JP5664189B2 - Polyester resin film for mold release - Google Patents

Description

  The present invention relates to a polyester resin film for mold release. In particular, the present invention relates to a polyester resin film for mold release that is suitable as a mold release film that is used for transfer, especially for simultaneous molding transfer.

  As a method of applying a design to a molded body having a flat surface or a curved surface, a method of transferring the design using a transfer film provided with a decorative layer is utilized. The transfer film has a decorative layer that gives functions, information, and design such as a high hardness layer, metal layer, and design layer to the release film, and an adhesive layer that is integrated with the resin product as necessary. Formed. The release film is obtained by laminating a release layer directly or via an adhesive layer on a release film based on a resin film such as polyester. Various decorations can be made through this release layer. A layer is provided.

  Examples of a transfer method to a molded body that is a transfer target include a hot stamping method and a simultaneous molding transfer method.

  The hot stamping method is a method of transferring the decorative layer of the transfer film to the transfer object by pressing with a heating roll or the like, and the transfer object is often limited to a flat one. Therefore, the molding simultaneous transfer method described later is suitable for decorating the three-dimensional shape.

  In a molding method called simultaneous molding transfer, for example, a design is given by the following process. First, the transfer film is placed in a mold such as an injection molding machine so that the surface side of the decorative layer is in contact with the resin that flows later. Next, the transfer film is given a certain shape by fluid decompression, fluid pressurization, solid pressurization by a mold, or the like. In addition, molds such as injection molding machines are closed, high-temperature resin is flowed in, resin products are molded, and at the same time, the heat and pressure of the resin are used to integrate with the decoration layer via an adhesive layer, etc. Is done. Then, it cools and is peeled from a base material along a mold release layer later, and the resin molding to which the design was provided is obtained.

  A film serving as a base material for a transfer film is required to have rigidity in the vicinity of room temperature in order to obtain process stability when a release layer or a decorative layer is laid. In addition, flexibility in the vicinity of the molding temperature is also important for shape formation in the simultaneous molding transfer method and integration with the decorative layer via the adhesive layer. In order to achieve both rigidity and flexibility, for polyester resins and the like, (1) increase the molecular orientation of the resin by stretching, or (2) acid components and alcohols that increase the glass transition temperature. Applying polymer copolymerized components, (3) Stiffness is controlled by placing a hard layer on the surface in the thickness direction, etc. (4) Reducing thickness and lowering glass transition temperature Techniques such as ensuring flexibility by applying a polyester resin copolymerized with an acidic component or an alcohol component have been studied. (Patent Documents 1 to 4)

Japanese Patent Laid-Open No. 07-196821 JP 07-237283 A JP 2004-009596 A Japanese Patent No. 40696686

  The release film that becomes the base material of the transfer film is generally thin and flexible so that it can be easily shaped. However, in the state of the roll wound up in multiple layers, there is a problem that wrinkles and blocking due to air entrainment are likely to occur. In particular, in recent years, decoration with transfer films has been required to be applied to various designs such as pearl tone and high gloss, and application to metal tone has been widely studied as an alternative to plating from the viewpoint of reducing environmental impact. . For this reason, poor planarity of the release film such as wrinkles is a factor that causes a reduction in quality.

  In order to improve these, unevenness is imparted to the surface of the base material to improve air escape and slipperiness. For example, it is preferable to form a concavo-convex structure on the surface of the film by mixing a lubricant into the resin constituting the release film, coating a lubricant mixed with the lubricant, etc., and exhibiting slipperiness. However, as mentioned above, a thin and flexible release film causes micro unevenness and scratches, so it is necessary to check the design of the decorative layer, detect scratches, and detect delicate hairlines. This leads to a bad decoration layer. In addition, high definition of the design has been extended, and high transparency has been demanded for the release film in order to confirm a fine design.

  The present invention has been made against the background of such prior art problems. That is, an object of the present invention is to provide a polyester resin film for mold release that is suitable for a design that exhibits mirror surface properties by transfer and is excellent in transparency.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have reached the present invention.
That is, this invention consists of the following structures.
The first invention has a resin composition layer containing particles on at least one surface of the film base material, the film base material contains substantially no particles, and the resin composition layer contains particles A. The amount is 0.1 to 30% by mass, the content of the particle B is 0 to 10% by mass, the average particle size dA of the particle A is 0.01 to 2 μm, and the average particle size dB of the particle B is 0.01 to 0.2 μm, the average particle diameter dA of the particles A, the average particle diameter dB of the particles B, the thickness t of the resin composition layer satisfy the following relationships (1) and (2), and the elastic modulus is 30 ° C. The surface reflection intensity (Wa) of the resin composition layer in the wavelength region of 0.1 mm to 0.3 mm measured using a wave scan device is 4.0 MPa at 1000 MPa or more, 2200 MPa or less at 100 ° C., and haze is 2.0% or less. Polyester resin film for mold release characterized by the following: It is.
(1) dA> dB
(2) dA> t
According to a second aspect of the invention, the surface reflection intensity (Wa) in the wavelength region of 0.1 mm to 0.3 mm measured using a wave scan device after laminating 50 films and applying a pressure of 10 MPa for 24 hours. The polyester resin film for release, which is 4.0 or less.
The third invention is characterized in that the average particle size dA of the particles A is 0.1 to 1.2 μm, and the particle size distribution (dA75 / dA25) is 1.1 to 1.5. Polyester resin film.
4th invention is the said polyester resin film for mold release characterized by the thickness t of the said resin composition layer being 0.06 micrometer or less.
In the fifth invention, the average particle diameter dB of the particles B is 0.02 to 0.15 μm, and the ratio (dB / t) to the thickness t of the resin composition layer is 0.1 to 1.5. Yes, the polyester resin film for mold release characterized by satisfying the following relationship (3).
(3) dA>t> dB
6th invention is a release film characterized by having a release layer in the at least one surface of the said polyester resin film for mold release.
7th invention is a transfer film which has a decoration layer in the mold release layer surface of the said mold release film.

  The polyester resin film for mold release of the present invention is a thin and flexible substrate made of a polyester resin having transparency, and has a good appearance suitable for giving a mirror surface design by transfer. And to maintain it. Therefore, as a base material for transfer films applied to decoration for automobile interior and exterior members, household electrical appliance membrane switches, mobile phone members, building material members, etc. It can be suitably used as a base material for a transfer film for simultaneous molding transfer suitable for decoration.

