F100 ₂₅ exceeds 300 MPa, the moldability becomes poor. In particular, when molding is performed using a mold having irregularities and depressions, a film before molding may be followed by lightly following those molds in advance. In such a case, it is difficult to mold the film, and the finished product may have poor design properties.

Moreover, it is preferable that the 100% elongation stress (F100 ₁₀₀ ) at 100 ° C. is 1 to 100 MPa for the films of the present invention. The upper limit of F100 ₁₀₀ is preferably 90 MPa, more preferably 80 MPa, and particularly preferably 70 MPa from the viewpoint of moldability. On the other hand, the lower limit of F100 ₁₀₀ is preferably 5 MPa, more preferably 10 MPa, further preferably 20 MPa, and particularly preferably more than 35 MPa from the viewpoint of elasticity and shape stability when using a molded product.

(Production method)
The polyester film for molding of the present invention is preferably a biaxially oriented laminated polyester obtained by sequential biaxial stretching or simultaneous biaxial stretching. Hereinafter, the most preferred sequential biaxial stretching method will be described.

  First, the raw material pellets are sufficiently vacuum-dried. Next, the polyester sheet is melted at a temperature equal to or higher than the melting point using an extruder, the polyester sheet is extruded from a die by a co-extrusion method, and is closely adhered to a rotary cooling roll to obtain an unstretched polyester film. As a method of closely contacting the rotary cooling roll, a known electrostatic contact method, air knife method, air chamber method, or the like can be used. Moreover, you may cool by blowing air from the opposite surface of a rotary cooling roll as needed. The unstretched polyester film is guided to a roll-type longitudinal stretching machine and heated to 80 to 125 ° C., and then stretched 2.5 to 5.0 times in the longitudinal direction due to the peripheral speed difference of the roll to obtain a uniaxially stretched film. Longitudinal stretching may be carried out in one stage or in multiple stages.

  Thereafter, the uniaxially stretched polyester film was guided to a grip-type lateral stretching machine, heated to 80 to 180 ° C., stretched 2.5 to 5.0 times in the lateral direction, and then heat-set at 200 to 240 ° C. Then, if necessary, it is relaxed by 1 to 10% in the longitudinal direction and / or the transverse direction, and then wound up with a film winder to obtain a biaxially stretched polyester film.

As the step of applying the easy-adhesion layer, any method such as a method of applying before stretching of the film, a method of applying after longitudinal stretching, or a method of applying to the film surface after the orientation treatment is possible. The in-line coating method, which is applied before the completion of the crystal orientation of the material polyester film and then stretched in at least one direction and then completes the crystal orientation of the polyester film, can exhibit the effects of the present invention more remarkably. So is the preferred method

  As a method for providing an easy-adhesion layer, a conventionally used method such as a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, or a reverse roll coating method can be applied.

(Surface shape)
Since the base film of the present invention is used for insert molding, it is excellent in moldability and relatively thin. Therefore, when it rolls up in a roll state, it is easy to produce a deformation | transformation on the film surface by winding pressure. In particular. When a vapor-deposited layer with a metallic luster is provided on the surface of the film and a very high level of mirror surface is applied, even if the surface has a fine surface irregularity that was not visible in the film state, it is reflected on the mirror surface due to scattering by reflected light. Distortion has occurred in this map, and it has been recognized as an appearance defect.

  As a result of intensive studies on the generation mechanism of such distortion of the mapping, it was found that the non-uniformity of the particle shape of the particles added for imparting air release properties is a factor. That is, when the particle shape is non-uniform, local uneven distribution occurs in the fine irregularities on the film surface, and when the film is laminated in a multilayer as a film roll, the uneven distribution of such irregularities is accumulated, and the fineness called orange peel is accumulated. It was found that an uneven film surface uneven structure was produced. The fine concavo-convex structure on the film surface thus formed is finer than the concavo-convex structure expressed as a mat or the like, and has a structure larger than the surface protrusion structure expressed by a three-dimensional surface roughness (SRa) or the like. It was a thing. In other words, the surface of the film itself was invisible, but it was a fine surface irregularity shape that could be visually recognized when a mirror finish was applied. It was recognized that such uneven distribution of uneven shapes due to particles tends to occur when the film has a low sensation, such as a thin film having a thickness of 100 μm or less, and further 80 μm or less.

  The mapping distortion is caused by the fact that the reflection of light differs depending on the uneven structure of the metallic luster surface. The concavo-convex structure on the film surface, which causes mapping distortion, can be evaluated by a microwave scan (manufactured by Gardner) that optically measures a light-dark pattern of wavelengths. In the wave scan, a laser point light source irradiates a laser beam at an angle inclined by 60 ° from a normal to the film surface, and a detector measures reflected light at the same angle opposite to the normal. This apparatus moves the laser point light source over the film surface and scans it, thereby measuring the brightness of the reflected light point by point at a predetermined interval and detecting the optical profile of the film surface. The detected optical profile can be spectrally analyzed through a frequency filter to analyze the surface structure. The characteristic spectrum of this device is as follows. du: wavelength 0.1 mm or less, Wa: wavelength 0.1-0.3 mm, Wb: wavelength 0.3-1 mm, Wc: wavelength 1-3 mm, Wd: wavelength 3-10 mm, We: wavelength 10-30 mm, SW : Wavelength 0.3 to 1.2 mm, LW: Wavelength 1.2 to 12 mm. As a result of intensive studies, the present inventor has found that the reflection intensity (Wa) in the wavelength region of 0.1 to 0.3 mm is a profile resulting from the fine surface uneven structure of the present invention.

  That is, when the film surface of the present invention is measured with a wave scan device, the reflection intensity (Wa) in the wavelength region of 0.1 to 0.3 mm is preferably 4.0 or less, more preferably 3.5 or less, Preferably it is 3.0 or less. The film of the present invention has a smooth reflection on the film surface when it is used as an alternative to plating because the reflection intensity on the film surface is not more than the above upper limit.

(particle)
In order to control the reflection intensity (Wa) in the wavelength range of 0.1 to 0.3 mm on the film surface within the above range, the average particle diameter, particle size distribution, concentration, and the easy-adhesion layer of the particles constituting the easy-adhesion layer It is preferable to control the thickness. Specifically, it is preferable to have the following configuration.

  The easy-adhesion layer of the present invention preferably contains at least particles having a particle size distribution (d75 / d25) of 1.1 to 1.5 and an average particle size of 0.04 to 1.2 μm.

  When the surface of the film is smooth, the air entrained between the films cannot be completely removed when the film is rolled up, and wrinkles are likely to occur in the film derived from the entrained air part. When a film having such a defect is used as a substitute for plating, an appearance defect occurs, and a suitable mirror surface appearance may not be obtained. Such appearance defects are likely to occur when the film has a low sensation, such as a thin film having a thickness of 100 μm or less, and further 80 μm or less. Therefore, it is preferable that the easy-adhesion layer of the present invention contains particles having an average particle size of 0.04 to 1.2 μm. The average particle diameter of the particles is more preferably 0.05 to 1.0 μm, and still more preferably 0.06 to 0.90 μm. When the lower limit of the average particle diameter is not less than the above, effective protrusions are formed on the surface of the easy-adhesion layer, and a film having no appearance defect can be suitably obtained by improving air bleeding. Further, when the average particle size of the particles is not more than the above upper limit, a smooth surface feel can be obtained. The average particle diameter of the particles can be measured from a scanning microscope observation image of the surface of the film easy-adhesion layer or an electron microscopic image of the film easy-adhesion layer section, and can also be obtained by a Coulter counter method. Especially, it can obtain | require suitably by measuring the particle diameter of the particle | grains exposed on the surface of an easily bonding layer from the scanning microscope observation image of the film easily bonding layer surface.

  When the thickness of the easy adhesion layer is t (μm) and the average particle diameter of the particles is d (μm), the ratio (d / t) is 1 to 100, preferably 2 to 50, more preferably It is preferable that it is 5-20. When (d / t) is equal to or more than the above lower limit, surface protrusions effective for air escape are easily formed on the surface of the easy-adhesion layer. Moreover, when (d / t) is less than or equal to the above upper limit, the particles are less likely to fall off (dropping of the particles from the easy-adhesion layer), and a stable friction coefficient is easily obtained during processing.

  From the above relationship, the thickness of the easy-adhesion layer of the present invention is specifically preferably 0.02 to 0.50 μm, more preferably 0.03 to 0.10 μm, and still more preferably 0.04 to 0.08 μm. is there.

  Since the easy-adhesion layer of the present invention has the above-described configuration, it has good air escape properties. Specifically, the air escape index measured by the method described below is preferably 350 seconds or less, more preferably less than 200 seconds, and even more preferably less than 50 seconds. Since the air escape index is less than or equal to the above upper limit, air escape is good even when the film of the present invention is wound on a roll in the film forming step, and even when stored as a film roll, wrinkles are less likely to occur. On the other hand, the lower limit of the air escape index is preferably 30 seconds or more, and more preferably 35 seconds or more. When the air escape index is equal to or more than the above lower limit, powder falling of the particle protrusions is more preferably suppressed.

  It is desirable that the film of the present invention has good appearance when the vapor-deposited decorative surface is the back surface. Therefore, the content of the particles in the easy adhesion layer is preferably 0.01 to 3% by mass, more preferably 0.05 to 2.5% by mass, and still more preferably 0.10 to 2.0% by mass. . When the particle content is not less than the above lower limit, the air release property when winding as a film roll can be maintained well. Moreover, when the particle content is not more than the above upper limit, the powder protrusion of the particle protrusions is more preferably suppressed, and suitable transparency is easily obtained.

