JP2016064974A - Laminated film for glass laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film for a glass laminate which keeps transparency without precipitating a cyclic trimer in a step of laminating a heat-ray shielding layer on a laminated polyester film and a step of processing a glass laminate, and has favorable appearance.SOLUTION: A laminated film has a resin layer (α) containing an aliphatic urethane structure on at least one surface of a laminated polyester film including at least three layers. A surface free energy of the resin layer (α) is 30 mN/m or more and 45 mN/m or less. The laminated polyester film having the resin layer (α) satisfies the following requirements (a) and (b): (a) a change (ΔH) in haze before and after the laminated film is heated at 135°C for 30 minutes is 1.0% or less; and (b) a thermal shrinkage when the laminated film is heated at 135°C for 30 minutes in both a longitudinal direction and a width direction of the film is 2.0% or more and 4.5% or less.SELECTED DRAWING: None

Description

  The present invention relates to a laminated film for laminated glass.

  2. Description of the Related Art In recent years, in architectural and vehicle window glasses, functions such as ultraviolet ray shielding and infrared ray shielding (heat ray reflection) have been increasing. As a method for imparting a function to glass, a method using a laminated glass having an intermediate film provided with a functional layer between two glass plates is known. Above all, laminated glass that shields heat from the outside (heat-shielded laminated glass) suppresses the inflow of heat from the outside of the summer, especially sunlight, and reduces the temperature rise in the room and the interior of the car, thereby reducing the amount of air conditioning used. Because it can reduce and contribute to energy saving, it is attracting attention as a window glass of buildings and windows of vehicles such as automobiles and trains.

  As such a heat ray shielding laminated glass, a laminated glass in which a plurality of glasses are bonded with an intermediate film formed of a resin having a heat ray shielding function is widely used. For example, a heat ray absorbing agent is contained in the resin forming the intermediate film and the heat ray is shielded by the heat ray absorbent (for example, Patent Document 1), or a heat ray shielding layer is vacuum-deposited on a film formed of polyester or the like. There is known a method (for example, Patent Documents 2 to 4) using a laminate formed by a method, a sputtering method, a coating method, or the like as an intermediate film.

JP-A-8-217500 JP-A-56-32352 JP-A-6-191906 JP 2000-927 A

  However, in the method using a heat ray absorbent as in Patent Document 1, the glass temperature partially rises by absorbing heat rays incident from the outside, and the glass body may be damaged due to a difference from the outside air temperature. . Moreover, in the method of laminating a heat ray shielding layer on a film formed of polyester or the like as in Patent Documents 2 to 4, oligomers are precipitated from the film formed of polyester or the like due to the thermal load applied when laminating the heat ray shielding layer. However, this may impair transparency. Analysis of this oligomer gave the knowledge that the cyclic trimer is the main component. Therefore, in order to suppress the decrease in the transparency of the polyester film due to the heat load, it is necessary to suppress the precipitation of the cyclic trimer on the film surface. Moreover, when using for the laminated glass of a shape with a curved surface, a film may not follow the curved surface of glass, a wrinkle may arise and an external appearance may be impaired.

  In view of the above-described problems of the prior art, the present invention maintains transparency by suppressing the precipitation of oligomers (particularly cyclic trimers) even in the process of laminating a heat ray shielding layer on a laminated film and the process of processing laminated glass. It is an object of the present invention to provide a laminated film for laminated glass that is excellent in adhesiveness with laminated glass and has a good appearance without causing wrinkles in the laminated glass processing step.

In order to solve the above problems, the present invention has the following configuration.
(1) A laminated film having a resin layer (α) containing an aliphatic urethane structure on at least one side of a laminated polyester film comprising at least three layers, the surface free energy of the resin layer (α) being 30 mN / m As mentioned above, it is 45 mN / m or less, and the laminated film for laminated glass with which the laminated film satisfy | fills the requirements of the following (a) and (b).
(A) The haze change (ΔH) before and after heating the laminated film at 135 ° C. for 30 minutes is 1.0% or less.
(B) The heat shrinkage rate when the laminated film is heated at 135 ° C. for 30 minutes is 2.0% or more and 4.5% or less in both the film longitudinal direction and the width direction.
(2) The laminated film for laminated glass according to (1), wherein the internal haze is 0.5% or less.
(3) The laminated film for laminated glass according to (1) or (2), wherein the thickness of the resin layer (α) is 30 nm or more and 100 nm or less.
(4) The laminated film for laminated glass according to any one of (1) to (3), wherein the resin layer (α) contains particles having an average particle diameter of 20 nm to 300 nm.
(5) The laminated film for laminated glass according to any one of claims 1 to 4, wherein the haze is 1.5% or less.
(6) The laminated polyester film according to any one of (1) to (5), wherein both outermost polyester layers of the laminated polyester film satisfy the following requirements (a), (b), and (c): Laminated film.
(A) The thickness of both polyester layers of the outermost layer is 5 μm or more. (B) The cyclic trimer content of the polyester composition constituting both polyester layers of the outermost layer is the polyester of both outermost layers. 0.5% by weight or less based on the entire polyester composition constituting the layer (c) The polyester composition constituting both polyester layers of the outermost layer contains a germanium element (7) The laminated polyester The germanium element contained in the polyester composition constituting both polyester layers of the outermost layer of the film is 10 to 400 ppm relative to the entire polyester composition constituting both polyester layers of the outermost layer. The laminated film for laminated glass according to any one of (1) to (6).
(8) The cyclic trimer content contained in the polyester composition constituting the polyester layer excluding the outermost layer of the laminated polyester film is based on the entire polyester composition constituting the polyester layer excluding the outermost layer. The laminated film for laminated glass according to any one of (1) to (7), which is 2.0% by weight or less.
(9) The laminated film for laminated glass according to any one of (1) to (8), wherein the total light transmittance is 88% or more.

  According to the present invention, in the process of laminating a heat ray shielding layer on a laminated film and the laminated glass processing process, the precipitation of the cyclic trimer is suppressed to maintain the transparency, the adhesiveness with the laminated glass is excellent, and the appearance is good. A laminated film for laminated glass can be provided.

  Embodiments of the present invention will be described below, but the present invention is not construed as being limited to the embodiments including the following examples, and can achieve the object of the invention and depart from the gist of the invention. Various changes within the range not to be made are naturally possible.

  The laminated polyester film of the laminated film of the present invention is produced by a polycondensation reaction between a difunctional component such as an aromatic dicarboxylic acid or an alkyl ester thereof and a glycol component. In particular, those containing polyethylene terephthalate as the main component are preferred.

  Such polyester may be a copolymer obtained by copolymerizing a small amount of the third component as long as the basic properties of the laminated polyester film of the present invention are not impaired, or may be a mixture of these polyesters. Examples of the copolymer component include dicarboxylic acid components such as 2,6-naphthalenedicarboxylic acid and isophthalic acid, oxycarboxylic acid components such as p-oxyethoxybenzoic acid, and tetramethylene glycol, propylene glycol, neopentyl glycol, poly Examples of the diol component include oxyalkylene glycol, p-xylylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol, and 5-sodium sulforesorzine.

  The polyester in the present invention can be obtained by a conventionally known method. For example, after obtaining a low-polymerization degree polyester directly by reaction of dicarboxylic acid and diol, a polymerization reaction is performed in the presence of a polymerization catalyst, or a lower alkyl ester of dicarboxylic acid and diol are reacted with a conventionally known transesterification catalyst. Thereafter, it can be obtained by a method of performing a polymerization reaction in the presence of a polymerization catalyst. As the polymerization catalyst, a known catalyst such as an antimony compound, a germanium compound, or a titanium compound can be used.

  The polyester may be converted into chips after solution polymerization and further solid-phase polymerization may be performed as necessary under heating under reduced pressure or in an inert gas stream such as nitrogen.

  The polyester constituting the laminated polyester film of the present invention includes various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, heat stabilizers, lubricants, infrared rays. An absorber, an ultraviolet absorber, or the like may be added.

The laminated polyester film of the present invention is a polyester film composed of at least three layers, and it is a preferred embodiment that both the outermost polyester layers satisfy the following requirements (a), (b), and (c). .
(A) The thickness of both polyester layers of the outermost layer is 5 μm or more.
(B) The cyclic trimer content of the polyester composition constituting both polyester layers of the outermost layer is 0.5% by weight or less with respect to the entire polyester composition constituting both polyester layers of the outermost layer. about.
(C) The polyester composition constituting both polyester layers of the outermost layer contains a germanium element.

  The laminated polyester film of the present invention has a polyester layer composed of a polyester composition having a low cyclic trimer content in the outermost layer, thereby suppressing the precipitation of the cyclic trimer on the film surface by heating, An increase in haze (deterioration of transparency) due to precipitation of the cyclic trimer on the surface can be suppressed. That is, the cyclic trimer content of the polyester composition constituting both polyester layers of the outermost layer is 0.5% by weight or less with respect to the entire polyester composition constituting both polyester layers of the outermost layer. Is more preferable, and 0.4% by weight or less is more preferable. When the cyclic trimer content of the polyester composition constituting both polyester layers of the outermost layer exceeds 0.5% by weight, it is cyclic on the surface of the laminated polyester film in the step of laminating the heat ray shielding layer and the laminated glass processing step. A trimer may precipitate and transparency may deteriorate. In the laminated polyester film of the present invention, the polyester constituting the outermost layer on one side and the polyester constituting the other outermost layer may be the same polyester or different polyesters.

  In the laminated polyester film of the present invention, the cyclic trimer content of the polyester composition constituting the polyester layer excluding the outermost layer is 2 with respect to the entire polyester composition constituting the polyester layer excluding the outermost layer. It is preferable that it is 0.0 weight% or less. More preferably, it is 1.5% by weight or less. When the cyclic trimer content of the polyester composition constituting the polyester layer excluding the outermost layer exceeds 2.0% by weight, the cyclic trimer content of the polyester composition constituting the outermost polyester layer is reduced. Even if it does, precipitation of the cyclic trimer from the polyester layer except the outermost layer may occur, and the precipitation of the cyclic trimer on the film surface may not be prevented. Moreover, the lower limit of the cyclic trimer content of the polyester composition constituting the polyester layer excluding the outermost layer is not particularly limited, but 0.5% by weight or more is preferable from the viewpoints of economy and production stability.