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

(Composition of base film)
The base film of the present invention has flexibility (moldability) necessary for simultaneous molding transfer and rigidity (morphological stability) suitable for lamination of the decorative layer. Such characteristics can be defined by the elastic modulus of the film at each temperature. That is, if the elastic modulus at 30 ° C. indicating the stability of the form is small, strain in the in-plane direction is generated in the step of providing the release layer and the decoration layer, and it is difficult to ensure flatness. Therefore, the elastic modulus at 30 ° C. is preferably 1000 MPa or more, more preferably 1500 MPa or more, further preferably 2000 MPa or more, and still more preferably 3000 MPa or more. On the other hand, if the elastic modulus at 30 ° C. is large, it may be difficult to follow the roll in the step of providing the release layer and the decoration layer. Therefore, the elastic modulus at 30 ° C. is preferably 8000 MPa or less, more preferably 7000 MPa or less, further preferably 6000 MPa or less, and still more preferably 5000 MPa or less.

  In addition, if the elastic modulus at 100 ° C., which is an index of moldability, is large, it is difficult to obtain flexibility in shape formation and integration with the decoration layer via the adhesive layer. Therefore, the elastic modulus at 100 ° C. is desirably 2200 MPa or less, preferably 2000 MPa or less, and more preferably 1800 MPa or less. On the other hand, if the elastic modulus at 100 ° C. is small, distortion or meandering due to tension during passage of the process may easily occur. Therefore, the elastic modulus at 100 ° C. is preferably 10 MPa or more, more preferably 30 MPa or more, and further preferably 100 MPa or more.

  In order to control the elastic modulus of the base film within the above range, it is preferable to add a third component to the polyester resin composition constituting the base film, or to control the orientation and the like by stretching. Specifically, the aspect is as follows.

  The polyester-based resin used for the substrate of the release film of the present invention is a resin composed of a general dicarboxylic acid structural unit and a diol structural unit, and monomers applicable to the dicarboxylic acid structural unit include terephthalic acid and isophthalic acid. Phthalic acid, 2-methylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, tetralindicarboxylic acid, etc. Aromatic dicarboxylic acids and their ester-forming derivatives, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, norbornane dicarboxylic acid Acid, tricyclodecanedi Carboxylic acid, saturated alicyclic dicarboxylic acids such as penta cyclododecane dicarboxylic acids, and, like their ester forming derivatives thereof. Moreover, as a monomer applicable to a diol structural unit, ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene glycol, neopentyl glycol, etc. Polyether compounds such as aliphatic diols, polyethylene glycol, polypropylene glycol, polybutylene glycol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalenediethanol, , 3-Decahydronaphthalene diethanol, 1,4-decahydronaphthalene diethanol, 1,5-decahydronaphthalene diethanol, 1,6-decahydronaphthalene diethanol, 2,7-decahydride Alicyclic diols such as naphthalene diethanol, tetralin dimethanol, norbornene dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol, 4,4 '-(1-methylethylidene) bisphenol, methylene bisphenol (bisphenol) F), 4,4′-cyclohexylidene bisphenol (bisphenol Z), bisphenols such as 4,4′-sulfonyl bisphenol (bisphenol S), and alkylene oxide adducts of the bisphenols. In addition, aromatic dihydroxy compounds such as hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylbenzophenone, and alkylene oxide adducts of the aromatic dihydroxy compounds And diols having a cyclic acetal skeleton.

  In the above polyester-based resins, aromatic dicarboxylic acids as dicarboxylic acid structural units and their ester-forming derivatives are preferred from the viewpoint of versatility, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acids, or their Ester-forming derivatives are preferred, and terephthalic acid and / or isophthalic acid and / or naphthalenedicarboxylic acids with respect to the total dicarboxylic acid component is 70 mol in terms of compatibility when mixed with other polyester resins. % Or more, preferably 85 mol% or more, particularly preferably 95 mol% or more.

  Moreover, as a diol structural unit in said polyester-type resin, aliphatic diols, such as ethylene glycol, trimethylene glycol, 1, 4- butanediol, propylene glycol, neopentyl glycol, are preferable from a versatility viewpoint, and branched. From the viewpoint of transparency and moldability, application of neopentyl glycol, which is an aliphatic glycol, and 1,4-cyclohexanedimethanol, which is an alicyclic glycol, is preferable, and 15 to 60 mol% is preferable in all diol components, and 20 to 20 mol% is preferable. 50 mol% is particularly preferable. Furthermore, in addition to these diol structural units, it is desirable to apply 1,3-propanediol or 1,4-butanediol from the viewpoint of moldability, and the total diol component is preferably 70 mol% or more, particularly preferably. 90 mol% or more is preferable.

  In this invention, it is preferable to aim at coexistence of a moldability and form stability by containing the above 3rd components as a polyester-type resin which comprises a film. Specifically, it is preferable to use a polyester resin obtained by blending a copolyester alone or one or more types of homopolyester or copolyester. As a polyester resin composition used for the film of the present invention, for example, when terephthalic acid or ethylene glycol is the main component, the other third component is preferably 3 to 50 mol%, more preferably 4 to 30 mol%. More preferably, 5 to 20 mol% is included. Further, a blend of polyethylene terephthalate and a homopolyester such as polybutylene terephthalate or polytrimethylene terephthalate may be used, and the copolymer polyester may be further blended.

  In addition, such a polyester-based resin is a monoalcohol such as butyl alcohol, hexyl alcohol, and octyl alcohol, or a polyhydric alcohol having a valence of 3 or more such as trimethylolpropane, glycerin, and pentaerythritol, as long as the object of the present invention is not impaired. Monocarboxylic acids such as benzoic acid, propionic acid, and butyric acid can be used as raw material monomers, and, as long as transparency is not impaired, antistatic agents, surfactants, plasticizers, and light stabilizers are used as necessary. Additives such as agents and waxes can be included. In order to achieve high transparency, it is preferable not to add particles to the polyester resin.

  As the base material, one or more of the above-mentioned polyester-based resins are singly or extruded by dry blending, a single layer, or, for example, two types of two layers of A / B configuration, B / A / B configuration In the case of using a polyester resin having different dicarboxylic acid constitutional units and / or diol constitutional units, it is possible to make a laminated structure of two types, three layers, and three types, three layers, C / A / B. In addition, when the difference regarding each structural unit in each layer is 8 mol% or less, more preferably 5 mol% or less, it is possible to expect a reduction in peeling force between layers.