  Since the particle | grain density | concentration in an easily bonding layer is the said range, it has the high transparency preferable for the insert molding of this invention. Specifically, the haze of the film of the present invention is preferably 2.0% or less, more preferably 1.5% or less, still more preferably 1.2% or less, and even more preferably 1.0. % Or less, particularly preferably 0.8% or less. Since the film of the present invention has good transparency as described above, a good mirror-like surface appearance can be obtained even if, for example, a vapor deposition layer is provided on the back side of the film and is integrally molded with the substrate. In addition, in order to make the transparency of a film into the said range, it is preferable to set it as the structure which contains particle | grains only in an easily bonding layer and does not contain particle | grains substantially in the polyester film used as a base material. In addition, “substantially no particles are contained in the base film” means, for example, in the case of inorganic particles, a content that is below the detection limit when inorganic elements are quantified by fluorescent X-ray analysis. This is because contaminants derived from foreign substances may be mixed without intentionally adding particles to the base film.

  In the present invention, in order to achieve a good mirror appearance, the particle size distribution (d75 / d25) of the particles contained in the easy-adhesion layer of the present invention is preferably 1.1 to 1.5. The particle size distribution (d75 / d25) of the particles is preferably 1.4 or less, more preferably 1.3 or less. When the particle size distribution of the particles is not more than the above upper limit, uneven unevenness of the film surface is reduced, and even if a thin film is rolled, it is difficult for orange peel to occur. The particle size distribution of the particles is preferably close to 1, but 1.1 is the lower limit from the viewpoint of industrial productivity. The means for controlling the particle size distribution within the above range is not particularly limited. For example, coarse particles are removed by using filtration such as a filter, a particle falling speed, a blower, an electrostatic device, etc., and particle aggregation is less likely to occur. A particle type can be selected, or organic particles that can easily obtain a narrow particle size distribution can be employed. The particle size distribution of the organic particles can be suitably controlled by adjusting the concentration of the surfactant added during the adjustment. In particular, the crosslinked organic particles obtained by emulsion polymerization are suitable because a narrow particle size distribution is easily obtained. The particle size distribution can be measured from a scanning microscope observation image on the surface of the film easy-adhesion layer, an electron microscopic image of the film easy-adhesion layer section, or can be obtained by a Coulter counter method. Especially, it can obtain | require suitably by measuring the particle diameter of the particle | grains exposed on the surface of an easily bonding layer from the scanning microscope observation image of the film easily bonding layer surface.

  Examples of the particles contained in the easy-adhesion layer in the present invention include titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay and the like, or a mixture thereof. General inorganic particles such as calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride and other inorganic particles, styrene, acrylic, melamine, benzoguanamine, silicone, etc. Organic polymer-based particles and the like. Of these, organic polymer particles such as styrene and acrylic are preferred because particles having a narrow particle size distribution can be easily obtained.

  In the present invention, it is preferable that at least one kind of particles satisfy the above requirements. In addition to the above particles, a plurality of inorganic particles having different average particle diameters are used in combination for the purpose of blocking resistance and scratch resistance. This is also a preferred embodiment. The other particles used in this case preferably have an average particle size smaller than that of the particles, and more preferably smaller than the thickness of the easy adhesion layer. By adding such relatively small other particles, the hardness of the surface of the easy-adhesion layer can be imparted and the blocking resistance can be improved.

  The average particle size of such particles having a small average particle size (hereinafter, this particle is also referred to as particle B, and the above-mentioned particles are sometimes referred to as particle A) is preferably 20 to 150 nm, preferably 30 to 100 nm. More preferably, 40-80 nm is still more preferable. When the average particle diameter of the particles B is dB and the thickness of the easy adhesion layer is t, the ratio (dB / t) is preferably 1.5 to 0.1, and more preferably 1.2 to 0.3. By using small particles smaller than the particles A and equivalent to the thickness of the easy-adhesion layer as the particles B, it is possible to improve the blocking resistance without impairing the film surface feeling. When adding the particle | grains B, 30 mass% or less is preferable as solid content concentration in an easily bonding layer, 15 mass% or less is more preferable, and 10 mass% or less is more preferable. The transparency of a film can be hold | maintained by making the addition density | concentration of the particle | grains B below the said upper limit. The average particle size of the particles B is also preferably obtained by measuring the particle size of the particles exposed on the surface of the easy-adhesion layer from the scanning microscope observation image of the surface of the film easy-adhesion layer like the particle A. be able to.

  Moreover, since the easily bonding layer of this invention has the said structure, it has favorable blocking resistance. Specifically, the static friction coefficient of the easy-adhesion layer surface measured by the method described later is preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.7 or less. The dynamic friction coefficient is preferably 0.8 or less, more preferably 0.7 or less, and further preferably 0.6 or less. Since the static friction coefficient and / or the dynamic friction coefficient is not more than the above upper limit, the film of the present invention has suitable handleability in various molding processes.

  Since the easy-adhesion layer of the present invention has the above-described configuration, even when a thin film is wound up in a roll shape, an orange peel hardly occurs, and a clear mapping can be obtained by mirror surface treatment.

(Binder resin)
It is preferable that the easily bonding layer of this invention has suitable adhesiveness with respect to functional layers, such as a printing layer and a decoration layer. Specifically, easy adhesion means having a residual rate of 70% or more by an adhesion test described later. The easily adhesive layer of the present invention preferably contains a binder resin. As the binder resin, at least one kind of polyester resin, polyurethane resin, or polyacrylic resin can be used. In particular, a structure containing a polyester resin and a polyurethane resin as an easy-adhesion layer is preferable for providing a suitable mirror-like surface feeling when metal deposition is performed while exhibiting suitable adhesion with a decorative layer such as printing or vapor deposition. .

(Polyester resin)
The easy adhesion layer preferably contains a polyester resin. The polyester resin is suitable for improving the adhesion between the base film and the printed layer.

  The polyester resin contained in the easy-adhesion layer may be blended in the range of 5 to 90% by mass with respect to the entire solid content of the easy-adhesion layer in order to impart adhesion between the base polyester film and the easy-adhesion layer. Preferably, it is 30 to 80% by mass.

  As the polyester resin, a copolymer polyester in which a copolymer component is introduced to lower the glass transition temperature is preferable from the viewpoint of adhesiveness. The copolymer polyester preferably has water solubility or water dispersibility from the viewpoint of coatability. As such a copolyester, a copolyester having at least one group selected from the group consisting of sulfonic acid groups or alkali metal bases thereof (hereinafter referred to as sulfonic acid group-containing copolyester) is used. Is preferred.

  Here, the sulfonic acid group-containing copolymer polyester means a polyester in which at least one group selected from the group consisting of a sulfonic acid group or an alkali metal base thereof is bonded to a part of a dicarboxylic acid component or a glycol component. However, a co-polymer prepared by using an aromatic dicarboxylic acid component containing at least one group selected from the group consisting of a sulfonic acid group or an alkali metal base thereof in a ratio of 2 to 10 mol% with respect to the total acid component. Polymerized polyester is preferred.

  As an example of such a dicarboxylic acid, 5-sodium sulfoisophthalic acid is suitable. In this case, as other dicarboxylic acid components, terephthalic acid, isophthalic acid, phthalic acid, p-β-oxyethoxybenzoic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxydiphenyl, 4,4 ′ -Dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid, sebacic acid, cyclohexane-1,4-dicarboxylic acid and the like.

  In order to increase the surface hardness and maintain good blocking resistance, 96 to 90 mol% of the total acid content is preferably an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid. More preferably, 4 to 10 mol% of the aromatic dicarboxylic acid contains at least one group selected from the group consisting of the sulfonic acid groups or alkali metal bases thereof.

  As the glycol component for producing the sulfonic acid group-containing copolymer polyester, ethylene glycol is mainly used. In addition, addition of propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, bisphenol A ethylene oxide addition Products, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like can be used. Among them, it is preferable to use ethylene glycol, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexane dimethanol or the like as a copolymerization component in terms of improving compatibility with polystyrene sulfonate.

(Polyester graft copolymer)
A polyester-based graft copolymer is also suitable as the polyester resin used for the easy adhesion layer. Since the polyester-based graft copolymer can form a highly self-crosslinked structure, it has a good effect on moisture and heat resistance. The polyester-based graft copolymer is grafted with a polymerizable unsaturated monomer containing an acid anhydride having at least one double bond to a hydrophobic copolymer polyester resin from the viewpoint of heat and moisture resistance of the easy-adhesion layer. It is preferable to use one. Hereinafter, suitable polyester-based graft copolymers will be described.

  “Grafting” is to introduce a branched polymer made of a polymer different from the main chain into the main chain of the main polymer. In the present invention, a polymerizable unsaturated monomer containing an acid anhydride having at least one double bond using a radical initiator in a state where a hydrophobic copolymerizable polyester resin is dissolved in an organic solvent It is preferable to carry out graft polymerization by reacting. The reaction product after completion of the grafting reaction is a hydrophobic copolymerizable polyester resin that has not undergone grafting, in addition to the graft copolymer of the desired hydrophobic copolymerizable polyester and polymerizable unsaturated monomer. And a polymer of the above unsaturated monomer that has not been grafted to the hydrophobic copolymerizable polyester. The polyester-based graft copolymer used in the present invention is not only the above-mentioned polyester-based graft copolymer, but also an unreacted hydrophobic copolymerizable polyester and a polymer of unsaturated monomers that have not been grafted. Also refers to a reaction mixture containing

The acid value of a polyester-based graft copolymer obtained by graft polymerization of a polymerizable unsaturated monomer to a hydrophobic copolymerizable polyester resin is preferably 600 eq / 10 ⁶ g or more. More preferably, it is 1200 eq / 10 ⁶ g or more. When the acid value of the graft copolymer is 600 eq / 10 ⁶ g or more, the adhesion to the base film is good.