  In the laminated polyester film of the present invention, it is preferable that the thickness of both outermost polyester layers is 5 μm or more. More preferably, it is 7 μm or more. When the thickness is less than 5 μm, the cyclic trimer is precipitated on the film surface from the polyester layer excluding the outermost layer due to the thermal load received in the process of making laminated glass or the process of laminating the heat ray shielding layer. It cannot be suppressed, the haze increases, and the transparency of the laminated glass may be impaired. The upper limit of the thickness of the outermost polyester layer is not particularly defined, but if it exceeds 20 μm, stable film formation becomes difficult and it may be difficult to improve productivity.

  In general, as a method for producing a polyester having a low cyclic trimer content, a polyester obtained by melt polymerization is further subjected to solid-phase polymerization at a temperature below the melting point of the polyester, A method of performing heat treatment under an active gas is known. However, after obtaining a polyester having an intrinsic viscosity of, for example, 0.45 to 0.70 dl / g by melt polymerization, solid phase polymerization is performed to obtain a polyester having a reduced cyclic trimer content. Since it becomes as high as 0.70 dl / g or more, the melt viscosity at the time of melt extrusion is high, and stable film formation may be difficult. Moreover, when melt viscosity is high, the load to an extruder becomes large and it may become difficult to raise production capacity. That is, a single-layer polyester film made of polyester having a low cyclic trimer content and a high intrinsic viscosity suppresses cyclic trimer precipitation on the film surface and maintains high transparency when subjected to a thermal load. Although it is possible, it is difficult to stably form a film, and it is difficult to improve production capacity. In order to make the intrinsic viscosity of the polyester after solid phase polymerization stable enough to form a film stably, the intrinsic viscosity of the polymer obtained by melt polymerization is lowered to, for example, 0.45 dl / g or less, and this is subjected to solid phase polymerization. Although it is possible to obtain a polyester with a low intrinsic viscosity and a low cyclic trimer, if the intrinsic viscosity after melt polymerization is low, the diameter when discharging into a strand after melt polymerization becomes unstable, and the resulting chip shape Is not stable. For example, in the case of solid-phase polymerization of polyethylene terephthalate, the polymerization rate of solid-phase polymerization is improved by removing ethylene glycol generated by the polycondensation reaction outside the system. When solid phase polymerization is used, there is a difference in the surface area of each chip, so that the degree of polymerization (inherent viscosity) varies greatly. When film formation is performed using a polyester chip having a large variation in the degree of polymerization (intrinsic viscosity), film breakage occurs during film formation, and it is difficult to obtain a film having stable characteristics. In addition, when a film is formed using a polyester chip having a large variation in shape, it may cause a biting failure when supplied to an extruder. In addition, as a method of reducing the content of the cyclic trimer, in the method of heat treatment under an inert gas at normal pressure, solid phase polymerization does not proceed and the intrinsic viscosity does not increase, but acetaldehyde generated during heating Since the decomposition gas such as is not excluded from the system, the color tone and transparency are likely to deteriorate. Therefore, from the viewpoint of productivity improvement due to stable film formation and reduced load on the extruder, the laminated polyester film of the present invention comprises at least three layers, and the outermost polyester layer comprises the aforementioned (x), (y), It is a preferable aspect to satisfy the preferable requirement of (z).

  In the laminated polyester film of the present invention, the intrinsic viscosity of the polyester composition constituting both the outermost polyester layers is preferably 0.7 to 0.9 dl / g. Moreover, it is preferable that the intrinsic viscosity of the polyester composition which comprises the polyester layer except an outermost layer is 0.4-0.7 dl / g. By setting the intrinsic viscosity of the polyester composition within the above range, stable film formation can be achieved, and the load on the extruder can be reduced to easily increase the production capacity.

  The thickness of the laminated polyester film of the present invention is preferably 25 μm to 125 μm, more preferably 38 μm to 100 μm from the viewpoint of suppressing wrinkles in the laminated glass processing step. When the film thickness is less than 25 μm, the workability when using laminated glass may deteriorate. On the other hand, when the film thickness is thicker than 125 μm, wrinkles may easily occur in the laminated glass processing step.

  The laminated polyester film of the present invention preferably has an internal haze of 0.5% or less. The internal haze is a value obtained by a measurement method described later, and is an index that represents the transparency of the film excluding the influence of the film surface shape (protrusions, irregularities, etc.) caused by foreign matter or particles inside the film. is there. Preferably it is 0.3% or less, More preferably, it is 0.2% or less. When a laminated polyester film having an internal haze exceeding 0.5% is used as a laminated glass, the transparency is impaired and the visibility is inferior. In order to set the internal haze in the above range, a method of reducing the particles contained in the polyester constituting the laminated polyester film, a method of reducing the cyclic trimer contained in the polyester constituting the polyester film, and a polyester film are constituted. For example, a polyester obtained by using a catalyst (for example, germanium) that hardly generates foreign matters as the polyester to be used can be used.

  Furthermore, the laminated film of the present invention preferably has a haze of 1.5% or less. In the present invention, the haze is a value obtained by a measurement method described later, and is an index representing transparency like the internal haze, but not only the haze caused by foreign matter or particles inside the film, but also the film surface. It also includes the influence of the shape (projections and irregularities). Preferably it is 1.0% or less, More preferably, it is 0.5% or less. When the haze of the film is greater than 1.5%, transparency may be impaired when a laminated glass is used. In order to make the haze within the above range, a method of reducing the particles contained in the polyester constituting the outermost layer of the laminated polyester film, a method of reducing the cyclic trimer contained in the polyester constituting the outermost layer of the polyester film , A method using a polyester obtained by using a catalyst (for example, germanium) that does not easily generate foreign matters as a polyester constituting the outermost layer of the polyester film, and an average particle diameter of particles contained in the resin layer (α) as a specific range. The method of doing is mentioned.

  The laminated film of the present invention preferably has a total light transmittance of 88% or more. More preferably, it is 90% or more. If the total light transmittance is less than 88%, the visibility may be deteriorated. On the other hand, when the heat ray shielding component is reduced in order to prevent deterioration in visibility, the target heat ray shielding performance may not be achieved.

  The laminated polyester film of the present invention preferably contains a germanium element in the polyester composition constituting both the outermost polyester layers. By including a germanium element in the polyester composition constituting both polyester layers of the outermost layer, an increase in the cyclic trimer content in the film forming step is suppressed, and a processing step of laminating a heat ray shielding layer and Precipitation of the cyclic trimer on the film surface due to heat load in the laminated glass processing step can be suppressed. The reason is estimated as follows. As a polymerization catalyst for polyester, an antimony compound, a germanium compound, a titanium compound, or the like is generally known. However, a germanium compound has a lower thermal decomposition activity than an antimony compound or a titanium compound. Therefore, the polyester obtained using a germanium compound as a polymerization catalyst is considered to be able to suppress the progress of thermal decomposition even under conditions where a thermal load is applied, and to suppress the formation of a cyclic trimer. . Moreover, since the polyester obtained by performing polycondensation reaction using a germanium compound has few foreign materials, transparency is favorable and it can make an internal haze and a haze small. From the viewpoint of suppressing the formation of the cyclic trimer and the precipitation of the cyclic trimer on the film surface, and from the viewpoint of setting the internal haze of the laminated polyester film in a preferable range, the polyester composition constituting the outermost polyester layer It is preferable that the germanium element contained therein is 10 to 400 ppm with respect to the entire polyester composition constituting the outermost polyester layer.

  The laminated film of the present invention needs to have a haze change (ΔH) of 1.0% or less before and after heating at 135 ° C. for 30 minutes. More preferably, it is 0.5% or less. When ΔH is larger than 1.0%, the haze of the film rises due to the thermal load received when the heat ray shielding layer is laminated on the laminated film of the present invention, and the transparency is lowered when the laminated glass is formed.

  The increase in haze due to heating is thought to be due to the precipitation of cyclic trimers on the film surface. In order to make ΔH within the above range, the cyclic trimer content of the polyester constituting both polyester layers of the outermost layer is reduced, or the polyester constituting both polyester layers of the outermost layer is subjected to heat load. For example, a method using a polyester with a small amount of precipitated cyclic trimer when it is subjected, and a method of containing a specific structure in the resin layer (α).

  The laminated film of the present invention needs to have a thermal shrinkage ratio of 2.0% or more and 4.5% or less in both the film longitudinal direction and the width direction when heat-treated at 135 ° C. for 30 minutes. More preferably, they are 2.5% or more and 4.0% or less, More preferably, they are 3.0% or more and 3.5% or less. If the heat shrinkage rate is less than 2.0%, the film cannot follow the shape of the laminated glass when it is processed into a laminated glass, which causes wrinkles and causes poor appearance. Wrinkles that occur when processing into laminated glass are more likely to occur as the curved surface of the laminated glass is curved. Therefore, by limiting the heat shrinkage rate to the above range, the shape of applicable laminated glass is limited. Disappears. On the other hand, if the heat shrinkage rate is greater than 4.5%, the wrinkle of the curved portion is suppressed when processed into a laminated glass, but the shrinkage of the product edge occurs due to the heat shrinkage, resulting in a large product loss. End up. The thermal shrinkage rate can be set to the above range by controlling the film forming conditions (particularly the heat treatment conditions). For example, when the film of the present invention is a film made of polyethylene terephthalate, the heat treatment temperature after the stretching step is in the range of 160 to 210 ° C., and after the first stage heat treatment in the range of 160 to 180 ° C., 190 to 190 ° C. By performing the second stage heat treatment in the range of 210 ° C., the thermal shrinkage rate can be set in the above range. In the present invention, for a film whose longitudinal direction and width direction are unknown, the refractive index of the film is analyzed, and the direction having the maximum refractive index is regarded as the width direction, and the direction orthogonal thereto is regarded as the longitudinal direction.

  The laminated film of the present invention has a resin layer (α) on at least one side of the laminated polyester film in order to obtain adhesion with laminated glass.

  The resin layer (α) included in the laminated film of the present invention needs to have a surface free energy (the sum of dispersion force and polar force) of 30 mN / m or more and 45 mN / m or less. The surface free energy, the dispersion force, and the polar force as used in the present invention refer to values calculated by a measurement method described later.