  Such a substrate depends on the layer structure and layer structure, but if the glass transition temperature is low, the flatness is likely to be impaired due to thermal wrinkles, etc., and it becomes difficult to lay a release layer or a decoration layer, and if it is high, it is three-dimensional. It becomes difficult to follow the shape. Therefore, the glass transition temperature is preferably 40 to 100 ° C, more preferably 45 to 90 ° C, and further preferably 60 to 90 ° C.

  In addition, if the melting point is low, breakage and the like may occur due to heating when following the three-dimensional shape, and if it is high, it is necessary to increase the temperature in extrusion, and the load on the equipment becomes large. 200-270 degreeC is preferable and 200-260 degreeC is more preferable.

In addition, from the viewpoint of suppressing thermal wrinkles and the like in the drying process when providing the release layer and the decoration layer, the rigidity EI that is the product of the cross-sectional secondary moment I per unit width 1 mm at 100 ° C. and the elastic modulus E is 0. is preferably .01N · mm ² or more, more preferably 0.05 N · mm ² or more, and more preferably 0.1 N · mm ² or more. In order to control the rigidity within the above range, the thickness of the substrate is preferably 10 to 150 μm, more preferably 15 to 125 μm, still more preferably 20 to 100 μm, still more preferably 20 to 75 μm, still more preferably 20 to 65 μm. preferable.

  In obtaining such a base material, first, one or more types of polyester resins used for the base material are singly or dry blended to perform extrusion to obtain a sheet-like material. In this case, the same type of polyester resin having different intrinsic viscosity, different types of polyester resins, and the like can be obtained by a known method such as a combining adapter method, a multi-slot method, or a multi-manifold method. A laminated structure such as a two-type two-layer configuration, a two-type three-layer configuration of B / A / B configuration, or a three-type three-layer configuration of C / A / B can also be used.

  Next, the method is not particularly limited, but the sheet-like material is stretched 1.6 to 4.2 times in the machine direction and / or 1.6 to 4.2 times in the width direction, and then dimensional stability and the like are increased. It is preferable to obtain a film-like substrate by performing a heat treatment for the main purpose. By imparting orientation to the film, it is possible to more suitably stabilize the form during film processing. In addition, as a specific method, after extending | stretching this sheet-like material to the machine direction (MD) in the temperature range of +10 degreeC-+50 degreeC of glass transition temperature, -20 degreeC-+15 degreeC with respect to this temperature range After using the MD / TD method that stretches in the transverse direction (TD) in the temperature range of, a heat treatment is performed in the temperature range of −5 ° C. to −30 ° C. of the melting point to obtain a film-like substrate. In the heat treatment, a tension heat treatment or a relaxation heat treatment can be selected.

  As for the stretching method, there is a sequential biaxial stretching method such as a TD / MD method that stretches in the longitudinal direction after stretching in the width direction, but the longitudinal direction and the width direction are stretched almost simultaneously. The simultaneous biaxial stretching method is desirable, and with respect to the stretching ratio, if necessary, multistage stretching in which stretching in the same direction is performed in multiple stages may be performed.

(Surface characteristics of release film)
The polyester resin film for mold release of the present invention has a mirror surface state excellent in surface feeling. Such surface feeling can be represented by the reflection intensity on the film surface measured using a wave scanning device.

  The surface reflection intensity (Wa) in the wavelength region of 0.1 mm to 0.3 mm is a value measured by the method described later, and generally indicates surface irregularities called “skin skin”, “orange peel” and the like. is there. This can be observed as a distortion of the map on the film surface by visual observation. When this value is large, a phenomenon in which the outline is blurred when viewed by reflecting a fluorescent lamp or the like becomes visible. The reflection strength (Wa) of the film surface of the polyester resin film for release of the present invention is preferably 4.0 or less, more preferably 3.5 or less, and further preferably 3.0 or less. Since the reflection intensity (Wa) in the release film of the present invention is not more than the above upper limit, the design applied by the transfer method has a good appearance and can exhibit high specularity.

  Furthermore, a general release film becomes a release film by coating a release layer. When the film is wound around a roll through the process, a pressure of 6 to 8 MPa is applied in the radial direction when it is high. . Thereby, surface unevenness | corrugation arises in a release film. Similarly, the release film becomes a transfer film by laying a decorative layer or the like, and when wound around a roll through the process, a pressure of 6 to 8 MPa is applied in the radial direction when it is high. Therefore, surface irregularities are generated in the decorative layer of the transfer film. Therefore, it is preferable for the base film to maintain a predetermined appearance even under a certain pressure. Such a situation can be reproduced by laminating 50 films at a level not affected by the pressing flat plate and applying a pressure of 10 MPa. Therefore, even after 50 sheets are laminated and a pressure of 10 MPa is applied to the release film of the present invention, the reflection intensity (Wa) is preferably 4.0 or less, more preferably 3.5 or less. Furthermore, 3.0 or less is more preferable. The release film of the present invention is a good release film or transfer film because the surface reflection strength (Wa) is not more than the above upper limit even after stacking 50 sheets and applying a pressure of 10 MPa. Appearance can be suitably maintained, and a mirror surface can be suitably exhibited as a design applied by a transfer method.

  Furthermore, when the transparency of the film is low, there is a problem in inspections such as pattern confirmation of the decorative layer and detection of scratches. Therefore, the haze of the release polyester resin film of the present invention is preferably 2.0% or less, more preferably 1.5% or less, and further preferably 0.7% or less. Since the haze in the release film of the present invention is not more than the above upper limit, it has high transparency.

(Resin composition layer)
In order to control the surface characteristics and transparency of the film within the above ranges, it is preferable to control the particle configuration constituting the film, particularly the particle configuration added to the resin composition layer on the film surface, within a predetermined range. Therefore, the polyester resin film for mold release of the present invention preferably has a resin composition layer containing specific particles laminated on at least one surface of the substrate. The preferred particle configuration contained in the resin composition layer is as follows.

  The resin composition layer of the present invention preferably contains at least one kind of particle, particle A. If the average particle diameter dA of the particles A is small, the air entrained between the films in the roll cannot be removed, and acne-like irregularities and wrinkles are generated around it. As a result, surface irregularities called “yuzu skin”, “orange peel” and the like are generated. Accordingly, the average particle diameter dA is preferably 0.01 to 10 μm, more preferably 0.05 to 4 μm, further preferably 0.1 to 1.2 μm, and 0.2 to 1.0 μm. It is even more preferable. In particular, when a particle B described later is also added, it is more preferably 0.1 to 1.2 μm, and still more preferably 0.2 to 1.0 μm.