  Moreover, the mass ratio of the hydrophobic copolymerizable polyester resin and the polymerizable unsaturated monomer for obtaining the graft copolymer is polyester / polymerizable unsaturated monomer = 40/60 to 95/5. The range is desirable, more desirably 55/45 to 93/7, and most desirably 60/40 to 90/10. When the mass ratio of the hydrophobic copolymerizable polyester resin is less than 40% by mass, the glass transition point (Tig) of the obtained easy-adhesion layer is increased, the followability at the time of molding is lowered, and in a moisture and heat resistant environment. In some cases, the adhesiveness of the resin may deteriorate. On the other hand, when the mass ratio of the hydrophobic copolymerizable polyester resin is larger than 95% by mass, blocking tends to occur.

  The graft copolymer is in the form of an organic solvent solution or dispersion, or an aqueous solvent solution or dispersion. In particular, a dispersion of an aqueous solvent, that is, a form of a water-dispersed resin is preferable from the viewpoint of working environment and applicability. Such a water-dispersed resin is usually obtained by graft polymerization of at least one hydrophilic polymerizable unsaturated monomer onto the hydrophobic copolymerizable polyester resin in an organic solvent, followed by water addition and organic It can be obtained by distilling off the solvent.

  The glass transition point (Tig) of the graft copolymer is preferably 70 ° C. or lower, more preferably 50 ° C. or lower. When the glass transition point (Tig) is 70 ° C. or less, the following property at the time of molding after decoration is good, and excellent adhesiveness is easily obtained even in a moist heat resistant environment.

(Hydrophobic copolymerizable polyester resin)
In the present invention, the hydrophobic copolymerizable polyester resin is essentially water-insoluble which does not inherently disperse or dissolve in water. When a polyester resin that is dispersed or dissolved in water is used for graft polymerization, adhesion in a heat-and-moisture resistant environment may deteriorate. The composition of the dicarboxylic acid component of this hydrophobic copolymerizable polyester resin is as follows: aromatic dicarboxylic acid 60 to 99.5 mol%, aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid 0 to 40 mol%, polymerizable unsaturated It is preferable that it is 0.5-10 mol% of dicarboxylic acid containing a double bond. If the aromatic dicarboxylic acid is less than 60 mol%, or if the aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid exceeds 40 mol%, the adhesion may be lowered.

  Moreover, when the dicarboxylic acid containing a polymerizable unsaturated double bond is less than 0.5 mol%, it becomes difficult to efficiently graft the polymerizable unsaturated monomer to the hydrophobic copolymerizable polyester resin. On the other hand, when the amount exceeds 10 mol%, the viscosity is increased by the grafting reaction, and the uniform progress of the reaction is hindered. More preferably, the aromatic dicarboxylic acid is 70 to 98 mol%, the aliphatic dicarboxylic acid and / or the alicyclic dicarboxylic acid is 0 to 30 mol%, and the dicarboxylic acid containing a polymerizable unsaturated double bond is 2 to 7 mol%. It is.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid and the like. It is preferable not to use a hydrophilic group-containing dicarboxylic acid such as 5-sodium sulfoisophthalic acid because the blocking resistance, which is the object of the present invention, decreases. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1, Examples include 3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and acid anhydrides thereof. Examples of dicarboxylic acids containing polymerizable unsaturated double bonds include α, β-unsaturated dicarboxylic acids, fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, unsaturated double bonds Examples of the alicyclic dicarboxylic acid to be used include 2,5-norbornene dicarboxylic acid anhydride and tetrahydrophthalic anhydride. Of these, fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid are preferred from the viewpoint of polymerizability.

  On the other hand, examples of the glycol component include aliphatic glycols having 2 to 10 carbon atoms and / or alicyclic glycols having 6 to 12 carbon atoms and / or ether bond-containing glycols. Examples of the aliphatic glycol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6 -Hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, and the like. Examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol.

  Examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol, and glycols obtained by adding ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, such as 2,2-bis (4 -Hydroxyethoxyphenyl) propane and the like. Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used as necessary.

  In the hydrophobic copolymerizable polyester resin, 0 to 5 mol% of a trifunctional or higher polycarboxylic acid and / or polyol can be copolymerized. As the trifunctional or higher polycarboxylic acid, (anhydrous) Trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) and the like are used. On the other hand, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like are used as the trifunctional or higher functional polyol. The tri- or higher functional polycarboxylic acid and / or polyol is copolymerized in the range of 0 to 5 mol%, preferably 0 to 3 mol% with respect to the total acid component or the total glycol component. Gelation during polymerization tends to occur, which is not preferable. The molecular weight of the hydrophobic copolymerizable polyester resin is preferably in the range of 5000 to 50000 on a weight average. If the molecular weight is less than 5,000, the adhesiveness of the printed layer may be lowered. Conversely, if it exceeds 50,000, problems such as gelation during polymerization may occur.

(Graft site of polyester graft copolymer)
The polymerizable unsaturated monomer to be grafted to the hydrophobic copolymerizable polyester resin is a hydrophilic radical polymerizable monomer, and is a radical polymerization having a hydrophilic group or a group that can be changed to a hydrophilic group later. It is a possible monomer. Examples of the hydrophilic group include a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group, an amide group, and a quaternary ammonium base. On the other hand, examples of the group that can be changed to a hydrophilic group include an acid anhydride group, a glycidyl group, and a chloro group. Among these groups, a carboxyl group is preferable from the viewpoint of increasing the water dispersibility and the acid value of the graft copolymer. Accordingly, it is desirable to include at least one acid anhydride having a double bond as the polymerizable unsaturated monomer.

  Examples of the polymerizable unsaturated monomer include fumaric acid, monoethyl fumarate, diethyl fumarate, diester of fumaric acid such as dibutyl fumarate; maleic acid and its anhydride, monoethyl maleate, diethyl maleate Monoester or diester of maleic acid such as dibutyl maleate; itaconic acid and its anhydride, monoester or diester of itaconic acid; maleimide such as phenylmaleimide; styrene, α-methylstyrene, t-butylstyrene, chloromethyl Styrene derivatives such as styrene; vinyltoluene, divinylbenzene and the like. Acrylic polymerizable monomers that are one of polymerizable unsaturated monomers include, for example, alkyl acrylate, alkyl methacrylate (the alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl). Group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.): 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl methacrylate-containing acrylic monomer: acrylamide, methacrylamide, N-methyl methacrylamide, N-methyl acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N-dimethylol acrylamide N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, amide group-containing acrylic monomer of N-phenylacrylamide: N, N-diethylaminoethyl acrylate, amino group-containing acrylic monomer of N, N-diethylaminoethyl methacrylate : Glycidyl acrylate, epoxy group-containing acrylic monomer of glycidyl methacrylate: Acrylic monomers containing carboxyl groups or salts thereof such as acrylic acid, methacrylic acid and their salts (sodium salt, potassium salt, ammonium salt) It is done. However, acrylic polymerizable monomers are less preferred for use in the present invention because they are less effective in reducing the surface energy hydrogen bond strength component term (γsh) of the present invention. The polymerizable unsaturated monomer can be copolymerized using one kind or two or more kinds, but preferably contains at least one acid anhydride having a double bond. Among the above monomers, maleic anhydride is preferably used as the acid anhydride having a double bond. Styrene is preferred as another polymerizable unsaturated monomer to be combined with maleic anhydride. These acid anhydride esters may also be included.

(Polymerization initiator and other additives)
As the graft polymerization initiator that can be used in the present invention, organic peroxides and organic azo compounds known to those skilled in the art can be used. Benzoyl peroxide, t-butylperoxypivalate as organic peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) as organic azo compound Etc. The amount of the polymerization initiator used for the graft polymerization is at least 0.2% by mass, preferably 0.5% by mass or more, based on the polymerizable unsaturated monomer. In addition to the polymerization initiator, a chain transfer agent for adjusting the chain length of the branched polymer, for example, octyl mercaptan, mercaptoethanol, 3-t-butyl-4-hydroxyanisole and the like may be used as necessary. In this case, it is desirable to add in the range of 0 to 5% by mass with respect to the polymerizable unsaturated monomer.

  In addition, a dicarboxylic acid component or glycol component containing a small amount of an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like may be included as a copolymer component of the copolymer polyester. Furthermore, in order to improve the surface hardness of the resulting coating film, a monomer containing a multi-carboxyl group such as trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride is contained in a proportion of 5 mol% or less. It can also be used as a copolymerization component of the polyester. When these multi-carboxyl group-containing monomers exceed 5 mol%, the resulting sulfonic acid group-containing copolymer polyester becomes thermally unstable and is unfavorably easily gelled.

(Polyurethane)
In the present invention, it is preferable to use polyurethane for the easy-adhesion layer in order to impart flexibility and to provide excellent moldability. Polyurethane resins are roughly classified into polyester-based polyurethane resins, polyether-based polyurethane resins, and polycarbonate-based polyurethane resins. Any of these can be applied from the viewpoint of adhesiveness, and among them, it is preferable to use polycarbonate polyurethane from the viewpoint of blocking resistance and wet heat resistance. Polyester polyurethane resins are easily hydrolyzed in a moist heat environment, and polyether polyurethane resins are highly hygroscopic, so that the film strength of the easy-adhesion layer tends to decrease and adhesion may be insufficient. On the other hand, the polycarbonate-based urethane resin is preferable because it has a polycarbonate structure as a hard segment and thus has excellent moisture and heat resistance.

  As the polycarbonate-based polyurethane resin, a polycarbonate diol, an aliphatic and / or alicyclic diisocyanate, and a polymer to which a chain extender is added as necessary can be used. Note that these urethane constituents can be identified by nuclear magnetic resonance analysis or the like.

  The polycarbonate diol is represented by the following general formula.