  As an interlayer film of laminated glass, a film obtained by bonding a flexible polyvinyl butyral resin (PVB resin) and a laminated film may be used. At this time, when the surface free energy of the resin layer (α) is less than 30 mN / m, the adhesion between the laminated film and the PVB resin is deteriorated. On the other hand, when surface free energy exceeds 45 mN / m, the adhesiveness in a high-temperature, high-humidity environment will deteriorate. More preferably, they are 33 mN / m or more and 43 mN / m or less, More preferably, they are 35 mN / m or more and 40 mN / m or less.

The method for setting the surface free energy of the resin layer (α) of the present invention in the above range is not particularly limited, but representative methods include the following methods (I) to (II). .
(I) The resin composition (I) forming the resin layer (α) includes an aliphatic urethane resin (B) obtained by polymerizing an acrylic-modified polyester resin (A), an aliphatic polyisocyanate compound, and a polyol compound. A resin obtained from a resin, wherein the ratio of the resin (A) and the resin (B) is a specific ratio.
(II) The resin composition (I) forming the resin layer (α) includes an aliphatic urethane resin (B) obtained by polymerizing an acrylic-modified polyester resin (A), an aliphatic polyisocyanate compound, and a polyol compound. A method of containing a melamine compound and / or a carbodiimide compound (C) in addition to the resin and setting the ratio of the resin (A), the resin (B), and the melamine compound and / or the carbodiimide compound (C) to a specific ratio.

  In the present invention, the resin layer (α) needs to contain an aliphatic urethane structure. When the resin layer (α) contains an aliphatic urethane structure, it is possible to improve the adhesiveness with the PVB resin used between the laminated glasses.

  The resin layer (α) can be obtained by applying and drying a resin composition (I) described later on a laminated polyester film.

  The resin composition (I) forming the resin layer (α) containing the aliphatic urethane structure of the present invention preferably contains an acrylic modified polyester resin (A). By changing the content and composition of the acrylic-modified polyester resin (A) in the resin composition (I), the surface free energy of the resin layer (α) can be within the range of the present invention.

  The acrylic-modified polyester resin (A) that can be used in the present invention is one in which an acrylic resin component and a polyester resin component are mixed and / or bonded to each other, and includes, for example, a graft type and a block copolymer type. In addition, either the mixing ratio or copolymerization ratio of the acrylic resin component and the polyester resin component in the acrylic-modified polyester resin (A) may be higher.

  Acrylic-modified polyester resin (A) is, for example, adding a radical initiator to both ends of the polyester to polymerize the acrylic monomer, or adding a radical initiator to the side chain of the polyester to polymerize the acrylic monomer. Or by attaching a hydroxyl group to the side chain of the acrylic resin and reacting with a polyester having an isocyanate group or a carboxyl group at the terminal.

  Increasing the acrylic resin component in the acrylic-modified polyester resin (A) can lower the surface free energy of the resin layer (α), and decreasing the acrylic resin component increases the surface free energy of the resin layer (α). Can do. In order to make the surface free energy of the resin layer (α) within the scope of the present invention, the mass ratio of the acrylic resin component to the polyester resin component in the acrylic-modified polyester resin (A) (content of acrylic resin component [parts by mass] / The content [parts by mass] of the polyester resin component is preferably 10/90 or more and 90/10 or less.

  The acrylic-modified polyester resin (A) preferably has a structure represented by the following formulas (1) to (5). When the acrylic-modified polyester resin (A) has the structure of the formulas (1) to (5), when laminated with the laminated glass, the adhesion with the PVB resin used between the laminated glasses can be improved. . Especially, it is preferable that it is contained as a structure of the acrylic resin component of acrylic modified polyester resin (A).

  Specifically, in the acrylic resin component constituting the acrylic-modified polyester resin (A), a hydrophilic radical-polymerizable vinyl monomer is polymerized on the main chain of the acrylic resin composed of alkyl methacrylate and / or alkyl acrylate. It is preferable. By containing this hydrophilic radically polymerizable vinyl monomer in the acrylic resin component, the structure of the formulas (1) to (5) can be imparted to the acrylic-modified polyester (A).

  As alkyl methacrylate and / or alkyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, 2-hydroxy methacrylate Use ethyl, hydroxypropyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, etc. Is preferred. These can be used alone or in combination of two or more.

  Specific examples of the hydrophilic radical polymerizable vinyl monomer having a structure represented by the formula (1) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and the like. As a monomer having a structure of formula (2), a glycol ester such as ethylene glycol acrylate, ethylene glycol methacrylate, polyethylene glycol acrylate, or polyethylene glycol methacrylate, a monomer having a structure of formula (3) Acrylamide compounds such as acrylamide, methacrylamide, N-methylol acrylamide, methoxymethylol acrylamide, and the like. , Cationic monomers such as aminoalkyl methacrylate and quaternary ammonium salts thereof, monomers having the structure of formula (5) include glycidyl acrylate compounds such as glycidyl acrylate and glycidyl methacrylate, acrylic acid, Examples thereof include unsaturated acids such as methacrylic acid, maleic anhydride, itaconic acid and crotonic acid, and salts thereof. The hydrophilic radical polymerizable monomer may be used alone or in combination of several kinds. Furthermore, these hydrophilic monomers can be used in combination with other copolymerizable vinyl monomers.

  Other vinyl monomers that can be copolymerized include vinyl esters such as vinyl acetate and vinyl propionate, vinyl halides such as vinyl chloride and vinyl bromide, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and methacrylic acid. Examples include unsaturated carboxylic acid esters such as ethyl acrylate and butyl methacrylate, vinyl silanes such as dimethylvinylmethoxysilane and γ-methacryloxypropyltrimethoxysilane, olefins such as ethylene, propylene, styrene, and butadiene, and diolefin compounds. .

  The polyester resin component constituting the acrylic-modified polyester resin (A) has an ester bond in the main chain or side chain, and is composed of a dicarboxylic acid component and a diol component. As the carboxylic acid component constituting the polyester resin, aromatic, aliphatic, and alicyclic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids can be used. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 5-sodium sulfoisophthalic acid, 1,4-naphthalenedicarboxylic acid, and ester-forming derivatives thereof Can be used.

  As the glycol component of the polyester resin, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and the like are used. be able to.

  Further, when the polyester resin component is dissolved or dispersed in an aqueous solvent and used as an aqueous resin composition, a compound containing a sulfonate group or a carboxylate base is used to facilitate water-solubilization or water-dispersion of the polyester resin component. It is preferable to copolymerize a compound containing

  Examples of the compound containing a carboxylate group include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, 1,2, Examples include, but are not limited to, alkali metal salts such as 3,4-butanetetracarboxylic acid and 1,2,3,4-pentanetetracarboxylic acid, alkaline earth metal salts, ammonium salts, and the like. is not.

  Examples of the compound containing a sulfonate group include alkali metal salts, alkaline earth metal salts, and ammonium salts such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 5-sodium sulfoisophthalic acid, and 4-sulfoisophthalic acid. However, the present invention is not limited to this.

  The acrylic-modified polyester resin (A) used for the resin composition (I) that forms the resin layer (α) of the present invention can be produced, for example, by the following production method. First, a polyester resin component is produced as follows. For example, a first stage process in which a dicarboxylic acid component and a glycol component are directly esterified, or a dicarboxylic acid component and a glycol component are transesterified, and a second stage in which the reaction product of the first stage is subjected to a polycondensation reaction. It can manufacture by the method etc. which manufacture with a process. At this time, as the reaction catalyst, for example, alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compound, or the like can be used.

  Next, the polyester resin component is dispersed in a solvent. In particular, as a dispersion means in an aqueous solvent, the polyester resin is dissolved in an aqueous solution of an alkaline compound such as ammonia water, sodium hydroxide, potassium hydroxide, various amines or the like while stirring. Disperse. In this case, a water-soluble organic solvent such as methanol, ethanol, isopropanol, butyl cellosolve, or ethyl cellosolve may be used in combination.

  Subsequently, in order to produce the acrylic-modified polyester resin (A), a polymerization initiator and, if necessary, an emulsifying dispersant are added to the dispersion of the polyester resin component, and the acrylic resin component is gradually added while keeping the temperature constant. It can be added and then reacted for several hours to produce a dispersion of acrylic modified polyester. The obtained dispersion is a mixture of an acrylic-modified polyester resin component, a polyester resin component, and an acrylic resin component.

  The polymerization initiator is not particularly limited, but is a general radical polymerization initiator, for example, a water-soluble peroxide such as potassium persulfate, ammonium persulfate, hydrogen peroxide, or benzoyl peroxide or t-butyl hydroper Oil-soluble peroxides such as oxides or azo compounds such as azodiisobutyronitrile can be used.

  The resin layer (α) of the present invention is required to contain an aliphatic urethane structure. The aliphatic urethane structure is an aliphatic urethane resin obtained by polymerizing an aliphatic polyisocyanate compound and a polyol compound ( B) is preferred.

  First, the aliphatic polyisocyanate compound used in the present invention will be described. As the aliphatic polyisocyanate compound used in the present invention, those having a plurality of isocyanate groups in the molecule are preferable. For example, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2, 4-trimethylhexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, bis (4-isocyanatocyclohexyl) methane, dicyclohexylmethane 4,4-diisocyanatotrizine diisocyanate, hydrogenated xylylene diisocyanate And hydrogenated phenylmethane diisocyanate. In addition, the aliphatic polyisocyanate compound used for this invention may be one type, or may be two or more types.

  In the present invention, any of the aliphatic polyisocyanate compounds described above can be suitably used, and among them, it is preferable to use an alicyclic polyisocyanate compound. The aliphatic urethane resin (B) polymerized from the alicyclic polyisocyanate compound has a high glass transition point among the aliphatic urethane resins.

  Next, the polyol compound used in the present invention will be described. The polyol compound used in the present invention is not particularly limited as long as it has a plurality of hydroxyl groups. Examples of such polyol compounds include aromatic polyether polyols, aliphatic polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols. Hereinafter, specific examples of these polyol compounds will be described in order.

  Examples of the aromatic polyether polyol include bisphenol A ethylene oxide addition diol, bisphenol A propylene oxide addition diol, bisphenol A butylene oxide addition diol, bisphenol F ethylene oxide addition diol, bisphenol F propylene oxide addition diol, Examples thereof include a propylene oxide addition diol of bisphenol F, an alkylene oxide addition diol of hydroquinone, and an alkylene oxide addition diol of naphthoquinone.