  Furthermore, when the particle size distribution (dA75 / dA25) of the particle A is large, a local dent may be given to the base material, the decoration layer, and the like, so 1.5 or less is preferable and 1.4 or less is more preferable. The lower limit of the particle size distribution (dA75 / dA25) is preferably 1.1 from the viewpoint of industrial productivity.

  In addition, if the content of the particles A is small, the air entrapped between the films in the roll cannot be removed, and acne-like irregularities and wrinkles are generated in the periphery, and if the content is large, the dispersion of the particles becomes difficult and the transparency Decrease. Therefore, the content of the particles A is preferably 0.001 to 30% by mass, more preferably 0.01 to 15% by mass, and further 0.05 to 5% by mass satisfying these requirements. The haze of the release film of the present invention can achieve 2.0% or less.

  Furthermore, it is preferable that the resin composition layer includes particles B that are particles other than the particles A from the viewpoint of blocking resistance and scratch resistance. If the average particle size dB of the particles B is small, it will be difficult to contribute to the improvement of blocking resistance and scratch resistance. If the particle size B is large, “dent skin”, “orange peel” etc. Surface irregularities referred to as occur. Therefore, the average particle diameter dB is preferably 0.01 to 0.2 μm, and more preferably 0.02 to 0.15 μm.

  In addition, if the content of the particles B is small, it becomes difficult to contribute to the improvement of blocking resistance and scratch resistance, and if it is large, a decrease in transparency may occur. Therefore, the content of the particles B is preferably 0 to 10% by mass.

Here, it is preferable that the thickness t of the resin composition layer and the average particle diameters dA and dB satisfy the following relationships (1) and (2). As a result, surface protrusions effective for air escape are formed, a stable coefficient of friction is obtained during processing, and particles are less likely to fall off.
(1) dA> dB
(2) dA> t

  Furthermore, depending on the composition of the resin composition and the amount of particles to be added, if the thickness t of the resin composition layer is small, the particles may slip off, and if it is large, the transparency and scratch resistance may be reduced. There is a case. Therefore, the thickness t of the resin composition layer is preferably 0.02 to 0.50 μm, more preferably 0.03 to 0.10 μm, and still more preferably 0.04 to 0.08 μm. In particular, in order to satisfy the above formulas (1) and (2) and to give an effective surface uneven shape by the particles A, the thickness t of the resin composition layer is more preferably 0.06 μm or less.

  In addition, the thickness t of the resin composition layer has a ratio (dB / t) to the average particle diameter dB of the particles B of 0.1 to 1.5, and the relationship with the average particle diameter dA of the particles A is dA. It is preferable to satisfy> t> dB. With this, for the occurrence of acne-like irregularities that occur without the air trapped between the films in the roll and the surroundings being wrinkled, the occurrence of minute irregularities caused by local depressions in the base material, decoration layer, etc. It shows a suitably high improvement effect.

  Here, the air escape index (AirL) is a value measured by the method described later. The smaller this value, the more the film is formed as a roll during the coating process, the release layer, and the decorative layer. This indicates that the air escape is good, there are no acne-like irregularities and wrinkles around it, and it is possible to exhibit good winding properties. Specifically, the air escape index (AirL) is preferably 350 seconds or less, more preferably 200 seconds or less, and even more preferably 50 seconds or less. Since the air release index (AirL) of the release film of the present invention is not more than the above upper limit, it has good winding properties.

  Examples of the particles A include titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay, and a mixture thereof. Furthermore, as other general inorganic particles, calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride, etc., inorganic particles, styrene, acrylic, melamine, benzoguanamine, silicone And organic polymer particles such as those. Among these, organic polymer-based particles such as styrene-based, acrylic-based, and benzoguanamine-based particles that can easily obtain particles having a narrow particle size distribution are preferable.

  Similarly, the particle B may be titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay, or a mixture thereof. Furthermore, as other general inorganic particles, calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride, etc., inorganic particles, styrene, acrylic, melamine, benzoguanamine, silicone One of the preferred embodiments is the use of a combination of a plurality of inorganic particles having different average particle diameters for the purpose of improving the scratch resistance and blocking resistance of the resin composition described below. It is.

  The resin composition layer contains a binder resin. As the binder resin, at least one kind of polyester resin, polyurethane resin, or polyacrylic resin can be used.

  The polyester resin used in the resin composition layer of the present invention is preferably a copolyester resin having a branched glycol component as a constituent component. The branched glycol component referred to here is, for example, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2-methyl-2-butyl-1,3- Propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-isopropyl-1,3-propanediol, 2-methyl-2-n-hexyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 2-ethyl-2-n -Hexyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, 2-n-butyl-2-propyl-1,3-propanediol, and 2,2- Such -n- hexyl-1,3-propanediol.

  The branched glycol component is contained in the total glycol component in a proportion of preferably 10 mol% or more, more preferably 20 mol% or more. As the glycol component other than the above compounds, ethylene glycol is most preferable. If it is a small amount, diethylene glycol, propylene glycol, butanediol, hexanediol, 1,4 cyclohexanedimethanol or the like may be used.

  The dicarboxylic acid component contained as a constituent in the copolymerized polyester resin is most preferably terephthalic acid, dimethyl terephthalate, isophthalic acid, or dimethyl isophthalate. If the amount is small, other dicarboxylic acids; diphenylcarboxylic acid and 2,6-naltalenedicarboxylic acid aromatic dicarboxylic acid may be added and copolymerized.

  In addition to the dicarboxylic acid component, 5-sulfoisophthalic acid is preferably used in the range of 1 to 10 mol% in order to impart water dispersibility, for example, 4-sulfonaphthalene isophthalic acid-2,7-dicarboxylic acid. And acid and 5- (4-sulfophenoxy) isophthalic acid and its salts.

  In particular, a polyester-based graft copolymer capable of forming a highly self-crosslinked structure is preferable in order to prevent process contamination due to slipping of particles A contained in the resin composition layer, and the hydrophobic copolyester resin has at least A grafted product of a polymerizable unsaturated monomer containing an acid anhydride having one type of double bond is preferred because it is less susceptible to the influence of humidity and the like.