HO — [— R—O—COO—] _n —R—OH
(R is an aliphatic or alicyclic substituent)

  The polycarbonate diol is obtained, for example, by reacting one or more compounds selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate with diols and / or polyether polyols.

  Examples of the alkylene carbonate include ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate and the like.

  Examples of diaryl carbonates include diphenyl carbonate, phenyl-naphthyl carbonate, dinaphthyl carbonate, 4-methyl diphenyl carbonate, 4-ethyl diphenyl carbonate, 4-propyl diphenyl carbonate, 4,4'-dimethyl-diphenyl carbonate, 4,4 Examples include '-diethyl-diphenyl carbonate and 4,4'-dipropyl-diphenyl carbonate.

  Examples of dialkyl carbonates include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n-amyl carbonate, diisoamyl carbonate. Etc.

  As a co-reactant for these carbonates, as examples of diols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2- Methyl-1,3-propanediol, neopentyl glycol, 2-methyl-pentanediol, 3-methyl-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,3,5-trimethylpentane Diol etc. are mentioned.

  Examples of polyether polyols include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran and alkylene oxide adducts of diols. Examples of diols used herein include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, isomer pentanediols, and isomer hexane. Diols or octanediols such as 2-ethyl-1,3-hexanediol, 1,2-bis (hydroxymethyl) -cyclohexanone, 1,3-bis (hydroxymethyl) -cyclohexanone, 1,4-bis (hydroxymethyl) ) -Cyclohexanone, trimethylolpropane, glycerin and the like. Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, and tetrahydrofuran. , Styrene oxide, epichlorohydrin and the like, which are also possible to use a mixture of two or more.

  The diols and polyether polyols described above may be used alone or in combination of two or more. Any of these can react with one or more compounds selected from the group consisting of the aforementioned alkylene carbonates, diaryl carbonates, and dialkyl carbonates by known methods to form polycarbonate diols.

  In the present invention, the compositional molar ratio of the polyol, which is a constituent component of urethane, is preferably 3 to 100 mol%, and preferably 5 to 50 mol% when the total polyisocyanate component of urethane is 100 mol%. Is more preferable, and it is more preferable that it is 6-20 mol%. In particular, in the case of polycarbonate polyol, if the composition molar ratio is low, the heat and heat resistance effect may not be obtained. Moreover, when the said composition molar ratio is high, adhesiveness may fall.

  Examples of the polyisocyanate that is a constituent component of the urethane of the present invention include isomers of toluylene diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, and isophorone. Diisocyanates and alicyclic diisocyanates such as 4,4-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, and aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, Alternatively, polyisocyanates obtained by adding one or more of these compounds with trimethylolpropane or the like in advance may be mentioned.

  Chain extenders include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol, polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol, ethylenediamine Diamines such as hexamethylenediamine and piperazine, aminoalcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol, and water.

  The easy-adhesion layer of the present invention is preferably provided by an in-line coating method described later using an aqueous coating solution. Therefore, it is desirable that the urethane resin of the present invention is water-soluble. The “water-soluble” means that it dissolves in water or an aqueous solution containing less than 50% by mass of a water-soluble organic solvent.

  In order to impart water solubility to the urethane resin, a sulfonic acid (salt) group or a carboxylic acid (salt) group can be introduced (copolymerized) into the urethane molecular skeleton. Since the sulfonic acid (salt) group is strongly acidic and it may be difficult to maintain moisture resistance due to its hygroscopic performance, it is preferable to introduce a weakly acidic carboxylic acid (salt) group.

  In order to introduce a carboxylic acid (salt) group into a urethane resin, for example, as a polyol component, a polyol compound having a carboxylic acid group such as dimethylolpropionic acid or dimethylolbutanoic acid is introduced as a copolymer component to form a salt. Neutralize with an agent. Specific examples of the salt forming agent include trialkylamines such as ammonia, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, N such as N-methylmorpholine and N-ethylmorpholine. -N-dialkylalkanolamines such as alkylmorpholines, N-dimethylethanolamine, N-diethylethanolamine and the like. These can be used alone or in combination of two or more.

  In order to impart water solubility, when a polyol compound having a carboxylic acid (salt) group is used as a copolymerization component, the composition molar ratio of the polyol compound having a carboxylic acid (salt) group in the urethane resin is the same as that of the urethane resin. When the total polyisocyanate component is 100 mol%, it is preferably 3 to 60 mol%, more preferably 10 to 40 mol%. If the composition molar ratio is less than 3 mol%, water dispersibility may be difficult.

  In the present invention, the glass transition point (Tig) of the polyurethane resin is preferably controlled within a specific range. That is, the glass transition point (Tig) of the polyurethane of the present invention has a lower limit of 40 ° C., preferably 50 ° C., and an upper limit of 100 ° C., preferably 90 ° C. When the glass transition point (Tig) of the polyurethane resin is less than 40 ° C., the blocking resistance may be lowered. On the other hand, when the temperature exceeds 100 ° C., the flexibility and adhesiveness of the easy-adhesion layer may decrease. In order to control the glass transition point (Tig) of the polyurethane within the above range, the following polyol component or molecular weight of the polyurethane can be appropriately selected and adjusted.

  In the present invention, the blending ratio of the copolymer polyester and the polyurethane is such that the polyester / polyurethane (mass ratio) = 80 / 20-30 / 70 is preferable. The blending ratio is more preferably 75/25 to 40/60. When the copolyester / polyurethane (mass ratio) = 100/0 to 90/10, the flexibility of the easy-adhesion layer may be lowered, and when 20/80 to 0/100, the blocking resistance and the adhesion may be lowered.

  The easy-adhesion layer of the present invention is mainly composed of polyester that exhibits suitable adhesion to a base film made of polyester and polyurethane that is highly compatible with the decorative layer, and therefore has excellent initial adhesion. Indicates. Furthermore, in order to improve the heat and moisture resistance, it is necessary to use a polyester-based graft copolymer capable of forming a high degree of self-crosslinking as the polyester and a polycarbonate-based polyurethane that is not easily hydrolyzed as the polyurethane. Is preferred. The present inventor considers that the combination of the polyester-based graft copolymer and the polycarbonate-based polyurethane is particularly suitable for imparting wet heat resistance as follows. That is, the polyester-based graft copolymer of the present invention has an acid anhydride as a constituent component as a side chain. On the other hand, the polyurethane of the present invention has a carbonate group. These side chains and carbonate groups exhibit a hydrogen bond-like interaction, and it is considered that the durability as an easy adhesion layer is exhibited to a higher degree.

  The minimum of the glass transition point (Tig) of the easily bonding layer of this invention is 30 degreeC, Preferably it is 35 degreeC, and an upper limit is 55 degreeC, Preferably it is 50 degreeC. If the glass transition point (Tig) of the easy-adhesion layer is less than 35 ° C., sufficient moisture and heat resistance may not be obtained, and blocking resistance may also be reduced. If the glass transition point (Tig) of the easy-adhesion layer exceeds 55 ° C., the flexibility of the easy-adhesion layer may decrease. In order to suitably achieve both the heat and moisture resistance and the moldability, it is preferable to set the glass transition point (Tig) of the easy-adhesion layer in such a range. Even if the polyester component and the polyurethane component each have a glass transition point (Tig) within the above range, when an easy-adhesion layer having a crosslinked structure is laminated together with a crosslinking agent in the film forming step, the glass transition point (Tig) May exceed 38 ° C. Moreover, in order to maintain the glass transition point (Tig) even if it has a crosslinked structure, an appropriate amount of crosslinking agent, an amount of polyurethane and an amount of polyester graft copolymer, and a hydrophobic copolymer The mass ratio between the polymerizable polyester resin and the polymerizable unsaturated monomer is preferably within the above-mentioned range. The glass transition point is based on JIS-K7121 in a state where it is laminated as an easy-adhesion layer in a film forming process, that is, in a state where a polyester-based graft copolymer and a polycarbonate-based polyurethane are crosslinked with a crosslinking agent. The extrapolated glass transition start temperature (Tig) measured by the method is meant.

(Crosslinking agent)
From the viewpoint of blocking resistance, the easy-adhesion layer of the present invention preferably contains a crosslinking agent. Thereby, an appropriate cross-linked structure is formed in the easy-adhesion layer, and therefore the addition of a cross-linking agent is suitable for imparting moisture heat resistance. The blending ratio of the crosslinking agent is preferably 5 to 40 parts by mass, and more preferably 8 to 25 parts by mass with respect to 100 parts by mass of the total amount of the polyester resin and the polyurethane resin. When the blending ratio of the crosslinking agent is less than 5 parts by mass with respect to 100 parts by mass of the total amount of the polyester resin and the polyurethane resin, the blocking resistance may be lowered or the adhesiveness may be lowered. Conversely, when it exceeds 40 parts by mass, the flexibility for following the moldability may be reduced.

  Examples of the cross-linking agent include phenol formaldehyde resins of condensates with formaldehyde such as alkylated phenols and cresols; adducts of urea, melamine, benzoguanamine, and the like with formaldehyde, and the adducts having 1 to 6 carbon atoms. An amino resin such as an alkyl ether compound composed of alcohol; a polyfunctional epoxy compound; a polyfunctional isocyanate compound; a blocked isocyanate compound; a polyfunctional aziridine compound;

  Examples of the phenol formaldehyde resin include alkylated (methyl, ethyl, propyl, isopropyl or butyl) phenol, p-tert-amylphenol, 4,4′-sec-butylidenephenol, p-tert-butylphenol, o-, m-, p-cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl-o-cresol, p-phenylphenol, xylenol, etc. And the condensates of phenols and formaldehyde.