  Examples of the aliphatic polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, polyisobutylene glycol, a copolymer polyol of propylene oxide and tetrahydrofuran, and a copolymer weight of ethylene oxide and tetrahydrofuran. Among the combination polyols, copolymer polyols of ethylene oxide and propylene oxide, copolymer polyols of tetrahydrofuran and 3-methyl_tetrahydrofuran, copolymer polyols of ethylene oxide and 1,2-butylene oxide, and aliphatic polyether polyols Examples of the alicyclic polyether polyol include hydrogenated bisphenol A ethylene oxide addition diol and hydrogenated bisphenol A propylene. Rene oxide addition diol, hydrogenated bisphenol A butylene oxide addition diol, hydrogenated bisphenol F ethylene oxide addition diol, hydrogenated bisphenol F propylene oxide addition diol, hydrogenated bisphenol F butylene oxide addition diol, dicyclopentadiene dimethylol Examples thereof include compounds and tricyclodecane dimethanol.

  Examples of the polyester polyol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 3-methyl. Polyhydric alcohols such as -1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, Examples thereof include polyester polyols obtained by reacting with polybasic acids such as sebacic acid.

  Examples of the polycarbonate polyol include 1,6-hexane polycarbonate.

  Examples of the polycaprolactone polyol include ε-caprolactone, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neo Examples thereof include polycaprolactone diols obtained by reacting divalent diols such as pentyl glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol.

  Other examples of the polyol compound that can be used in the present invention include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 1,4. -Cyclohexanedimethanol, poly β-methyl-δ-valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, polydimethylsiloxane-terminated diol compound, polydimethylsiloxane carbitol-modified polyol .

In addition, the polyol compound used for this invention may be one type, or may be two or more types.

  From the above points, the specific structure of the aliphatic urethane resin (B) used in the present invention is particularly preferably composed of the following aliphatic polyisocyanate compound and aliphatic polyether polyol. Aliphatic polyisocyanate compounds include 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, bis (2-isocyanate). Examples thereof include ethyl) fumarate, bis (4-isocyanatocyclohexyl) methane, dicyclohexylmethane 4,4-diisocyanatotrizine diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated phenylmethane diisocyanate.

  Examples of the aliphatic polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, and polyisobutylene glycol.

  The aliphatic urethane resin (B) used in the present invention is obtained by dissolving or dispersing a chain extender in water as required in addition to the aliphatic polyisocyanate compound and the polyol compound. Polymerized.

  As chain extenders, ethylene glycol, 1,4-butanediol, trimethylolpropane, triisopropanolamine, N, N-bis (2-hydroxypropyl) aniline, hydroquinone-bis (β-hydroxyethyl) ether, resorcinol- Polyols such as bis (β-hydroxyethyl) ether, ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, tolylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminodiphenylmethane, diaminodicyclohexylmethane, piperazine, isophoronediamine, diethylenetriamine, dipropylene Examples include polyamines such as triamine, hydrazines, and water.

  The content of the aliphatic urethane resin (B) in the resin composition (I) forming the resin layer (α) is not particularly limited, but relative to the resin composition (I) forming the resin layer (α) In addition, it is preferably 6% by mass or more. More preferably, it is 20 mass% or more and 50 mass% or less.

  The total content of the acrylic-modified polyester resin (A) and the aliphatic urethane resin (B) in the resin composition (I) forming the resin layer (α) is based on the resin composition (I). It is preferable that it is 60 mass% or more. When the total content of (A) and (B) is 60% by mass or more, the adhesiveness becomes good, and good adhesiveness can be maintained even in a high temperature and high humidity environment.

  Moreover, in the resin composition (I) forming the resin layer (α), the mass ratio of the content of the acrylic-modified polyester resin (A) and the aliphatic urethane resin (B) (content of (A) [parts by mass] ] / (B) content [parts by mass] is preferably 50/50 to 90/10. When the content [mass part] of (A) / content [mass part] of (B) is 50/50 to 90/10, the surface free energy of the resin layer (α) may be within a preferable range. In addition, the adhesiveness is good, and good adhesiveness can be maintained even in a high temperature and high humidity environment.

  Further, in the resin composition (I), in addition to (A) and (B), a melamine compound and / or a carbodiimide compound (C) described later, a lubricant, inorganic particles, organic particles, a surfactant, a surface treatment agent, etc. These various additives can be contained.

  In the present invention, the resin composition (I) forming the resin layer (α) contains a melamine compound and / or a carbodiimide compound (C) in addition to the acrylic-modified polyester resin (A) and the aliphatic urethane resin (B). It is preferable to make it. The total mass of the melamine compound and the carbodiimide compound (C) is obtained when the total mass of the acrylic modified polyester resin (A) and the aliphatic urethane resin (B) is 100 parts by mass in the resin composition (I). It is preferably 10 parts by mass or more and 40 parts by mass or less. When the total mass of the compound (C) is 10 parts by mass or more and 40 parts by mass or less, the surface free energy of the resin layer (α) can be within a preferable range, and while maintaining the adhesiveness, Properties such as flexibility and toughness can be improved.

  Specifically, the melamine compound that can be used in the present invention is etherified by subjecting methylol melamine derivative obtained by condensing melamine and formaldehyde to dehydration condensation reaction of lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol. And the like.

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

  The compound having a carbodiimide group is not particularly limited as long as it has at least one carbodiimide structure represented by the following formula (6) per molecule. Particularly preferred are polycarbodiimide compounds having two or more in them. In particular, when a polymer type isocyanate compound having a plurality of carbodiimide groups is used at the terminal or side chain of a polymer such as polyester resin or acrylic resin, the resin layer of the present invention is provided on the polyester film, In this case, not only the hardness of the resin layer is improved and the oligomer precipitation is suppressed, but also adhesion to various inks and hard coat agents, wet heat and heat resistance, flexibility, and toughness can be preferably used.

Formula (6) -N = C = N-
A known technique can be applied to the production of the carbodiimide compound, and it is generally obtained by polycondensation of a diisocyanate compound in the presence of a catalyst. As the diisocyanate compound that is a starting material of the polycarbodiimide compound, aromatic, aliphatic, and alicyclic diisocyanates can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate. , Isophorone diisocyanate, dicyclohexyl diisocyanate and the like can be used. Furthermore, in order to improve the water solubility and water dispersibility of the polycarbodiimide compound within the range not losing the effect of the present invention, a surfactant is added, polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, hydroxy A hydrophilic monomer such as an alkyl sulfonate may be added or used.

In addition, other compounds such as known crosslinking agents such as oxazoline compounds, epoxy compounds, and isocyanate compounds can be optionally used. __
In the method of forming the resin layer (α) of the present invention, the resin layer (α) is formed by applying the resin composition (I) containing the aliphatic urethane resin (B) on at least one surface of the laminated polyester film. Obtained by the process. In this formation method, it is preferable that the resin composition (I) further contains an acrylic-modified polyester resin (A) in addition to the aliphatic urethane resin (B).

  When the resin composition (I) containing the acrylic modified polyester resin (A) and the aliphatic urethane resin (B) is applied on the laminated polyester film, the resin composition (I) contains a solvent. Also good. That is, the acrylic-modified polyester resin (A) and the aliphatic urethane resin (B) may be dissolved or dispersed in a solvent to form a coating solution, which may be applied to a thermoplastic resin film. After the application, the solvent is dried and heated to obtain a film on which the resin layer (α) is laminated. In the present invention, an aqueous solvent is preferably used as the solvent. This is because by using an aqueous solvent, rapid evaporation of the solvent in the heating step can be suppressed, and not only a uniform resin layer can be formed, but also the environmental load is excellent.

  Here, the aqueous solvent is soluble in water such as water or water and alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, and glycols such as ethylene glycol, diethylene glycol and propylene glycol. A certain organic solvent is mixed at an arbitrary ratio.

  The method of applying the resin composition (I) to the laminated polyester film can be either an in-line coating method or an off-coating method, but is preferably an in-line coating method. The in-line coating method is a method of applying in the process of manufacturing a laminated polyester film. Specifically, it refers to a method of coating at any stage from melt extrusion of a polyester resin to biaxial stretching followed by heat treatment and winding up, and is generally substantially non-obtainable after melt extrusion and rapid cooling. Crystalline unstretched (unoriented) polyester film (A film), then uniaxially stretched (uniaxially oriented) polyester film (B film) stretched in the longitudinal direction, or biaxially before heat treatment stretched further in the width direction It is applied to any one of stretched (biaxially oriented) polyester film (C film).

  In the present invention, the resin composition (I) is applied to any of the A film and B film of the polyester film before the crystal orientation is completed, the solvent is evaporated, and then the polyester film is uniaxially or It is preferable to employ a method of stretching in the biaxial direction and heating to complete the crystal orientation of the polyester film and providing a resin layer. According to this method, the production of the laminated polyester film, the application of the resin composition (I), the drying of the solvent, and the heating (that is, the formation of the resin layer) can be performed at the same time. There is. Moreover, it is easy to make the thickness of the resin layer thinner in order to perform stretching after coating.

  Especially, the method of apply | coating resin composition (I) to the film (B film) uniaxially stretched to the longitudinal direction, drying a solvent, and extending | stretching to the width direction after that, and heating is excellent. After applying to an unstretched film, compared to the method of biaxial stretching, the stretching process is less than once, so it is difficult for defects and cracks of the resin layer due to stretching to occur, and a resin layer excellent in transparency and smoothness can be formed. Because.

  On the other hand, the off-line coating method is different from the film-forming process on the film after the A film is stretched uniaxially or biaxially and subjected to heat treatment to complete the crystal orientation of the polyester film, or the A film. This is a method of applying a resin composition in the process. In this invention, it is preferable to provide by the in-line coating method from the various advantages mentioned above.

  Therefore, the best method for forming the resin layer (α) in the present invention is to apply a resin composition using an aqueous solvent on a polyester film using an in-line coating method, dry the aqueous solvent, and heat. It is a method of forming.