  Examples of the polyurethane resin used in the resin composition layer of the present invention include polyester polyol and polyether ester polyol. Examples of the polyester polyol and the polyether ester polyol mainly include linear or branched compounds. These include polysaturated or unsaturated carboxylic acids such as succinic acid, adipic acid, phthalic acid and maleic anhydride, or the carboxylic acid anhydride, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl Polyhydric saturated and unsaturated alcohols such as glycol, 1,6-hexanediol and trimethylolpropane, polyalkylene ether glycols such as relatively low molecular weight polyethylene glycol and polypropylene glycol, or mixtures of these alcohols; Can be obtained by condensation.

  Furthermore, polyesters obtained from lactones and hydroxy acids can be used as polyester polyols, and polyether esters obtained by adding ethylene oxide or propylene oxide to polyesters prepared in advance can be used. it can.

  In particular, in order to impart appropriate ductility to the resin composition layer and prevent process contamination due to sliding of the specific particles A and the like contained, it is generally large in polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin. Among the classifications, it is preferable to use a polycarbonate-based polyurethane resin in view of blocking resistance.

  Although the following can be illustrated as a monomer component which comprises an acrylic resin, It can manufacture by a well-known method and is not specifically limited in the range which does not inhibit the effect of this invention.

  Monomers to be used for the polymerization of the acrylic resin include alkyl acrylate and alkyl methacrylate (the alkyl group is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl). Group, lauryl group, stearyl group, cyclohexyl group, phenyl group, benzyl group, etc.) and a copolymer having a functional group as described below for copolymerization.

  That is, the functional group includes a carboxyl group, a methylol group, an acid anhydride group, a sulfonic acid group, an amide group or an alkylolated amide group, an amino group (including a substituted amino group), an alkylolated amino group, and a hydroxyl group. An epoxy group can be exemplified, and these salts and esterified products may be copolymerized.

  Examples of the compound having a carboxyl group and / or a salt thereof or an acid anhydride group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, alkali metal salts of these carboxylic acids, ammonium salts, or An anhydride etc. are mentioned.

  Examples of the compound having a sulfonic acid group and / or a salt thereof include vinyl sulfonic acid, styrene sulfonic acid, alkali metal salts and ammonium salts thereof.

  Examples of the compound having an amide group or an alkylolated amide group include acrylamide, methacrylamide, N-methyl methacrylamide, methylol acrylamide, methylol methacrylamide, ureido vinyl ether, β-ureido isobutyl vinyl ether, ureido ethyl acrylate, and the like. Can be mentioned.

  Examples of the compound having an amino group or an alkylolated amino group and / or a salt thereof include diethylaminoethyl vinyl ether, 2-aminoethyl vinyl ether, 3-aminopropyl vinyl ether, 2-aminobutyl vinyl ether, dimethylaminoethyl methacrylate, dimethylaminoethyl. Examples thereof include vinyl ethers, and those obtained by methylolation of their amino groups, quaternary salts with alkyl halides, dimethyl sulfate, sultone, and the like.

  Examples of the compound having a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, β-hydroxyvinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, polyethylene glycol Examples include monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, and polypropylene glycol monomethacrylate.

  Examples of the compound having an epoxy group include glycidyl acrylate and glycidyl methacrylate.

  Preferable specific examples of the acrylic resin having a crosslinkable functional group include quaternary obtained by copolymerizing acrylic acid having a crosslinkable functional group and N-methylolacrylamide in a desired ratio in methyl methacrylate, ethyl acrylate and / or butyl acrylate. Examples thereof include, but are not limited to, acrylic copolymers.

  In addition to the above, the following compounds may be used in combination. That is, acrylonitrile, methacrylonitrile, styrenes, butyl vinyl ether, maleic acid mono or dialkyl ester, itaconic acid mono or dialkyl ester, methyl vinyl ketone, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl pyridine, vinyl pyrrolidone, vinyl trisalkoxysilane Of course, it is not limited to these.

  These monomers having a crosslinkable functional group and other compounds may be copolymerized with a monomer as a basic skeleton at an arbitrary ratio, and two or more monomers may be copolymerized. As a specific example of the preferred ratio, the ratio of the monomer having a crosslinkable functional group to the monomer serving as the basic skeleton is usually about 1 to 10% by mass.

  The glass transition temperature of the acrylic resin can be arbitrarily set depending on the monomer used.For example, to obtain a polymer having a high glass transition temperature, the copolymerization amount of methyl methacrylate is increased, and for obtaining a resin having a low glass transition temperature, it is long. Copolymerization of chain alkyl acrylates is effective. Moreover, since the toughness of a resin composition layer increases by making the molecular weight of an acrylic resin into 450,000 or more, it is especially preferable.

  Moreover, it is also preferable that the resin composition layer of this invention contains a crosslinking agent from the point of blocking resistance. The blending ratio of the crosslinking agent is preferably 5 to 40 parts by mass, more preferably 8 to 25 parts by mass with respect to 100 parts by mass of the binder resin. If the blending ratio of the crosslinking agent is less than 5 parts by mass with respect to 100 parts by mass of the binder resin, the blocking resistance may decrease, which is not preferable. Conversely, when it exceeds 40 parts by mass, the flexibility for following the moldability may be reduced.

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

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

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

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

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

  In the resin composition layer of the present invention, known additives, for example, antioxidants, heat stabilizers, weathering stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, as long as the effects of the present invention are not impaired. Organic or inorganic particles, antistatic agents, nucleating agents and the like may be added.

  The resin composition layer can be provided by a coating method or a coextrusion method. In particular, as a coating method, a conventionally used method such as a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, or a reverse roll coating method can be applied.

  The method of providing the resin composition layer is not particularly specified, but a method of applying before stretching of the film as a substrate, a method of applying after longitudinal stretching, and a method of applying at the stage of performing heat treatment after stretching are possible. Among them, the in-line coating method, in which the film is applied before completion of the film orientation and then stretched in at least one direction and then the film orientation is completed, is preferable because the effect of the present invention can be expressed more remarkably. Is the way

(Release layer)
Next, release processing will be described.
The release film of the present invention is a film formed by forming a release layer on at least one surface of the polyester resin film of the present invention. The release layer is preferably provided on the surface opposite to the resin composition layer from the viewpoint of slipperiness with the mold and air escape. The release layer preferably contains one or more selected from silicone resins and fluororesins as a main component.