  Examples of amino resins include methoxylated methylol urea, methoxylated methylol N, N-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like. Are preferably methoxylated methylol melamine, butoxylated methylol melamine, methylolated benzoguanamine, and the like.

  Examples of the polyfunctional epoxy compound include diglycidyl ether of bisphenol A and oligomer thereof, diglycidyl ether of hydrogenated bisphenol A and oligomer thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene Glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and Polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl Examples include ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like.

  As the polyfunctional isocyanate compound, a low-molecular or high-molecular aromatic or aliphatic diisocyanate or a trivalent or higher polyisocyanate can be used. Examples of the polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and trimers of these isocyanate compounds. Furthermore, an excess amount of these isocyanate compounds and low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, or polyester polyols, poly The terminal isocyanate group containing compound obtained by making it react with polymer active hydrogen compounds, such as ether polyols and polyamides, can be mentioned.

  Among the crosslinking agents, a blocked isocyanate crosslinking agent is preferable as the crosslinking agent used in the present invention. By adding a blocked isocyanate-based crosslinking agent, it becomes possible to achieve both high adhesiveness and blocking resistance.

  The blocked isocyanate crosslinking agent can be prepared by subjecting the isocyanate compound and the blocking agent to an addition reaction by a conventionally known appropriate method. Examples of the isocyanate blocking agent include phenols such as phenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; thiophenols such as thiophenol and methylthiophenol; oximes such as acetoxime, methyl etiketooxime, and cyclohexanone oxime. Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol ; Lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propyllactam; aromatic amines; imides; acetylacetone, acetoacetate Active methylene compounds such as malonic acid ethyl ester; mercaptans; imines; ureas; diaryl compounds; and sodium bisulfite and the like.

  In the coating liquid of the present invention, known additives, for example, antioxidants, heat stabilizers, weathering stabilizers, UV absorbers, organic lubricants, pigments, dyes, organics, as long as the effects of the present invention are not impaired. Alternatively, inorganic particles, an antistatic agent, a nucleating agent, or the like may be added.

(Molded body)
The insert molding polyester film of the present invention can be suitably used as an alternative to plating. A metallic decorative layer is applied to either side of the polyester film for insert molding of the present invention. The metallic decoration layer can be formed by physical vapor deposition using a metal, an alloy, a metal oxide, or a material obtained by adding silicon or the like to these as an evaporation material. The physical vapor deposition method is a method in which a vaporized material is vaporized by some method in a vacuumed container, and the vaporized vaporized material is deposited on a base placed nearby to form a thin film. Depending on the vaporization method of the evaporation material, it can be divided into an evaporation system and a sputtering system. Examples of the evaporation system include EB deposition, ion plating, and pulse laser deposition. Examples of the sputtering system include RF (radio frequency) sputtering, magnetron sputtering, counter target type magnetron sputtering, and ECR sputtering.

  The vapor deposition material may be any one or more of tin, indium, aluminum, zinc, gold, silver, copper, titanium, nickel, or an alloy based on any of these. What is selected specifically may be selected according to the type of desired metallic luster. Among these, indium is excellent in extensibility, and thus is suitable for the moldable plating substitute film of the present invention.

  The thickness of the metal vapor deposition layer is preferably 5 nm or more and 80 nm or less. If it is 5 nm or more, a suitable metallic luster can be easily obtained, and if it is 80 nm or less, cracks during molding can be suitably suppressed.

  In addition to physical vapor deposition, a mirror ink or the like may be applied or printed. The surface to be decorated may be an easy adhesion layer surface or a non-adhesion layer surface. The surface which changes to plating can be show | played by overlapping and integrally molding the film which gave the decoration with a base material.

  As the substrate, a sheet or film having moldability can be used. The constituent material of the substrate is not particularly limited, but a polymer resin is preferably used. Examples of polymer resins include acrylic resins such as polyurethane resins and polymethyl methacrylate resins, acrylonitrile-butadiene-styrene resins (ABS resins), polyester resins such as polycarbonate resins and polyethylene terephthalates, olefin resins such as polypropylene, and polyethylene resins. Fluorine resin or the like can be used. The substrate and the molding polyester film may be directly laminated, but may be laminated via an adhesive layer, a heat seal layer, or the like.

  A method for integrally molding the obtained laminate is not particularly limited, but can be integrally formed by vacuum molding, pressure molding, mold molding, or the like.

  The obtained molded body is, for example, interior decoration or exterior decoration material for automobiles, television, refrigerator, washing machine, stereo, home appliances such as portable devices, mirror products such as compact mirrors for makeup, vehicles such as automobiles, It is suitable as a nameplate (including a display plate and a panel) used for ships, aircraft, buildings, play equipment (ski goggles, etc.), amusement devices, and other various mechanical devices. In particular, it is more suitable for uses under high-temperature and humid heat (bathrooms such as bathtubs, washstands, kitchens, sanitary, outdoor materials such as building materials, exteriors, and solar panels, automobile interiors, and attics.

Next, examples and comparative examples of the present invention will be shown. First, the measurement / evaluation method used in the present invention is shown below. Hereinafter, Examples 1 to 3 will be read as Reference Examples 1 to 3.

(1) Glass transition point (Tig)
The glass transition point (Tig) of the easy adhesion layer was measured by scraping only the easy adhesion layer from the film.
The measurement was based on JIS K7121 and the glass transition start temperature (Tig) was calculated | required from the DSC curve using the differential scanning calorimeter (The Seiko Instruments Inc. make, DSC6200).
Measurement conditions (a) Measurement temperature range: 0 to 200 ° C
(B) Temperature increase rate: 20 ° C./min
(C) With nitrogen gas flow

(2) Intrinsic Viscosity 0.1 g of the chip sample was precisely weighed and dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane = 6/4 (mass ratio), and measured at 30 ° C. using an Ostwald viscometer. In addition, the measurement was performed 3 times and the average value was calculated | required.

(3) Haze Based on JIS-K7105, it evaluated using the integrating-sphere type light transmittance measuring apparatus (made by Nippon Denshoku Industries Co., Ltd.).

(4) Thickness of easy adhesion layer A film cross section is cut at right angles to the film surface with a microtome, a cross-sectional photograph of the film is taken with a transmission electron microscope (TEM), and the thickness of the resin component is measured on the photograph. The same measurement was performed 10 times at different locations, and the average of the measured values was taken as the resin component thickness (μm).

(5) Melting point (Tm) of raw material (object)
Using a differential scanning calorimeter (Mac Science, DSC3100S), about 7 mg of a film sample is placed in a sample pan, the pan is capped, and the temperature is raised from room temperature to 300 ° C. in a nitrogen gas atmosphere at 20 ° C./min. The temperature was increased at a rate and measured. The melting point was determined at the melting peak temperature defined in Section 9.1.

(6) Stress at 100% elongation With respect to the longitudinal direction and the width direction of the obtained film, a sample was cut into a strip shape having a length of 180 mm and a width of 10 mm, respectively, with a single-blade razor. Subsequently, the strip-shaped sample was pulled using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), and 100% elongation stress (MPa) in each direction was determined from the obtained load-strain curve.

  Note that the stress at 100% elongation at 25 ° C. was measured in an atmosphere at 25 ° C. under an initial length (distance between marked lines) of 40 mm, a distance between chucks of 100 mm, a crosshead speed of 100 mm / min, and a chart speed of the recorder of 200 mm / min. It carried out on the conditions of min and load cell 25kgf. In addition, this measurement was performed 10 times and the average value was used.

  In addition, the tensile test was performed under the same conditions as described above for the measurement of stress at 100% elongation at 100 ° C. At this time, the sample was held for 30 seconds in an atmosphere at 100 ° C. and then measured. In addition, the measurement was performed 10 times and the average value was used.

(7) Appearance 1 (Wave scan method)
The obtained film having a length of about 100 m was wound into a film roll and allowed to stand at room temperature for about 12 hours. Then, the film was cut out, and a black sheet (GA board FS black 26) was laid on the surface opposite to the easy adhesion layer surface. The easy-adhesion layer surface of the film was measured using a wave scan (BYK Gardner). Evaluation was made based on the value of the reflected intensity Wa in the displayed wavelength range of 0.1 to 0.3 mm. The reflection intensity Wa in the wavelength range of 0.1 to 0.3 mm is an index of the amplitude of the surface roughness, and the amplitude due to a fine uneven shape such as orange beer on the film surface can be evaluated. A smaller value indicates higher surface smoothness.

(8) Appearance 2 (visual evaluation)
The obtained film with a length of about 100 m is wound up in a film roll shape and allowed to stand at room temperature for about 12 hours, and then about 100 mm thick metal (In) is deposited on the film, and an image of a fluorescent lamp on the surface is imprinted. In addition, the mapping state of the fluorescent lamp was visually observed and evaluated in the following five stages.
1: No distortion of the mapping is observed at all. 2: Slight distortion of the mapping is observed, but it can be used. 3: Although the distortion of the mapping is considerably observed, it can be used. 4: Clear mapping. Distortion is seen on the entire surface and can not be used

(9) Particle size distribution of particles A The particle size distribution value was determined by measuring particles exposed on the surface of the easy-adhesion layer by a photographic method using an S3500 scanning electron microscope (magnification 800 times) manufactured by Hitachi, Ltd. and converting the particles to equivalent spheres. For the particle size distribution, the particle size of about 500 particles was measured, and the volume was integrated from the small particle side. With respect to the total volume, the particle size distribution when the cumulative ratio is 25% is d25, the particle size when the cumulative ratio is 75% is d75, and the ratio (d75 / d25) indicates the sharpness of the particle size distribution. The closer this value is to 1, the sharper. In the case where particles B coexist, the particle population having a large particle diameter was measured by the above method as a population.