  When preparing the resin composition (I), an aqueous solvent is preferably used as the solvent. Resin composition (I) is an acrylic-modified polyester resin (A), aliphatic urethane resin (B), melamine compound and / or carbodiimide compound (C), and aqueous solvent optionally dispersed in water or water as necessary. It can produce by mixing and stirring by desired weight ratio in this order. Subsequently, various additives such as a lubricant, inorganic particles, organic particles, a surfactant, an antioxidant, and a thermal initiator are added in any order as necessary so as not to deteriorate the characteristics of the resin layer provided by the resin composition. Can be mixed and stirred. In particular, those containing particles in the resin layer (α) are more preferable because the slipperiness and blocking resistance are improved. In this case, inorganic particles are preferable as the contained particles, and silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, and the like can be used.

  In the present invention, the resin constituting the resin layer (α) contains particles, and the average particle size of the particles obtained by the measurement method described later is 20 nm or more and 300 nm or less, while having high transparency. The laminated polyester film is preferred because it can impart easy slipperiness. When the average particle size of the particles exceeds 300 nm, light may be scattered on the surface of the particles, and transparency may be impaired, for example, haze of the laminated glass increases. When the average particle diameter of the particles is less than 20 nm, the formed protrusions are small, so that the slipping property of the film is deteriorated, and wrinkles may be generated when the film is wound, or blocking may occur. More preferably, it is 50 nm or more and 150 nm or less.

  The amount of the particles added is 0.05 to 5 in terms of the solid content weight ratio in the coating liquid containing the resin composition (I) forming the resin layer (α) with respect to the resin composition (I). The weight% is preferable because aggregation of particles can be suppressed and formation of coarse protrusions and deterioration of transparency can be suppressed. More preferably, it is 0.1 to 3% by weight. When the amount of particles to be added is more than 5% by weight, transparency may deteriorate due to an increase in the number of irregularities on the surface of the laminated film. On the other hand, when the amount of added particles is less than 0.05% by weight, the number of protrusions on the surface of the laminated film is reduced, so that the slipping property is deteriorated and wrinkles may be generated in the laminated glass forming step.

  The thickness of the resin layer (α) of the laminated film of the present invention is preferably 30 nm or more and 100 nm or less, more preferably 40 nm or more and 80 nm or less. When the thickness of the resin layer (α) is less than 30 nm, when laminated with the laminated glass, the adhesiveness with the PVB resin used between the laminated glasses may be lowered, and the thickness of the resin layer (α) is 100 nm. If it exceeds, blocking may occur when the film is wound, haze of the laminated film may increase, and coating spots may increase when coated inline or offline.

  Next, although the detail of the manufacturing method of the laminated | multilayer film of this invention is demonstrated using the polyethylene terephthalate film as the example, this invention is limited and limited to the thing obtained by this example.

  The polyethylene terephthalate chip is dried, then supplied to two extruders, melted at 280 to 300 ° C., laminated using a three-layer feed block, and discharged from the die. The discharged sheet is extruded onto a cooling body such as a casting drum, and is cooled and solidified to obtain a casting film. At this time, using a wire-like, tape-like, needle-like or knife-like electrode, it is brought into close contact with a cooling body such as a casting drum by electrostatic force and rapidly cooled and solidified, or from a slit-like, spot-like, or planar device. A method in which air is blown out and brought into close contact with a cooling body such as a casting drum to rapidly cool and solidify is preferable.

  The casting film thus obtained is stretched within a range of 2.5 to 4.5 times in the longitudinal direction with a roll heated to 75 to 110 ° C. to obtain a uniaxially stretched film.

  The uniaxially stretched film thus obtained is subjected to a surface treatment such as a corona treatment, a flame treatment, or a plasma treatment as necessary, and then a coating solution is applied to one or both sides by a coating method. Next, both ends of the film are gripped with clips, stretched in the range of 2.5 to 5.0 times in the width direction at 90 to 150 ° C., and subsequently heat treated at a temperature of 160 to 210 ° C. In this heat treatment step, it is preferable to perform different two-stage heat treatment from the viewpoint of setting the thermal shrinkage rate at 135 ° C. within the scope of the present invention, and specifically, the first-stage heat treatment is carried out in the range of 160 to 180 ° C. After that, by performing the second stage heat treatment in the range of 190 to 210 ° C., the thermal shrinkage rate can be made the range specified in the present application. During the heat treatment step, a relaxation treatment of 0.5 to 5% may be performed in the width direction as necessary.

  The laminated film of the present invention obtained as described above is used for laminated glass. For example, to obtain a laminated glass excellent in transparency by using a film in which a polyvinyl butyral layer is laminated on at least one side of the laminated film of the present invention as an intermediate layer and sandwiching two glass plates on both sides of the intermediate layer Can do. The polyvinyl butyral layer may contain various functional agents that are usually added. The glass plate is not particularly limited as long as it is of a type used for automobile window glass, building window glass, and the like. As a laminated structure of a laminated film, a polyvinyl butyral layer, and two glass plates, for example, the structure of glass plate / polyvinyl butyral layer / laminated film / polyvinyl butyral layer / glass plate is exemplified, but it is not limited to such an embodiment. Absent. Moreover, it is preferable to use what provided the functionality by providing the heat-shielding layer etc. on the surface of the laminated film, since a highly functional laminated glass can be provided.

  The following examples further illustrate the invention. However, the present invention is not limited to the following examples without departing from the gist thereof. In addition, the evaluation method of the physical property in a following example and a comparative example is as follows.

(1) Haze and total light transmittance Three points (three pieces) of square-shaped laminated film samples having a side of 5 cm are prepared. The sample is then allowed to stand for 40 hours in a normal state (23 ° C., relative humidity 50%). For each sample, a haze measurement “NDH5000” manufactured by Nippon Denshoku Industries Co., Ltd. is used. The haze measurement is JIS “How to determine the haze of a transparent material” (K7136 2000 version), and the total light transmittance measurement is JIS “ The test is carried out by a method in accordance with “Test method for total light transmittance of transparent plastic material” (K7361-1, 1997 edition). The haze and total light transmittance of each of the three points (three) are averaged to obtain the haze and total light transmittance of the polyester film.

(2) Haze change (ΔH)
First, the haze is measured in the same manner as (1) to determine the haze before processing. Next, a polyester film sample having a length of 30 cm and a width of 20 cm was prepared and suspended in the hot air oven “HIGH-TEMP-OVEN PHH-200” manufactured by Espec Co., Ltd. set at 135 ° C. (air flow gauge “7”). Heat for 30 minutes. Thereafter, the polyester film sample was allowed to stand for 1 hour by air cooling. After that, 3 points (3 pieces) of a square-shaped polyester film sample having a side of 5 cm are cut out from the polyester film sample, the haze is measured in the same manner as (1), and the values of 3 points (3 pieces) are averaged and processed. Of haze. The haze change (ΔH) was determined by the following formula.

Haze change (ΔH) = (Haze after treatment) − (Haze before treatment)
(3) Internal haze Internal haze was measured using fully automatic direct reading haze computer “HGM-2DP” manufactured by Suga Test Instruments Co., Ltd. The polyester film was immersed in a tetralin solution, and the internal haze was determined from the following formula from the diffuse transmittance and the total light transmittance.

(4) Measurement of layer thickness Five points (five pieces) of the laminated film were cut into ultra-thin slices, and the cross-section was TEM (transmission type) by RuO ₄ dyeing, OsO ₄ dyeing, or dyeing ultra-thin film slice method by double staining of both. Observation and photography were performed with an electron microscope. From the cross-sectional photograph, the measured values of the resin layer (X) thickness of five (5) samples were averaged to measure the layer thickness of the resin layer (α).

(5) Intrinsic viscosity The value calculated from the following formula from the solution viscosity measured at 25 ° C in orthochlorophenol was used. That is, ηsp / C = [η] + K [η] ² · C
Here, ηsp = (solution viscosity / solvent viscosity) −1, C is the weight of dissolved polymer per 100 m of solvent (g / 100 ml, usually 1.2), and K is the Huggins constant (assuming 0.343). The solution viscosity and solvent viscosity were measured using an Ostwald viscometer.

  If there is insoluble matter such as inorganic particles in the solution in which the polyester composition is dissolved, the solution is filtered and weighed, and the value obtained by subtracting the weight of the filtrate from the weight of the measured sample is taken as the measured sample weight. Correction was performed.

(6) Cyclic trimer content 20 mg of the polyester composition is dissolved in OCP (o-chlorophenol) at 150 ° C. for 30 minutes and cooled at room temperature. Thereafter, 1,4-diphenylbenzene was added as an internal standard, 2 ml of methanol was added and the polymer was separated using a high-speed centrifuge, and the liquid layer portion was then analyzed using a high-speed liquid chromatograph LC-10ADvp manufactured by Shimadzu Corporation. It was measured.

  In the case of measuring the cyclic trimer content of the polyester composition constituting the outermost polyester layer of the polyester film, the polyester composition constituting the polyester layer is cut out from the outermost layer of the polyester film. .

  Moreover, after measuring the ratio of the layer thickness of each layer of a polyester film by the method of (4), when measuring cyclic trimer content of the polyester composition which comprises the polyester layer except the outermost layer of the polyester film. The cyclic trimer content of the entire polyester film is measured in the same manner as described above, and the cyclic trimer content of the polyester composition constituting the polyester layer excluding the outermost layer is determined by weight proportional distribution.

  If there is insoluble matter such as inorganic particles in the solution in which the polyester composition is dissolved, the solution is filtered and weighed, and the value obtained by subtracting the weight of the filtrate from the weight of the measured sample is taken as the measured sample weight. Correction was performed.

(7) Heat shrinkage rate Two lines are drawn on the film surface so that the width is 10 mm and the measurement length is about 100 mm, and the distance between the two lines is measured at 23 ° C., and this is defined as L0. This polyester film sample was left in a hot air oven “HIGH-TEMP-OVEN PHH-200” manufactured by ESPEC CORP. Set at 135 ° C. (air flow gauge “7”) for 30 minutes under a load of 3 g, and then again 2 The distance between the lines of the book was measured at 23 ° C., and this was taken as L1, and the heat shrinkage rate was determined by the following equation. The measurement was carried out by 5 samples in the longitudinal direction and in the width direction, and the average value was evaluated.
Thermal contraction rate (%) = (L0−L1) / L0 × 100
When analyzing the film, if the longitudinal direction or the width direction of the film is not known, the direction having the maximum refractive index in the film is regarded as the width direction, and the direction orthogonal thereto is regarded as the longitudinal direction. The direction of the maximum refractive index in the film may be obtained by measuring the refractive index in all directions of the film with an Abbe refractometer, for example, in the slow axis direction with a phase difference measuring device (birefringence measuring device) or the like. It may be obtained by determining.