  As the silicone resin, a silicone resin generally used as a release agent can be used, and a silicone generally used in the field described in “Silicon material handbook” (Toray Dow Corning, 19933.8) and the like. It can be used by selecting from resins. Generally, a thermosetting or ionizing radiation curable silicone resin (including resin and resin composition) is used. As the thermosetting silicone resin, for example, condensation reaction type and addition reaction type silicone resins can be used, and as the ionizing radiation curable silicone resin, ultraviolet or electron beam curable silicone resins can be used. A release layer is formed by applying these on a film as a substrate and drying or curing.

  The curable silicone resin preferably has a degree of polymerization after curing of about 500 to 200,000, particularly about 1,000 to 100,000, and specific examples thereof include the following resins: Shin-Etsu Chemical ( KS-718, KS-774, KS-775, KS-778, KS-779H, KS-830, KS-835, KS-837, KS-838, KS-839, KS-841, KS- 843, KS-847, KS-847H, X-62-2418, X-62-2422, X-62-2125, X-62-2492, X-62-2494, X-62-5048, X-62- 470, X-62-2366, X-62-630, X-92-140, X-92-128, KS-723A ・ B, KS-705F, KS-708A, KS-883, KS-7 9, KS-719; TPR-6701, TPR-6702, TPR-6703, TPR-3704, TPR-6705, TPR-6721, TPR-6722, TPR-6700, XSR-7029, YSR manufactured by Toshiba Silicon Co., Ltd. -3022, YR-3286; DK-Q3-202, DK-Q3-203, DK-Q3-204, DK-Q3-205, DK-Q3-210, DK-Q3-240, manufactured by Dow Corning DK-Q3-3003, DK-Q3-3057, SFXF-2560; SD-7226, SD-7229, SD-7320, BY-24-900, BY-24- manufactured by Toray Dow Corning Silicone Co., Ltd. 171, BY-24-312, BY-24-374, SRX-375, SYL-OFF23, SRX-244 Such as ICI Japan made of (stock) SILCOLEASE425; SEX-290. Further, silicone resins described in JP-A-47-34447 and JP-B-52-40918 can also be used. These curable silicone resins may be used alone or in combination of two or more.

  As the fluororesin, a fluororesin generally used as a release agent can be used. Examples of such a fluororesin include, for example, a polymer (including an oligomer) composed of a fluorine-containing vinyl polymerizable monomer or a copolymer thereof, a fluorine-containing vinyl polymerizable monomer and a vinyl polymerizable monomer not containing a fluorine atom. Examples thereof include a copolymer with a monomer or a mixture thereof, and a resin having 5 to 80 mol% of fluorine atoms.

  In addition to the silicone resin and fluororesin, the release layer may contain additives that are usually used in the field as long as the effects of the present invention are not impaired. Examples thereof include an antifoaming agent, a coating property improving agent, a thickener, an antistatic agent, an antioxidant, an ultraviolet absorber, a magnetizing agent, and a dye. The thickness of the release layer is not particularly limited, but is preferably in the range of 0.05 to 5 μm.

(Transfer film)
A transfer film is configured by laminating decorative layers such as a design layer and an adhesive layer on the release layer of the release film. Depending on the purpose, a hard coat layer and a metal vapor deposition layer are also laminated as a decorative layer. Furthermore, a functional agent such as an antistatic agent or an antibacterial agent is added to these release layer and transfer layer to give the function. In particular, by using a decorative layer such as a mirror ink or a metal vapor deposition layer, a suitable mirror surface property can be imparted by the film of the present invention.

Next, examples and comparative examples of the present invention will be shown. First, the measurement / evaluation method used in the present invention is shown below. Hereinafter, Examples 6 and 18 will be read as Reference Examples 6 and 18.

(1) Intrinsic viscosity ([η])
For the viscosity number obtained in accordance with JIS K 7367-5 "Plastics-Determination of viscosity of diluted solution using capillary viscometer-Part 5: Thermoplastic polyester (TP) homopolymer and copolymer" Under the following measurement conditions, the intrinsic viscosity [η] was defined as the value when the mass concentration c = 0 from the relationship of the viscosity number to the mass concentration c of the solution.
Solvent: Phenol / 1,1,2,2-tetrachloroethane = 60/40 (wt%)
Tube: Ubbelohde viscosity tube Temperature: 30 ± 0.1 (° C)

(2) Transition temperature (Tm, Tg)
The melting peak temperature obtained from the DSC curve of differential scanning calorimetry (DSC) in accordance with JIS K 7121 “Plastic Transition Temperature Measurement Method” is the melting temperature (Tm), and the midpoint glass transition temperature is the glass transition temperature (Tg). did.

(3) Elastic modulus (E ')
In the temperature dependence curve obtained according to JIS K 7198 “Testing method for temperature dependence of dynamic viscoelasticity by non-resonant forced vibration method of plastic”, the dynamic storage elastic modulus at 30 ° C. and 100 ° C. is expressed as the elastic modulus ( E ′).

(4) Thermal contraction rate (SH)
The dimensional change rate at 150 ° C. obtained in accordance with the dimensional change of JIS C 2318 “Electric polyethylene terephthalate film” was defined as the heat shrinkage rate (SH).

(5) Rigidity (EI)
Deflection amount measured using a stand base installed in a heating furnace set at 30 ° C or 100 ° C in accordance with the bending resistance (Method B) in JIS L 1096 “Fabric and knitted fabric test method” Stiffness (EI) was calculated from δ), the length of the sample (L), and the previously calculated bending load (W) of the sample per unit length at a unit width of 1 mm. In addition, the sample applied the average value of the two directions of a vertical direction (MD) and a horizontal direction (TD).

(6) Haze (Hz)
In accordance with JIS K 7105 “Plastic Optical Properties Test Method”, haze was determined from the total light transmittance and diffuse transmittance obtained by an integrating sphere light transmittance measuring device.

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

(8) Thickness (t) of resin composition layer
A film section obtained by cutting with a microtome perpendicular to the film surface is photographed using a transmission electron microscope (TEM), and the thickness of the resin composition layer is measured on the photograph. This operation was performed 10 times at different locations, and the average of the measured values was taken as the thickness (t) of the resin layer.