(10) Average particle size of particles The average particle size of the particles was determined by the same method as the above particle size distribution, and expressed as the particle size d50 when the integrated ratio was 50% with respect to the total volume. When particles B coexist, the particle population having a large particle size is divided into a population and a population having a small particle size, the particle size of particles having a large particle size is defined as particle A, and the particle size of the smaller particle is defined as particle B. It measured by the said method.

(11) Friction evaluation (μs · μd)
A sample film was prepared by cutting the obtained film into an area of 8 cm × 5 cm. This was fixed to the bottom surface of a metal rectangular parallelepiped having a size of 6 cm × 5 cm and having a weight of 4.4 kg so that the easy adhesion layer surface was on the inside. At this time, the 5 cm width direction of the sample film and the 5 cm width direction of the metal cuboid were matched, one side in the longitudinal direction of the sample film was bent, and fixed to the side surface of the metal cuboid with an adhesive tape.
Next, a sample film was cut out in an area of 20 cm × 10 cm from the same base film, and the end portion in the longitudinal direction was fixed to a flat metal plate with an adhesive tape with the easy-adhesion layer surface facing up. The measurement surface of the metal rectangular parallelepiped with the sample film attached thereto was placed in contact, and the static friction coefficient (μs) and dynamic friction coefficient (μd) were measured under the conditions of a pulling speed of 200 mm / min, 23 ° C., and 65 RH. For the measurement, RTM-100 manufactured by Toyo BALDWIN was used, and the static friction coefficient (μs) and the dynamic friction coefficient (μd) were calculated according to JIS-7125.

(12) Air escape index As shown in FIG. 1, the film 4 is placed on the base 1 with the anti-adhesive layer face up. Next, the film presser 2 is placed on the film 4 and fixed to fix the film 4 while applying tension. Next, the film 5 is placed on the film presser 2 with the easy adhesion layer side down. Next, the film retainer 8 is placed on the film 5, and the film retainers 8, 2 and the base plate 1 are fixed using the screws 3. Next, the cavity 2 a provided in the film presser 2 and the vacuum pump 6 are connected via the pores 2 c provided in the film presser 2 and the pipe 7. When the vacuum pump 6 is driven, tension is applied to the film 5 by being sucked into the cavity 2a. At the same time, the overlapping surface of the film 4 and the film 5 is also depressurized through the pores 2d provided circumferentially in the film retainer 2, and the film 4 and the film 5 are in close contact with each other from the outer peripheral portion. start. The close contact can be easily known by observing the interference fringes from the upper part of the overlapping surfaces. Then, the time (seconds) is measured until the interference fringes spread on the front surface of the overlapped surface after the interference fringes are generated on the outer peripheral portion of the superposed surfaces of the films 4 and 5, and this time (seconds) is measured. Is taken as the air escape index. The measurement is repeated 5 times by replacing two films, and the average value is calculated as an air escape index. The smaller the air escape index value, that is, the shorter the time (seconds), the better the winding properties of the film.
The winding property was evaluated according to the following criteria.
◎: Air escape index less than 50 seconds ○: Air escape index 50 seconds to 200 seconds △: Air escape index 200 seconds to 350 seconds ×: Air escape index 350 seconds or more

(13) Adhesive UV curable ink (manufactured by Seiko Advance Co., Ltd., UVA710 Black) is printed on the film surface (the surface of the easy-adhesion layer if an easy-adhesion layer is provided) with a Tetron screen (# 300 mesh). Then, UV exposure was performed at 500 mJ / cm ² .
Put a 2mm square 100 square cross-cut surface with a cutter knife on the cured printed layer, and paste cellophane (Nichiban Co., Ltd., CT-24) on it so that no air bubbles enter it, and rub it over it. And make sure it is in close contact. Thereafter, both ends of the ink surface before and after the adhesive tape (registered trademark) were not adhered to each other were pressed by hand and rapidly peeled in the 90 ° direction.
The ink surface after peeling was observed, and the adhesiveness was evaluated on the basis of the following four steps based on the ink residual ratio (treated as the number of pieces peeled even at a part of the square) in 100 squares. ○ was accepted. The easy adhesion referred to in the present invention is defined as having an ink residual ratio of 90% or more when the above evaluation is performed.
A: Residual rate 100% (no peeling at all)
○: Residual rate 90% or more and less than 100% (can be used practically without problems)
Δ: Residual rate of 70% or more and less than 90% (adhesion is slightly weak, and there is a possibility that problems may occur in practice)
X: Residual rate less than 70% (adhesion failure)

(14) Adhesiveness after wet heat Oxidized polymerization ink (manufactured by Jujo Kako Co., Ltd., black) and diluent solvent (manufactured by Jujo Kako Co., Ltd., Tetron) are diluted with ink: diluting solvent = 4: 1, and the film surface (easily When an adhesive layer was provided, the surface was printed on a surface of the easy adhesive layer) using a Tetron screen (# 250 mesh) and then dried in a gear oven at 65 ° C. for 15 minutes.
Next, the ink-printed film is placed in 80 ° C. hot water for 2 minutes. After taking out and wiping away moisture, it is air-dried for 3 hours or more. Subsequently, a crosscut surface of 100 mm square of 2 mm is put on the printed surface with a cutter knife, and a cello tape (manufactured by Nichiban Co., Ltd., CT-24) is stuck on the printed surface so that no bubbles enter, and further, the surface is rubbed. Adhere sufficiently. Thereafter, both ends of the ink surface before and after the cellophane tape (registered trademark) were not adhered were pressed by hand, and the cross-cut surface was rapidly peeled in the 90 ° direction.
The ink surface after peeling was observed, and the adhesiveness was evaluated on the basis of the following four steps based on the ink residual ratio (treated as the number of pieces peeled even at a part of the square) in 100 squares. ○ was accepted. The easy adhesion referred to in the present invention is defined as having an ink residual ratio of 90% or more when the above evaluation is performed.
A: Residual rate 100% (no peeling at all)
○: Residual rate 90% or more and less than 100% (can be used practically without problems)
Δ: Residual rate of 70% or more and less than 90% (adhesion is slightly weak, and there is a possibility that problems may occur in practice)
X: Residual rate less than 70% (There is a problem with adhesiveness)

(15) Formability A polyurethane resin (Takenate A-975, Mitsui Chemicals) was applied to the anti-deposition layer of the film having the metal deposition layer obtained in (8) to provide an adhesive layer. The metal vapor-deposited surface is protected with a 38 μm-thick polyethylene terephthalate separate film, the counter-deposited surface side is laminated with a 100 μm-thick acrylic film, contact-heated with a hot plate heated to 100 to 140 ° C. for 4 seconds, and then a mold Press molding was performed at a temperature of 30 to 70 ° C. and a pressure holding time of 5 seconds. The shape of the mold was a cup shape, the opening had a diameter of 50 mm, the bottom part had a diameter of 40 mm, the depth was 40 mm, and all corners were curved with a diameter of 0.5 mm. . The obtained molded product was evaluated according to the following criteria.
A: Good cornering, no appearance defects such as wrinkles and mapping distortion, and high metallic gloss.
○: Although some wrinkles are recognized, there is no mapping distortion and a metallic glossy feeling is obtained.
Δ: Wrinkles and mapping distortion are partially observed.
X: Wrinkles or mapping distortion is observed on the entire surface, or the molded product is torn.

Example 1
(Preparation of hydrophobic polymerized polyester resin)
In a stainless steel autoclave equipped with a stirrer, thermometer and partial reflux condenser, 218 parts by weight of dimethyl terephthalate, 194 parts by weight of dimethyl isophthalate, 488 parts by weight of ethylene glycol, 200 parts by weight of neopentyl glycol and tetra-N-butyltitanium 0.5 weight part was prepared and transesterification was performed over 4 hours from 160 degreeC to 220 degreeC. Next, 13 parts by weight of fumaric acid and 51 parts by weight of sebacic acid were added, and the temperature was raised from 200 ° C. to 220 ° C. over 1 hour to carry out an esterification reaction. Next, the temperature was raised to 255 ° C. and the reaction system was gradually depressurized, and then reacted for 1 hour 30 minutes under a reduced pressure of 0.22 mmHg to obtain a hydrophobic copolyester resin. The obtained hydrophobic copolyester was light yellow and transparent.

(Preparation of water-dispersed polyester-based graft copolymer)
In a reactor equipped with a stirrer, thermometer, refluxing device and quantitative dropping device, 75 parts by mass of hydrophobic copolymer polyester, 56 parts by mass of methyl ethyl ketone and 19 parts by mass of isopropyl alcohol are heated and stirred at 65 ° C. Dissolved. After the resin was completely dissolved, 15 parts by mass of maleic anhydride was added to the polyester solution. Subsequently, a solution prepared by dissolving 10 parts by mass of styrene and 1.5 parts by mass of azobisdimethylvaleronitrile in 12 parts by mass of methyl ethyl ketone was dropped into the polyester solution at 0.1 ml / min, and stirring was further continued for 2 hours. After sampling for analysis from the reaction solution, 5 parts by mass of methanol was added. Next, 300 parts by mass of ion-exchanged water and 15 parts by mass of triethylamine were added to the reaction solution and stirred for 1.5 hours. Thereafter, the reactor internal temperature was raised to 100 ° C., and methyl ethyl ketone, isopropyl alcohol, and excess triethylamine were distilled off to obtain a water-dispersed polyester graft copolymer. The obtained polyester-based graft copolymer was light yellow and transparent, and the glass transition point was 40 ° C. This resin was designated as a polyester-based graft copolymer (a1).