(8) Metal content in the polyester composition constituting the film The metal content in the polyester composition constituting the film was measured using a fluorescent X-ray analyzer (model number: 3270) manufactured by Rigaku Corporation. The content (ppm) of the polyester composition constituting the polyester film was determined by line measurement. The quantification was performed using a calibration curve of the strength and each element amount prepared using a sample with a known metal amount quantified in advance using an atomic absorption method or the like.

  In addition, when measuring metal content in the polyester composition which comprises the outermost layer of a polyester film, the sample was extract | collected by shaving off a polyester composition from the outermost layer of a polyester film, and the measurement was performed.

(9) Average particle diameter of particles in coating layer A laminated film obtained by laminating a coating layer on a polyester film is cut into ultra-thin sections, and the cross section is stained with RuO ₄ staining, OsO ₄ staining, or double staining of both. According to the method, a TEM (transmission electron microscope) was used for observation at a magnification of 200,000 times, and a photograph was taken. The particle diameter (equivalent sphere diameter) in the coating layer was measured from the cross-sectional photograph, the particle diameters of the particles observed in 100 fields of view were determined, and the average value was taken as the average particle diameter.

(10) Aliphatic urethane structure forming the resin layer (α), confirmation of the formulas (1) to (5) The aliphatic urethane structure forming the resin layer (α) is determined by gas chromatography mass spectrometry (GC-MS). The weight peak of the aliphatic isocyanate compound and polyol compound cleaved at the urethane bond portion is confirmed. Next, in Fourier transform infrared spectroscopy (FT-IR), the presence or absence of peaks derived from the bonds between the aliphatic isocyanate compound, the polyol compound, and the atoms of the structures of formulas (1) to (5) Check. Further, in proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR), the position of the chemical shift derived from the position of the hydrogen atom of the aliphatic isocyanate compound and the polyol compound and the structures of formulas (1) to (5) and hydrogen The proton absorption line area derived from the number of atoms is confirmed. These results were comprehensively confirmed.

(11) Surface free energy The laminated film was allowed to stand for 24 hours in an atmosphere having a room temperature of 23 ° C. and a relative humidity of 65%. Thereafter, the contact angle of each of the four types of solutions of pure water, ethylene glycol, formamide, and diiodomethane with respect to the resin layer under the same atmosphere was measured using a contact angle meter CA-D type (manufactured by Kyowa Interface Science Co., Ltd.). ) To measure 5 points each. The average value of the three measured values excluding the maximum value and the minimum value of the five measured values is defined as the contact angle of each solution.

Next, using the contact angles of the four types of solutions obtained, “the surface free energy (γ) of the solid, which is proposed by Hata et al., Is represented by the dispersion force component (γ _S ^d) and the polar force component (γ _S ^p ) , And the hydrogen bonding force component (γ _S ^h ), and the geometric mean method based on the formula (expanded Fowkes formula) obtained by extending the Fowkes formula, The surface free energy, which is the sum of the polar forces, is calculated.

A specific calculation method is shown. The meaning of each symbol is described below. When γ _S ^L is the tension at the interface between the solid and the liquid, Equation (1) is established.
γ _S ^L : surface free energy of the resin layer and known solutions listed in Table 1 γ _S : surface free energy of the resin layer γ _L : surface free energy of known solutions listed in Table 1 γ _S ^d : of the resin layer Dispersion force component of surface free energy γ _S ^p : Polar force component of surface free energy of resin layer γ _S ^h : Hydrogen bond force component of surface free energy of resin layer γ _L ^d : Surface of known solution described in Table 1 Dispersion force component of free energy γ _L ^p : Polar force component of surface free energy of known solutions listed in Table 1 γ _L ^h : Hydrogen bond strength component of surface free energy of known solutions listed in Table 1 γ _S ^L _{= γ S + γ L -2 (} γ S d · γ L d) 1/2 -2 (γ S p · γ L p) 1/2 -2 (γ S h · γ L h) 1/2 ··· Formula (1).
The state when the smooth solid surface and the droplet are in contact with each other at the contact angle (θ) is expressed by the following equation (Young's equation). γ _S = γ _S ^L + γ _L cos θ (2)

When these mathematical formulas (1) and (2) are combined, the following formula is obtained.
_{^{(γ S d · γ L d}} ) 1/2 + (γ S p · γ L p) 1/2 + (γ S h · γ L h) 1/2 = γ L (1 + cosθ) / 2 ··· formula (3).

Actually, the four components of water, ethylene glycol, formamide, and diiodomethane have contact angles (θ) and the components of the surface tension of known solutions listed in Table 1 (γ _L ^d , γ _L ^p , γ _L ^h ) is substituted into Equation (3) to solve the four simultaneous equations. As a result, the surface free energy (γ), the dispersion force component (γ _S ^d ), the polar force component (γ _S ^p ), and the hydrogen bonding force component (γ _S ^h ) of the solid are calculated. The dispersion force corresponds to the dispersion force component (γ _S ^d ), and the polar force of the present invention corresponds to the sum of the polar force component (γ _S ^p ) and the hydrogen bonding force component (γ _S ^h ).
(12) Blocking resistance Two transparent laminated films obtained in the examples and comparative examples were prepared, and the rubber was placed on the first surface and the second surface which is the back surface of the first surface in close contact with each other. A roller (φ50) was placed and reciprocated by its own weight. Thereafter, the blocking state between the first surface and the second surface was observed and evaluated in the following manner. The case where the first surface and the second surface were not in contact was evaluated as “◎ (excellent)”, and the case where the surface was in close contact with each other was “◯ (good)”. The case where it was attached was evaluated as “△ (somewhat inferior)”, and the case where it adhered and adhered to almost the entire surface was evaluated as “× (defect)”.

(13) Appearance of laminated glass An interlayer film for laminated glass containing a polyvinyl butyral resin as a main component was produced by a conventionally known method. Next, an interlayer film for glass is laminated on both sides of the film, and these are placed between highly transparent glasses ("Celtier" manufactured by Asahi Glass Co., Ltd.), then placed in a rubber bag and removed for 20 minutes at a vacuum of 2660 Pa. After gassing, it was transferred to an oven while degassed, and further vacuum pressed while maintaining at 90 ° C. for 30 minutes. After pre-bonding in this manner, pressure bonding was performed for 20 minutes in an autoclave at 135 ° C. and a pressure of 118 N / cm ² to obtain a laminated glass.
The evaluation at the time of making a laminated glass using the obtained film was visually evaluated according to the following criteria.

(A) Adhesiveness: Floating between the film (intermediate film) inside the laminated glass, and peeling is not seen inside or outside the product.
○: It floats between the film (intermediate film) inside the laminated glass and no peeling is seen inside the product, but a slight float is seen on the outer peripheral part outside the product.
(Triangle | delta): It floats between the films (interlayer film) inside a laminated glass, and peeling is seen slightly in the edge part inside a product.
X: It floats between the films (interlayer film) inside the laminated glass, and peeling is widely seen inside the product.

(B) Film shrinkage (edge shrinkage) at the outer periphery of the wrinkles and laminated glass
(Double-circle): A wrinkle is not visible in the film (intermediate film) inside a laminated glass, and the film shrinkage of the outer peripheral part of a laminated glass is 1 mm or less.
○: Wrinkles are slightly visible on the outer periphery of the film (intermediate film) inside the laminated glass and the film shrinkage at the edge of the laminated glass is 1 mm or less. Or wrinkles are not visible on the outer periphery of the film (interlayer film) inside the laminated glass, and the film shrinkage at the edge of the laminated glass exceeds 1 mm and is 2 mm or less.
Δ: Slight wrinkles are visible on the outer periphery of the film (intermediate film) outside the laminated glass, and the film shrinkage at the edge of the laminated glass exceeds 2 mm and is 3 mm or less.
X: When many wrinkles are visible inside the product (intermediate film) of the laminated glass, or the film shrinkage at the edge of the laminated glass exceeds 3 mm.

(C) Appearance (cloudy)
A: When cloudiness is not visible on the film (intermediate film) inside the laminated glass.
○: When the film (intermediate film) inside the laminated glass is slightly cloudy on the outer periphery outside the product.
[Delta]: When the film inside the laminated glass (intermediate film) is slightly cloudy at the end of the product.
X: When the film (intermediate film) inside the laminated glass appears cloudy inside the product.

(Production Example 1-Polyester A1)
An ester in which about 123 parts by weight of bis (hydroxyethyl) terephthalate was previously charged in a slurry of 45 parts by weight of ethylene glycol with respect to 100 parts by weight of high-purity terephthalic acid and maintained at a temperature of 250 ° C. and a pressure of 1.2 × 10 ⁵ Pa. The esterification reaction layer was sequentially supplied over 4 hours, and after the completion of the supply, the esterification reaction was further performed over 1 hour, and the esterification reaction product was transferred to a polycondensation tank. Subsequently, 0.01 parts by weight of ethyl diethylphosphonoacetate was added to the polycondensation reaction tank to which the esterification reaction product had been transferred, and 0.04 parts by weight of magnesium acetate tetrahydrate was further added as a polymerization catalyst. It added so that it might become 0.04 weight part in conversion of an antimony atom with respect to polyester which can obtain an antimony trioxide. Thereafter, while stirring the low polymer at 30 rpm, the reaction system was heated from 250 ° C. to 285 ° C. over 60 minutes and the pressure was reduced to 40 Pa. The time to reach the final pressure was 60 minutes. When the predetermined stirring torque is reached, the reaction system is purged with nitrogen, returned to normal pressure, the polycondensation reaction is stopped, discharged into cold water at a temperature of 20 ° C. in a strand form, and immediately cut to obtain polyester A1 pellets. It was. The time from the start of decompression to the arrival of the predetermined stirring torque was 3 hours. The obtained polyester A1 had an intrinsic viscosity of 0.65 dl / g and a cyclic trimer content of 1.05% by weight.