(9) Average particle diameter (d) and particle size distribution (d75 / d25)
Take 3 or more photographs of the particles exposed on the resin layer surface of the film with a scanning electron microscope (800 times magnification), and set the equivalent area diameter of the particles as the particle size. The particle size when the ratio when accumulated from 25%, 50%, 75% of the total volume is d25, d50, d75, d50 is the average particle size (d), and d75 is divided by d25. Was defined as a particle size distribution (d75 / d25).
In addition, when two or more kinds of particles coexist, the particle size distribution of one kind of particle is defined from the particle size at which the number change starts to the minimum particle size at which the number change does not once occur.

(10) Surface reflection intensity (Wa): wave scan method A black sheet (GA board FS black 26) is laid on the surface opposite to the resin composition layer of the film, and wave scan (BYK Gardner, Inc.) is applied to the resin layer side of the film. The value (Wa) of the reflection intensity in the wavelength range of 0.1 to 0.3 mm obtained by running the product was evaluated (initial).
Further, 50 films cut into A4 size were laminated so that the resin composition layer was on the upper surface, and after applying a pressure of 10 MPa for 24 hours, the value of the reflection strength (Wa) as described above for the lowermost film. Was evaluated (after lamination).
Incidentally, the reflection intensity in the wavelength region of 0.1 to 0.3 mm is an index of surface roughness, and it is possible to evaluate fine irregularities generally called orange beer. The smaller this value, the more smooth the surface is. Indicates high.

(11) Processability of film Using a general coating machine, a coating for release layer (thermosetting silicone resin dissolved in MEK solvent) is applied to a dry thickness of 100 nm, and then a hot air system In the step of drying at (80 to 90 ° C.), the following criteria were ranked. In addition, (double-circle), (circle), and (triangle | delta) were set as the pass, and x was set as the disqualification.
◎: Almost no change in conditions such as tension and temperature is required to eliminate thermal wrinkles and meandering. ○: Conditions such as tension and temperature are required to eliminate thermal wrinkles and meandering.
Stable conditions can be set. △: Conditions such as tension and temperature need to be changed for thermal wrinkles and meandering.
The set condition is also narrow, or thermal wrinkles and meandering occur. ×: It is difficult to eliminate thermal wrinkles and meandering only by changing conditions such as tension and temperature.

(12) Rollability of film In the rolled product having a width of 1 m and a length of 800 m after passing through the above steps, the following criteria were ranked. In addition, (circle) and (triangle | delta) were set as the pass and x was set as the failure.
○: Acne-like irregularities and the surrounding wrinkles are not generated, and there is no blocking. △: Acne-like irregularities are slightly observed, but there are no wrinkles or blocking around it. ×: Acne-shaped irregularities and the surrounding area. Wrinkles are observed or there is blocking

(13) Appearance of the film: visual method A black sheet (GA board FS black 26) is laid on the surface opposite to the resin composition layer of the film, and the image is visually observed with a fluorescent lamp projected on the film. The following criteria were ranked. In addition, (double-circle), (circle), and (triangle | delta) were set as the pass, and x was set as the disqualification.
◎: No distortion or the like is observed in the mapping of the fluorescent lamp, etc. ○: Slight distortion or the like is observed in the mapping of the fluorescent lamp or the like △: The distortion is considerably observed in the mapping of the fluorescent lamp or the like ×: In the mapping of the fluorescent lamp or the like Distortion is considerably observed and outline is blurred

(14) Formability After 5 mm square printing is performed on the substrate, the substrate is heated with an infrared heater heated to 500 ° C., then the diameter of the opening is 50 mm, the diameter of the bottom is 40 mm, and the depth Vacuum forming was performed with a mold having a length of 20 mm and a curvature of a diameter of 0.5 mm at the corners around the bottom surface. In addition, the following reference | standard ranking was performed about the shaping state obtained on the optimal conditions in the heating time 10-20sec with respect to a base material, and the mold temperature of 40-90 degreeC conditions. In addition, (double-circle), (circle), and (triangle | delta) were set as the pass, and x was set as the disqualification.
A: (i) There is no tear in the shaped state,
(Ii) The radius of curvature of the corner is 1 mm or less and the printing deviation is 0.1 mm or less. ○: (i) There is no tear in the shaped state,
(Ii) Corner radius of curvature is 1 to 1.5 mm, or printing deviation is 0.1 to 0.2 mm.
Δ: (i) There is no tear in the shaped state,
(Ii) the radius of curvature of the corner exceeds 1.5 mm, and
Print misalignment exceeds 0.2 mm ×: (i) The shape is broken
Or
(Ii) There is no tearing in the shaped state, and the following two items (a) to (c) are applicable: (a) the corner radius of curvature exceeds 1.5 mm, and
Print misalignment exceeds 0.2 mm (b) Substrate is whitened and transparency is lowered (c) Appearance is poor with large wrinkles

(15) Appearance of molded product: visual method A layer composed of a release layer, a printing layer (black) and an adhesive layer is formed on the transfer film obtained in the examples, a transfer layer is produced, and the transfer layer is opened. It was obtained by performing simultaneous molding transfer using a fitting type mold having a diameter of 50 mm, a diameter of the bottom surface of 40 mm, a depth of 20 mm, and a curvature of a diameter of 0.5 mm around the corner of the bottom surface. The surface of the molded product was visually observed and ranked according to the following criteria. In addition, (double-circle), (circle), and (triangle | delta) were set as the pass, and x was set as the disqualification.
◎: No distortion or the like is observed in the mapping of the fluorescent lamp, etc. ○: Slight distortion or the like is observed in the mapping of the fluorescent lamp or the like △: The distortion is considerably observed in the mapping of the fluorescent lamp or the like ×: In the mapping of the fluorescent lamp or the like Distortion is considerably observed and outline is blurred

(Polymerization of polyester resin for substrate)
<Resin A: Polyethylene terephthalate>
Terephthalic acid (TPA) and ethylene glycol (EG) are charged into an esterification reaction kettle and subjected to esterification for 120 minutes under conditions of a pressure of 0.25 MPa and a temperature of 220 to 240 ° C., and then the inside of the reaction kettle is brought to normal pressure. Then, titanium tetrabutoxide or the like is added as a polymerization catalyst, and the reaction system is gradually depressurized while stirring to 0.5 hPa in 75 minutes, and the temperature is raised to 280 ° C. and melt viscosity at 280 ° C. Stirring was continued until the value reached a predetermined value, and the polymerization reaction was performed. Thereafter, the polymer was discharged into water and cooled to obtain a polyester resin A.