(Synthesis of polycarbonate urethane resin)
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 73.0 parts by mass of 1,3-cyclohexanebis (methyl isocyanate) as polyisocyanate and polyhexane having a number average molecular weight of 2000 Diol carbonate 112.7 parts by mass, neopentyl glycol 11.7 parts by mass, dimethylolpropionic acid 12.6 parts by mass, and as an organic solvent, acetonitrile 60 parts by mass, N-methylpyrrolidone 30 parts by mass, Under a nitrogen atmosphere, the temperature of the reaction solution was adjusted to 75 to 78 ° C., and 0.06 part by mass of stannous octylate was added as a reaction catalyst, and the reaction rate was reacted to 99% or more in 7 hours. Subsequently, this was cooled to 30 degreeC and the isocyanate group terminal prepolymer was obtained. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., and added with an isocyanate group-terminated prepolymer while stirring and mixing at 2000 min ⁻¹ to disperse in water. did. Thereafter, an aqueous solution (b1) of a water-dispersible polycarbonate-based urethane resin having a solid content of 35% was prepared by removing a portion of acetonitrile and water under reduced pressure. The glass transition point (Tig) was 86 ° C.

(Preparation of coating solution A)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the mixed amount of the blocked isocyanate compound is 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, the total resin solid content concentration is 2.8% by mass, and the average as particles Diluted with water / isopropyl alcohol mixed solvent (= 65/35; mass ratio) so that polymethyl methacrylate particles having a particle size of 0.04 μm are contained in an amount of 1.0% by mass based on the total resin. An agent was used.

(Manufacture of film raw materials)
Copolymer polyester chip having an intrinsic viscosity of 0.69 dl / g, comprising 100 mol% of terephthalic acid units as aromatic dicarboxylic acid components, 40 mol% of ethylene glycol units and 60 mol% of neopentyl glycol units as diol components. (A) and a chip (B) having an intrinsic viscosity of 0.69 dl / g polyethylene terephthalate were dried. Furthermore, the chip (A) and the chip (B) were mixed so as to have a mass ratio of 25:75.

(Manufacture of laminated film)
Subsequently, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C. with an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C., and at the same time, the amorphous mixture was adhered to the chill roll using an electrostatic application method. A stretched sheet was obtained.

  The obtained unstretched sheet was stretched 3.3 times at 90 ° C. in the longitudinal direction between the heating roll and the cooling roll.

  Subsequently, the aqueous coating liquid A shown above was applied to one side of the film by roll coating on the obtained uniaxially stretched film, and dried at 130 ° C. for 3 seconds to remove moisture.

  Thereafter, the end portion is continuously held by a clip and guided to a tenter, heated at a setting of 100 ° C., stretched 3.8 times, heat-treated at 230 ° C. for 5 seconds while being fixed in width, and further 205 By relaxing at 5 ° C. in the width direction at 5 ° C., a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained.

  Table 1 shows the evaluation results of the obtained polyester film for molding.

(Preparation of coating solution B)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the mixed amount of the blocked isocyanate compound is 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, the total resin solid content concentration is 2.8% by mass, and the average as particles Diluted with a mixed solvent of water / isopropyl alcohol (= 65/35; mass ratio) so as to contain 1.0% by mass of silica particles having a particle size of 0.06 μm with respect to the total resin, did.

Example 2
In Example 1, except that the coating solution A was replaced with the coating solution B, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution C)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size Water / isopropyl alcohol so that the silica particles of 0.13 μm are contained in an amount of 1.0% by mass with respect to the total resin and the silica particles having an average particle size of 0.06 μm are contained in an amount of 7.3% by mass with respect to the total resin. It diluted with the mixed solvent (= 65/35; mass ratio), and was set as the water-system coating agent.

Example 3
Except that the coating solution A was replaced with the coating solution C in Example 1, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution D)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size Water / isotope so that 0.82 μm of styrene / divinylbenzene crosslinked particles of 0.83 μm are contained in an amount of 0.02% by mass with respect to the total resin and silica particles having an average particle size of 0.06 μm are contained in an amount of 7.3% by mass with respect to the total resin It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 4
In Example 1, except that the coating solution A was replaced with the coating solution D, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution E)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size Water / isotope so that 0.83 μm of styrene / divinylbenzene crosslinked particles are contained in an amount of 0.05% by mass based on the total resin, and silica particles having an average particle size of 0.06 μm are contained in an amount of 7.3% by mass based on the total resin. It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 5
In Example 1, except that the coating solution A was replaced with the coating solution E, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution F)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 0.56% by mass and the average particle diameter In order to contain 0.83 μm of styrene / divinylbenzene crosslinked particles of 0.83 μm with respect to the total resin and 7.3% by mass of silica particles with an average particle diameter of 0.06 μm with respect to the total resin, It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 6
In Example 1, except that the coating liquid A was replaced with the coating liquid F, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.01 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution G)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 1.12% by mass and the average particle size In order to contain 0.83 μm of styrene / divinylbenzene crosslinked particles of 0.83 μm with respect to the total resin and 7.3% by mass of silica particles with an average particle diameter of 0.06 μm with respect to the total resin, It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 7
In Example 1, except that the coating solution A was replaced with the coating solution G, a molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.02 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution H)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size In order to contain 0.83 μm of styrene / divinylbenzene crosslinked particles of 0.83 μm with respect to the total resin and 7.3% by mass of silica particles with an average particle diameter of 0.06 μm with respect to the total resin, It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 8
In Example 1, except that the coating solution A was replaced with the coating solution H, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 m was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating liquid I)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed in an amount of 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 5.04% by mass and the average particle diameter In order to contain 0.83 μm of styrene / divinylbenzene crosslinked particles of 0.83 μm with respect to the total resin and 7.3% by mass of silica particles with an average particle diameter of 0.06 μm with respect to the total resin, It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 9
In Example 1, except that the coating liquid A was replaced with the coating liquid I, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.09 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution J)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed in an amount of 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 5.60% by mass and the average particle diameter In order to contain 0.83 μm of styrene / divinylbenzene crosslinked particles of 0.83 μm with respect to the total resin and 7.3% by mass of silica particles with an average particle diameter of 0.06 μm with respect to the total resin, It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 10
In Example 1, a polyester film for molding having a film thickness of 25 μm and an easy-adhesion layer applied thickness of 0.10 μm was obtained in the same manner as Example 1 except that the coating liquid A was replaced with the coating liquid J. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution K)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size Water / isotope is used so that 0.83 μm of styrene / divinylbenzene crosslinked particles are contained in an amount of 3.0% by mass based on the total resin and silica particles having an average particle size of 0.06 μm are contained in an amount of 7.3% by mass based on the total resin. It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 11
In Example 1, except that the coating solution A was replaced with the coating solution K, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating liquid L)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size Water / isotope is used so that 0.83 μm of styrene / divinylbenzene crosslinked particles of 0.83 μm are contained in the total resin and 5.0% by mass of silica particles having an average particle size of 0.06 μm in the total resin. It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 12
In Example 1, except that the coating solution A was replaced with the coating solution K, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution M)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size Water / isotope so that 0.47 μm styrene / divinylbenzene crosslinked particles are contained in an amount of 1.0% by mass with respect to the total resin and silica particles having an average particle size of 0.06 μm are contained in an amount of 7.3% by mass with respect to the total resin. It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 13
In Example 1, a polyester film for molding having a film thickness of 25 μm and an easy-adhesion layer applied thickness of 0.05 μm was obtained in the same manner as in Example 1 except that the coating liquid A was replaced with the coating liquid M. The characteristics and evaluation results of the obtained film are shown in Table 1.

Example 14
In Example 1, except that the coating liquid A was replaced with the coating liquid M, the molding polyester film having a film thickness after film formation of 75 μm and a coating thickness of the easy-adhesion layer of 0.05 μm was the same as in Example 1. Got. The characteristics and evaluation results of the obtained film are shown in Table 1.

Example 15
In Example 1, except that the coating liquid A was replaced with the coating liquid M, the molding polyester film having the film thickness after film formation of 20 μm and the coating thickness of the easy adhesion layer of 0.05 μm was the same as in Example 1. Got. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution N)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size Water / isopropyl alcohol so that 1.12 μm silica particles are contained in an amount of 1.7% by mass with respect to the total resin, and silica particles having an average particle size of 0.06 μm are contained in an amount of 7.3% by mass with respect to the total resin. It diluted with the mixed solvent (= 65/35; mass ratio), and was set as the water-system coating agent.

Example 16
In Example 1, except that the coating solution A was replaced with the coating solution N, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution O)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size Water / Isople so that 1.86 μm benzoguanamine / formaldehyde crosslinked particles are contained in an amount of 1.0% by mass based on the total resin and silica particles having an average particle size of 0.06 μm are included in the total resin at 7.3% by mass It was diluted with a mixed solvent of pill alcohol (= 65/35; mass ratio) to obtain an aqueous coating agent.

Comparative Example 1
In Example 1, except that the coating solution A was replaced with the coating solution O, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution P)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size Water / Isople so that 0.9% by weight of melamine / formaldehyde crosslinked particles with respect to the total resin and 1.0% by weight of silica particles with an average particle size of 0.06 μm are included with respect to the total resin. It was diluted with a mixed solvent of pill alcohol (= 65/35; mass ratio) to obtain an aqueous coating agent.

Comparative Example 2
In Example 1, except that the coating solution A was replaced with the coating solution P, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution Q)
The ratio of the solid content of the polyester-based graft copolymer (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is polyester-based graft copolymer / polyurethane resin (mass ratio) = 95/5. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size Water / isopropyl alcohol so that 1.58 μm silica particles are contained in an amount of 1.0% by mass relative to the total resin and silica particles having an average particle size of 0.06 μm are contained in an amount of 7.3% by mass with respect to the total resin It diluted with the mixed solvent (= 65/35; mass ratio), and was set as the water-system coating agent.