(Production Example 2-Polyester B1)
A slurry of 60 parts by weight of ethylene glycol with 100 parts by weight of dimethyl terephthalate is charged with about 123 parts by weight of bis (hydroxyethyl) terephthalate in advance together with 0.06 parts by weight of magnesium acetate tetrahydrate, a temperature of 250 ° C., a pressure of 1 .Sequentially supplied to the esterification reaction layer held at 2 × 10 ⁵ Pa over 4 hours, and after completion of the supply, the esterification reaction is carried out over another 1 hour, and this esterification reaction product is transferred to the polycondensation tank did. Subsequently, 0.026 part by weight of trimethyl phosphate is added to the polycondensation reaction tank to which the esterification reaction product has been transferred, and 0.02 weight of germanium dioxide dissolved finely in ethylene glycol as a polymerization catalyst. A solution of parts in tetraethylammonium hydroxide was added. Thereafter, while stirring the low polymer at 30 rpm, the reaction system was heated from 250 ° C. to 285 ° C. over 60 minutes and the pressure was reduced to 40 Pa. The time to reach the final pressure was 60 minutes. When the predetermined stirring torque was reached, the reaction system was purged with nitrogen, returned to normal pressure, the polycondensation reaction was stopped, discharged into cold water at a temperature of 20 ° C. in a strand form, and immediately cut to obtain polyester pellets. The time from the start of decompression to the arrival of the predetermined stirring torque was 3 hours. The obtained polymer had an intrinsic viscosity of 0.64 dl / g and a cyclic trimer content of 1.03% by weight.

  The polymer was dried under reduced pressure at 150 ° C., and then solid state polymerization was performed at a temperature of 240 ° C. for 8 hours under reduced pressure (133 Pa or less). The polymer was taken out and washed with water to obtain polyester B1 pellets. It was. The obtained polyester B1 had an intrinsic viscosity of 0.78 dl / g and a cyclic trimer content of 0.28% by weight.

(Production Example 3—Acrylic-modified polyester resin (A) and coating solution containing (A))
The polyester resin component is 50 parts by mass of terephthalic acid, 50 parts by mass of isophthalic acid, 50 parts by mass of ethylene glycol, and 30 parts by mass of neopentyl glycol together with 0.3 parts by mass of antimony trioxide and 0.3 parts by mass of zinc acetate. A reactor purged with nitrogen was charged and a polymerization reaction was carried out at 190 to 220 ° C. for 12 hours under atmospheric pressure while removing water to obtain polyester glycol. Next, 5 parts by mass of 5-sodium sulfoisophthalic acid was added to the polyester glycol obtained, and xylene was charged into the reactor as a solvent, and polymerization was performed for 3 hours while distilling off xylene at 260 ° C. under a reduced pressure of 0.2 mmHg. To obtain a polyester resin component. This polyester resin component was dissolved in water containing ammonia water and butyl cellulose.

  Next, the acrylic resin component contains 50 parts by mass of methyl methacrylate and 10 parts by mass of methacrylamide, and the acrylic resin component / polyester resin component = 50/50 in the aqueous dispersion containing the polyester resin component described above. It added so that it might become a mass ratio. Furthermore, 5 parts by mass of benzoyl peroxide was added as a polymerization initiator, and a polymerization reaction was carried out at 70 to 80 ° C. for 3 hours in a nitrogen purged reactor to obtain a coating liquid containing acrylic modified polyester (A).

(Production Example 4-Coating liquid containing aliphatic urethane resin (B) and (B))
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 70 parts by mass of 1,6-hexane diisocyanate as an aliphatic polyisocyanate compound, 30 parts by mass of polyisobutylene glycol as a polyol compound, As a solvent, 60 parts by mass of acetonitrile and 30 parts by mass of N-methylpyrrolidone were charged. Next, under a nitrogen atmosphere, the temperature of the reaction solution was adjusted to 75 to 78 ° C., 0.06 parts by mass of stannous octylate was added as a reaction catalyst, and the mixture was reacted for 7 hours. Subsequently, this was cooled to 30 degreeC and the isocyanate group terminal aliphatic urethane resin (B) was obtained. Next, water is added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., and stirred and mixed at 2000 rpm, and the isocyanate group-terminated aliphatic urethane resin (B) is added and dispersed in water. did. Then, the coating liquid containing an aliphatic urethane resin (B) was prepared by removing a part of acetonitrile and water under reduced pressure.

(Production Example 5-Resin composition (I))
60 parts by mass of the resulting acrylic-modified polyester resin (A), aliphatic urethane resin (B
) And 40 parts by mass of melamine compound (C), and Nicalac (registered trademark) MW-12LF (manufactured by Sanwa Chemical Co., Ltd.) was mixed to 60/40/20 parts by mass. In order to impart lubricity to the resin layer surface, silica particles having an average particle diameter of 80 nm (cataloid (registered trademark) SI-80P manufactured by Catalytic Chemical Co., Ltd.) were used as the acrylic particles. 3 mass parts was added with respect to a total of 120 mass parts of 60 mass parts, aliphatic urethane resin (B) 40 mass parts, and a melamine compound (C) 20 mass parts. The resin composition (I) was obtained by the above-described blending operation.

Example 1
After drying polyester A1 and polyester B1 under reduced pressure (1 Torr) for 6 hours at 150 ° C., polyester B1 is used as a raw material for the outermost polyester layer (B layer), and polyester A1 is removed from the outermost layer (A layer) Were fed to two extruders, and each was melted at 285 ° C. It is laminated in 3 layers of B layer / A layer / B layer by a feed block, extruded into a sheet form from a die, wound around a casting drum cooled to 20 ° C. using an electrostatic application method, cooled and solidified, and unstretched film Was made.

  The obtained unstretched film was heated to 95 ° C. with a heated roll group and an infrared heater and stretched 3.3 times in the longitudinal direction to obtain a uniaxially stretched polyester film.

  Next, the resin composition (I) was applied to a uniaxially stretched film with a coating thickness of about 10 μm using a bar coat. Subsequently, both end portions in the width direction of the uniaxially stretched film coated with the resin composition (I) were held with clips and led to the preheating zone. The atmospheric temperature of the preheating zone was set to 90 ° C. to 100 ° C., and the solvent contained in the resin composition (I) was dried. Subsequently, the film was continuously stretched 3.5 times in the width direction in a stretching zone at 100 ° C., then heat treated for 5 seconds in a heat treatment zone at 160 ° C., and then the resin layer (α) was applied for 5 seconds in the heat treatment zone at 195 ° C. Thus, a laminated film in which the crystal orientation of the polyester film was completed was obtained. At this time, in the heat treatment step, a relaxation treatment of 2.5% was performed in the width direction.

  In the obtained laminated film, the thickness of the film was 50 μm, and the thickness of the resin layer was about 60 nm. The breakdown of the layer thickness of the polyester layer (A layer) excluding the outermost layer and the outermost polyester layer (B layer) was B layer / A layer / B layer = 7 μm / 36 μm / 7 μm.

About the structure of the resin layer ((alpha)) of the laminated | multilayer film which came out, existence of the weight peak originating in the structure of an aliphatic urethane structure and Formula (3) was confirmed by gas chromatograph mass spectrometry (GC-MS). Next, the aliphatic urethane structure was confirmed by Fourier transform infrared spectroscopy (FT-IR), and the presence of peaks derived from the bonds between the atoms of the structure of formula (3) was confirmed. Finally, in proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR), the position of the hydrogen atom is determined from the position of the chemical shift derived from the position of the hydrogen atom in the aliphatic urethane structure, the structure of formula (3), and the proton absorption line area. Check the number. By combining these results, it was confirmed that the resin composition forming the resin layer (α) has an aliphatic urethane structure and a structure of the formula (3).

  The total light transmittance of this laminated film is 91.0%, the haze is 0.4%, the blocking resistance is good, and the cyclic trimer content of the polyester composition constituting the outermost polyester layer (B layer) Was 0.43% by weight, and the cyclic trimer content of the polyester composition constituting the polyester layer excluding the outermost layer was 1.18% by weight. Further, the haze change ΔH of the film before and after being heated at 135 ° C. for 30 minutes was 0.4%, and the heat shrinkage ratio was as good as 3.0% in the longitudinal direction and 3.2% in the width direction.

  The physical properties of the obtained laminated polyester film are shown in Table 2. In the laminated glass evaluation, the adhesive properties were excellent, the wrinkles and edge shrinkage were suppressed, and no haze was observed and the appearance was good.

(Example 2)
A laminated film was obtained in the same manner as in Example 1 except that heat treatment was performed in a heat treatment zone at 160 ° C. for 5 seconds and then heat treatment was performed in a heat treatment zone at 200 ° C. for 5 seconds.

  The physical properties of the obtained laminated film are shown in Table 2. In the laminated glass evaluation, the adhesive film was excellent in adhesiveness, wrinkles and edge shrinkage were suppressed, and no haze was observed, and it had a good appearance.

(Example 3)
A laminated film was obtained in the same manner as in Example 2, except that heat treatment was performed for 5 seconds in a heat treatment zone at 180 ° C., and then heat treatment was performed for 5 seconds in a heat treatment zone at 200 ° C.

  The physical properties of the obtained laminated film are shown in Table 2. In the laminated glass evaluation, the adhesive film was excellent in adhesiveness, wrinkles and edge shrinkage were suppressed, and no haze was observed, and it had a good appearance.

Example 4
Example 1 except that the lamination ratio of the polyester layer (A layer) excluding the outermost layer and the polyester layer (B layer) of the outermost layer was changed to B layer / A layer / B layer = 3 μm / 44 μm / 3 μm A laminated film having a thickness of 50 μm was obtained in the same manner as described above.

  The physical properties of the obtained laminated film are shown in Table 2. In laminated glass evaluation, it has excellent adhesiveness, wrinkles and edge shrinkage are suppressed, and although the outer peripheral part outside the product is slightly cloudy, it has a good appearance. It was.

(Example 5)
Example 1 except that the lamination ratio of the polyester layer (A layer) excluding the outermost layer and the polyester layer (B layer) of the outermost layer was changed to B layer / A layer / B layer = 5 μm / 28 μm / 5 μm A laminated film having a thickness of 38 um was obtained in the same manner as described above.