Comparative Example 3
In Example 1, a polyester film for molding having a film thickness of 25 μm and an easy-adhesion layer applied thickness of 0.05 μm was obtained in the same manner as in Example 1 except that the coating liquid A was replaced with the coating liquid Q. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution R)
The ratio of the solid content of the polyester graft copolymer (a1) and the water dispersible polycarbonate urethane resin (b1) obtained above is polyester graft copolymer / polyurethane resin (mass ratio) = 80/20. In addition, the blocked isocyanate compound is mixed to 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle size In order to contain 0.83 μm of styrene / divinylbenzene crosslinked particles of 0.83 μm with respect to the total resin and 7.3% by mass of silica particles with an average particle diameter of 0.06 μm with respect to the total resin, It diluted with the mixed solvent (= 65/35; mass ratio) of the purpyl alcohol, and it was set as the water-system coating agent.

Example 17
In Example 1, except that the coating liquid A was replaced with the coating liquid R, a molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution S)
The ratio of the solid content of the copolymerized polyester resin liquid (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is copolymerized polyester resin / polyurethane resin (mass ratio) = 40/60, and A total of 100 parts by mass of the copolyester resin and the polyurethane resin is mixed so that the blocked isocyanate compound is 20 parts by mass, and the total resin solid content concentration is 2.8% by mass and the average particle size is 0.83 μm. A mixed solvent of water / isopropyl alcohol so that the divinylbenzene crosslinked particles are contained in an amount of 1.0% by mass with respect to the total resin and the silica particles having an average particle size of 0.06 μm are contained in an amount of 7.3% by mass with respect to the total resin. It diluted with (= 65/35; mass ratio) to make an aqueous coating agent.

Example 18
In Example 1, except that the coating solution A was replaced with the coating solution S, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution T)
The ratio of the solid content of the copolymerized polyester resin liquid (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is copolymerized polyester resin / polyurethane resin (mass ratio) = 80/20, and A total of 100 parts by mass of the copolyester resin and the polyurethane resin is mixed so that the blocked isocyanate compound is 40 parts by mass, and the total resin solid content concentration is 2.8% by mass and the average particle size is 0.83 μm. A mixed solvent of water / isopropyl alcohol so that the divinylbenzene crosslinked particles are contained in an amount of 1.0% by mass with respect to the total resin and the silica particles having an average particle size of 0.06 μm are contained in an amount of 7.3% by mass with respect to the total resin. It diluted with (= 65/35; mass ratio) to make an aqueous coating agent.

Example 19
In Example 1, a polyester film for molding having a film thickness of 25 μm and a coating thickness of the easy adhesion layer of 0.05 μm was obtained in the same manner as in Example 1 except that the coating liquid A was replaced with the coating liquid T. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution U)
The ratio of the solid content of the copolymerized polyester resin liquid (a1) and water-dispersible polycarbonate-based urethane resin (b1) obtained above is copolymerized polyester resin / polyurethane resin (mass ratio) = 80/20, and A total of 100 parts by mass of the copolyester resin and polyurethane resin is mixed so that the blocked isocyanate compound is 8 parts by mass, and the total resin solid content concentration is 2.8% by mass and the average particle size is 0.83 μm. A mixed solvent of water / isopropyl alcohol so that the divinylbenzene crosslinked particles are contained in an amount of 1.0% by mass with respect to the total resin and the silica particles having an average particle size of 0.06 μm are contained in an amount of 7.3% by mass with respect to the total resin. It diluted with (= 65/35; mass ratio) to make an aqueous coating agent.

Example 20
In Example 1, a polyester film for molding having a film thickness of 25 μm and an easy-adhesion layer applied thickness of 0.05 μm was obtained in the same manner as in Example 1 except that the coating liquid A was replaced with the coating liquid U. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating solution V)
The ratio of the copolymerized polyester resin liquid (a1) obtained above and a polyurethane resin (product name: Takelac W511, manufactured by Mitsui Chemicals, Inc.) having a glass transition point of 35 ° C. (catalog value) is a copolymerized polyester resin / polyurethane resin (mass Ratio) = 80/20, and the total amount of solid content of the resin is 2.8 masses, with mixing to be 20 mass parts of the blocked isocyanate compound with respect to 100 mass parts of the total amount of the copolyester resin and the polyurethane resin. % And an average particle size of 0.83 μm of styrene / divinylbenzene crosslinked particles in an amount of 1.0% by mass based on the total resin, and silica particles having an average particle size of 0.06 μm in an amount of 7.3% by mass based on the total resin. The mixture was diluted with a mixed solvent of water / isopropyl alcohol (= 65/35; mass ratio) to obtain an aqueous coating agent.

Example 21
In Example 1, a polyester film for molding having a film thickness of 25 μm and an easy-adhesion layer applied thickness of 0.05 μm was obtained in the same manner as in Example 1 except that the coating liquid A was replaced with the coating liquid V. The characteristics and evaluation results of the obtained film are shown in Table 1.

(Preparation of coating liquid W)
The polyester-based graft copolymer (a1) obtained above and the solid content of the ether-based polyurethane resin (trade name Takelac W6020, manufactured by Mitsui Chemicals) having a glass transition point of 90 ° C. (catalog value) are polyester-based grafts. Copolymer / polyurethane resin (mass ratio) = 80/20 and mixed so that the blocked isocyanate compound is 20 parts by mass with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and polyurethane resin. Styrene-divinylbenzene crosslinked particles having a total resin solid content concentration of 2.8% by mass and an average particle size of 0.83 μm are 1.0% by mass based on the total resin, and silica particles having an average particle size of 0.06 μm are all resin Diluted with a mixed solvent of water / isopropyl alcohol (= 65/35; mass ratio) so as to contain 7.3% by mass with respect to the aqueous coating. And the.

Example 22
In Example 1, except that the coating liquid A was replaced with the coating liquid W, a molding polyester film having a film thickness of 25 μm and an easily adhesive layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

Example 23
In the preparation of the coating liquid H, a coating liquid (X) in which a melamine compound (Becamine M-3 solid content concentration: 60% by DIC) was changed to 16.7% by mass in the solid content instead of the blocked isocyanate compound was used. Except for the above, a laminated polyester film having an easy-adhesion layer coating thickness of 0.05 nm was obtained in the same manner as in Example 8. Table 1 shows the properties and evaluation results of the obtained single-layer film.

Comparative Example 4
A laminated polyester film having an easy-adhesion layer coating thickness of 0.05 nm was obtained in the same manner as in Example 4 except that only a polyethylene terephthalate chip (B) having an intrinsic viscosity of 0.69 dl / g was used as a film raw material. Table 1 shows the properties and evaluation results of the obtained single-layer film.

(Preparation of coating liquid Y)
The ratio of the solid content of the copolyester resin liquid (a1) obtained above and the water-dispersible polycarbonate urethane resin (b1) is copolyester resin / polyurethane resin (mass ratio) = 0/100, and Mixing so that the blocked isocyanate compound is 20 parts by mass with respect to 100 parts by mass of the polyurethane resin , and the total resin solid content concentration is 2.8% by mass and the average particle size is 0.83 μm. Water / isopropyl alcohol mixed solvent (= 65/35; mass ratio) so as to contain 1.0% by mass of silica particles having an average particle size of 0.06 μm with respect to the total resin of 7.3% by mass. ) To obtain an aqueous coating agent.

Example 24
In Example 1, except that the coating liquid A was replaced with the coating liquid Y, a molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1. The characteristics and evaluation results of the obtained film are shown in Table 1.

The polyester film for insert molding according to the present invention is suitable for forming a mirror-like decorative layer excellent in adhesiveness and surface feeling. Therefore, in decorative molding materials such as interior decorations and exterior decorations for automobiles, home appliance membrane switches, mobile phone base materials, building material members, etc. Is preferred.

1. Base 2,8. Film press 2a. Slot 2c. Hole 2d. 2. pores Screws 4,5. Film 6. 6. Vacuum pump Pipe X. Film overlap

Claims (6)

Having an easy-adhesion layer on at least one side of the polyester film,
The polyester film consists of copolymer polyester, or copolymer polyester and homopolyester,
The easy-adhesion layer includes at least one kind of particles whose essential particles are particles A having a particle size distribution (d75 / d25) of 1.1 to 1.5 and an average particle size d of 0.04 to 1.2 μm,
The ratio (d / t) between the average particle diameter d of the particles A and the thickness t of the easy-adhesion layer is 5 or more and 100 or less,
The thickness of the polyester film is 15-100 μm,
A polyester film for insert molding having a reflection intensity (Wa) of 4.0 mm or less in a wavelength range of 0.1 mm to 0.3 mm measured using a wave scanning device on the surface of the easy adhesion layer of the film. Polyester film for insert molding according to claim 1 wherein the easily-adhesive layer comprises polyester resin, polyurethane resin, or at least one of the binder resins of acrylic resin. The easy adhesion layer includes a polyester resin and a polyurethane resin,
The polyester resin is claimed in claim 2 in a hydrophobic copolymerizable polyester resin is at least one double bond polymerizable comprising an acid anhydride having an unsaturated single polyester dimer grafted graft copolymer Polyester film for insert molding. The polyester film for insert molding according to claim 2 or 3 , wherein the polyurethane resin is a polycarbonate-based polyurethane resin. Containing 0.01 to 3% by mass of the particle A with respect to the total resin of the easy adhesion layer,
The haze of the film is 2.0% or less, the static friction coefficient between the easy-adhesion layer surfaces is 0.9 or less, the dynamic friction coefficient between the easy-adhesion layer surfaces is 0.8 or less, and the air escape index is 200 seconds or less. 4. The polyester film for insert molding according to any one of 4 above.   The decorative film for plating substitutes which has a metal vapor deposition layer in one surface of the polyester film for insert molding in any one of Claims 1-5.