  The physical properties of the obtained laminated film are shown in Table 2. In laminated glass evaluation, it has excellent adhesiveness, wrinkles and edge shrinkage are suppressed, and although the outer peripheral part outside the product is slightly cloudy, it has a good appearance. It was.

(Example 6)
Example 1 except that the lamination ratio of the polyester layer (A layer) excluding the outermost layer and the polyester layer (B layer) of the outermost layer was changed to B layer / A layer / B layer = 7 μm / 61 μm / 7 μm A laminated film having a thickness of 75 μm was obtained in the same manner as described above.

  The physical properties of the obtained laminated film are shown in Table 2. In laminated glass evaluation, it has excellent adhesiveness, wrinkles and edge shrinkage are suppressed, and although the outer peripheral part outside the product is slightly cloudy, it has a good appearance. It was.

(Example 7)
Resin composition I was produced in the same manner as in Production Example 5 except that silica particles having an average particle diameter of 140 nm (Spherica (registered trademark) 140 manufactured by Catalyst Chemicals Co., Ltd.) were used as the inorganic particles. A laminated film having a thickness of 50 μm was obtained.

    The physical properties of the obtained laminated film are shown in Table 3. It has excellent anti-blocking property, and has an appearance in which a slight cloudiness is observed at the end of the laminated glass evaluation, although it has excellent adhesiveness and edge shrinkage is suppressed. Was.

(Example 8)
A resin composition I is produced in the same manner as in Production Example 5 except that 90 parts by mass of the acrylic-modified polyester resin (A) and 10 parts by mass of the aliphatic urethane resin (B) are mixed and the melamine compound (C) is not added. A laminated film having a thickness of 50 μm was obtained in the same manner as in Example 1.

  The physical properties of the obtained laminated film are shown in Table 3. In the laminated glass evaluation, the adhesive film was excellent in adhesiveness, wrinkles and edge shrinkage were suppressed, and no haze was observed, and it had a good appearance.

Example 9
Other than mixing 60/40/60 parts by mass of Nicalac (registered trademark) MW-12LF (manufactured by Sanwa Chemical Co., Ltd.) as an acrylic-modified polyester resin (A), aliphatic urethane resin (B), and melamine compound (C) Produced a resin composition I in the same manner as in Production Example 5, and obtained a laminated film having a thickness of 50 μm in the same manner as in Example 1.

  The physical properties of the obtained laminated film are shown in Table 3. It has excellent blocking resistance, has excellent adhesion in evaluation of laminated glass, suppresses wrinkles and edge shrinkage, has a good appearance without cloudiness. Was.

(Example 10)
A laminated film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the thickness of the resin layer (α) was 100 nm in Example 1.

  The physical properties of the obtained laminated film are shown in Table 3, but the blocking resistance is slightly inferior, and in the laminated glass evaluation, the adhesiveness is excellent, and wrinkles and edge shrinkage are suppressed, but the appearance of slightly clouding at the edge is shown. Had.

(Example 11)
A laminated film having a thickness of 50 um was obtained in the same manner as in Example 1 except that the thickness of the resin layer (α) was 30 nm in Example 1.

  The physical properties of the obtained laminated film are shown in Table 3. In the laminated glass evaluation, the adhesive film was excellent in adhesiveness, wrinkles and edge shrinkage were suppressed, and no haze was observed, and it had a good appearance.

(Example 12)
In combination with 3 parts by mass of silica particles having an average particle diameter of 80 nm as inorganic particles, silica particles having an average particle diameter of 140 nm (Spherica (registered trademark) 140 manufactured by Catalytic Chemical Co., Ltd.) are added by 60 parts by mass of an acrylic-modified polyester resin (A). A resin composition I was produced in the same manner as in Production Example 5, except that 1 part by mass was added to a total of 120 parts by mass of 40 parts by mass of the aliphatic urethane resin (B) and 20 parts by mass of the melamine compound (C). A laminated film having a thickness of 50 μm was obtained in the same manner as in Example 1.

Although the physical properties of the obtained laminated film are shown in Table 3, the anti-blocking property is excellent, and in the laminated glass evaluation, the adhesiveness is excellent, the edge shrinkage is suppressed, and the outer peripheral portion outside the product is slightly cloudy. It had a good appearance.
(Example 13)
A laminated film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the thickness of the resin layer (α) was set to 80 nm in Example 1.

  The physical properties of the obtained laminated film are shown in Table 3. Although the blocking resistance is good, the laminated glass is excellent in adhesiveness, wrinkles and edge shrinkage are suppressed, but the appearance is slightly cloudy at the end. Had.

(Comparative Example 1)
A laminated film was obtained in the same manner as in Example 1 except that heat treatment was performed in a heat treatment zone at 210 ° C. for 5 seconds and then heat treatment was performed in a heat treatment zone at 210 ° C. for 5 seconds.

  The physical properties of the obtained laminated film are shown in Table 4. In the laminated glass evaluation, although the adhesiveness was excellent and no fogging was observed, wrinkles and edge shrinkage were deteriorated.

(Comparative Example 2)
A laminated film was obtained in the same manner as in Example 1, except that heat treatment was performed for 5 seconds in a heat treatment zone at 160 ° C. and then heat treatment was performed for 5 seconds in a heat treatment zone at 180 ° C.

  The physical properties of the obtained laminated film are shown in Table 4. In the laminated glass evaluation, the adhesive properties were excellent, the outer peripheral part outside the product was slightly cloudy, and wrinkles and edge shrinkage deteriorated.

(Comparative Example 3)
A laminated film was obtained in the same manner as in Example 1 except that polyester A1 was used for the outermost polyester layer (B layer).
The physical properties of the obtained laminated film are shown in Table 4. In the laminated glass evaluation, the adhesiveness was excellent, and wrinkles and edge shrinkage were suppressed, but the haze deteriorated.

  Comparative Example 4 In addition to 60 parts by mass of the acrylic-modified polyester resin (A) and 40 parts by mass of the aliphatic urethane resin (B), Resem (registered trademark) N-137 (Chukyo) is used as a long-chain alkyl surface treatment agent. Resin composition I was produced in the same manner as in Production Example 5 except that 20 parts by mass of Ogyu Co., Ltd. was added, and a 50 μm thick laminated film was obtained in the same manner as in Example 1.

  The physical properties of the obtained laminated film are shown in Table 4. In the laminated glass evaluation, no fogging was observed, but the adhesiveness deteriorated, and wrinkles and edge shrinkage deteriorated.

(Comparative Example 5)
An acrylic modified polyester resin (A) was produced in the same manner as in Production Example 3 except that the mass ratio of acrylic resin component / polyester resin component = 8/92 was added in Production Example 3. The resin composition I was prepared in the same manner as in Production Example 5 except that 60 parts by mass of the resulting acrylic-modified polyester resin (A) and 40 parts by mass of the aliphatic urethane resin (B) were added and the melamine compound (C) was not added. A laminated film having a thickness of 50 μm was obtained in the same manner as in Example 1.

  The physical properties of the obtained laminated film are shown in Table 4. In the laminated glass evaluation, no fogging was observed, but the adhesiveness deteriorated, and wrinkles and edge shrinkage deteriorated.

(Comparative Example 6)
A resin composition I is produced in the same manner as in Production Example 5 except that 60 parts by mass of the acrylic-modified polyester resin (A) and 40 parts by mass of the melamine compound (C) are mixed and the aliphatic urethane resin (B) is not mixed. A laminated film having a thickness of 50 μm was obtained in the same manner as in Example 1.

  The physical properties of the obtained laminated film are shown in Table 4. In the laminated glass evaluation, adhesiveness, wrinkles, and edge shrinkage deteriorated.

  The laminated film of the present invention suppresses the precipitation of the cyclic trimer in the process of laminating the heat ray shielding layer on the laminated film and the laminated glass processing process, maintains transparency, and has excellent adhesion to the laminated glass, and Since wrinkles do not occur in the laminated glass processing step, it can be suitably used as a laminated glass film for windows of building materials, automobiles and the like.

Claims (9)

A laminated film having a resin layer (α) containing an aliphatic urethane structure on at least one side of a laminated polyester film comprising at least three layers, the surface free energy of the resin layer (α) being 30 mN / m or more, 45 mN / M or less, and the laminated film satisfies the following requirements (a) and (b).
(A) The haze change (ΔH) before and after heating the laminated film at 135 ° C. for 30 minutes is 1.0% or less.
(B) The heat shrinkage rate when the laminated film is heated at 135 ° C. for 30 minutes is 2.0% or more and 4.5% or less in both the film longitudinal direction and the width direction. The laminated film for laminated glass according to claim 1, wherein the internal haze is 0.5% or less. The laminated film for laminated glass according to claim 1 or 2, wherein the resin layer (α) has a thickness of 30 nm or more and 100 nm or less. The laminated film for laminated glass according to any one of claims 1 to 3, wherein the resin layer (α) contains particles having an average particle diameter of 20 nm or more and 300 nm or less. The laminated film for laminated glass according to any one of claims 1 to 4, wherein the haze is 1.5% or less. Both the polyester layers of the outermost layer of the said laminated polyester film satisfy | fill the requirements of following (a), (b), (c), The laminated | multilayer film for laminated glasses in any one of Claims 1-5.
(A) The thickness of both polyester layers of the outermost layer is 5 μm or more. (B) The cyclic trimer content of the polyester composition constituting both polyester layers of the outermost layer is the polyester of both outermost layers. 0.5% by weight or less based on the entire polyester composition constituting the layer (c) The polyester composition constituting both outermost polyester layers contains a germanium element The germanium element contained in the polyester composition constituting both polyester layers of the outermost layer of the laminated polyester film is 10 to 400 ppm relative to the entire polyester composition constituting both polyester layers of the outermost layer. The laminated film for laminated glass according to any one of claims 1 to 6. The cyclic trimer content contained in the polyester composition constituting the polyester layer excluding the outermost layer of the laminated polyester film is 2.0 with respect to the entire polyester composition constituting the polyester layer excluding the outermost layer. The laminated film for laminated glass according to any one of claims 1 to 7, wherein the laminated film is not more than% by weight. The laminated film for laminated glass according to any one of claims 1 to 8, wherein the total light transmittance is 88% or more.