<Resin B: Polytrimethylene terephthalate>
After charging the reaction kettle with dimethyl terephthalate (DMT) and 1,3-propanediol and carrying out the transesterification reaction at 170-210 ° C. at normal pressure for 180 minutes, the polyester system was used in the same manner as the polymerization of the resin A described above. Resin B was obtained.

<Resin C: Polybutylene terephthalate>
After charging the reaction kettle with dimethyl terephthalate (DMT) and 1,4-butanediol and carrying out the transesterification reaction at 170-210 ° C. at normal pressure for 180 minutes, the polyester system was used in the same manner as the polymerization of the resin A described above. Resin C was obtained.

<Resin D, E, F: Copolyester>
Esterification of terephthalic acid (TPA), isophthalic acid (IPA), ethylene glycol (EG), neopentyl glycol (NPG), and 1,4-cyclohexanedimethanol (CHDM) so that each has a predetermined molar ratio Thereafter, polyester resins D, F, and G were obtained with reference to the above-described resin A and / or resin B and / or resin C.
The above resins are shown in Table 1.

(Preparation of polyester resin for resin composition layer)
A transesterification reaction and a polycondensation reaction are carried out by a conventional method, and as a dicarboxylic acid component (based on the whole dicarboxylic acid component) 46 mol% terephthalic acid, 46 mol% isophthalic acid and 8 mol% sodium 5-sulfonatoisophthalate, A water-dispersible sulfonic acid metal base-containing copolymer polyester resin (a1) having a composition of 50 mol% ethylene glycol and 50 mol% neopentyl glycol (relative to the entire glycol component) was prepared as a glycol component.

(Preparation of coating solution A)
The melamine compound (DIC's Becamine M-3 solid content concentration 60%) is 20 parts by mass with respect to 100 parts by mass of the copolymerized polyester resin (a1) obtained above and the copolymerized polyester resin. Mix, styrene-divinylbenzene crosslinked particles having a total resin solid content concentration of 2.8% by mass and an average particle size of 0.8 μm, and 0.05% by mass of silica particles having an average particle size of 0.06 μm with respect to the total resin. The coating liquid A was obtained by diluting with a mixed solvent of water / isopropyl alcohol (= 65/35; mass ratio) so as to contain 7.3% by mass with respect to the total resin.

<Examples 1-3>
Resin A, resin B and resin E of the above-mentioned polyester-based resin for base materials are dry blended at a predetermined blending ratio, and kneaded and extruded using an extruder, and a skin layer / core layer / skin layer (ratio 10) Amorphous unstretched sheet while being melt-extruded from the slit so as to be (weight% / 80 weight% / 10 weight%), rapidly cooled and solidified on a chill roll having a surface temperature of 30 to 40 ° C. Got. And after extending the obtained unstretched sheet in the longitudinal (machine) direction at a predetermined temperature and a predetermined magnification with respect to the glass transition temperature in the longitudinal direction between the heating roll and the cooling roll, The coating liquid A shown is applied to one side of the film by a roll coating method, dried at 130 ° C. for 3 seconds, and then stretched in a transverse direction (perpendicular to the machine direction) at a predetermined temperature and a predetermined magnification. Next, relaxation is performed by 3 to 5% based on the temperature range of −10 to −35 ° C. with respect to the melting temperature, and the molds having the respective resin ratios have a thickness of 15 μm, 25 μm, 100 μm, and 125 μm. A film was obtained, and measurement and evaluation methods were carried out.

<Comparative Example 1>
Except that only the resin A is used as the above-mentioned polyester-based resin for the substrate, an extruded machine is basically used in the same manner as in Examples 1 to 3, and the extruded product is melt-extruded from the slit, and the surface temperature is 30. An amorphous unstretched sheet was obtained while rapidly solidifying on a chill roll of ˜40 ° C. and simultaneously adhering by an electrostatic application method. And after extending the obtained unstretched sheet in the longitudinal (machine) direction at a predetermined temperature and a predetermined magnification with respect to the glass transition temperature in the longitudinal direction between the heating roll and the cooling roll, The coating liquid A shown is applied to one side of the film by a roll coating method, dried at 130 ° C. for 3 seconds, and then stretched in a transverse direction (perpendicular to the machine direction) at a predetermined temperature and a predetermined magnification. Next, relaxation is performed by 3 to 5% based on a temperature range of −10 to −35 ° C. with respect to the melting temperature to obtain release films having thicknesses of 15 μm, 25 μm, 100 μm, and 125 μm, and measurement and evaluation The method was carried out.

In addition, Table 1 shows Examples 1 to 3 and Comparative Example 1 described above.

  In Examples 1 to 3 and Comparative Example 1, the softness and thickness of the substrate were changed. It is recognized that the surface reflection strength (Wa) tends to increase as the thickness becomes smaller. In addition, although the thickness of 15 μm of Example 1 was able to control thermal wrinkles and meandering, the level of process passage was Δ, and signs of easy fracture were observed.

<Example 4>
Except for dry blending resin C and resin D at a predetermined compounding ratio as the polyester-based resin for the base material, an extruded machine was used in the same manner as in Comparative Example 1, and the extruded product was removed from the slit. An amorphous unstretched sheet was obtained while melt-extrusion and rapid cooling and solidification on a chill roll having a surface temperature of 30 to 40 ° C., while being brought into close contact by an electrostatic application method. And after extending the obtained unstretched sheet in the longitudinal (machine) direction at a predetermined temperature and a predetermined magnification with respect to the glass transition temperature in the longitudinal direction between the heating roll and the cooling roll, The coating liquid A shown is applied to one side of the film by a roll coating method, dried at 130 ° C. for 3 seconds, and then stretched in a transverse direction (perpendicular to the machine direction) at a predetermined temperature and a predetermined magnification. Next, relaxation is performed by 3 to 5% based on a temperature range of −10 to −35 ° C. with respect to the melting temperature to obtain release films having thicknesses of 15 μm, 25 μm, 100 μm, and 125 μm, and measurement and evaluation The method was carried out.
<Example 5>
Except for dry blending resin A and resin F at a predetermined blending ratio as the above-mentioned polyester-based resin for the base material, the skin layer / core is basically kneaded and extruded in the same manner as in Examples 1 to 3. Layer / skin layer (ratio 10 wt% / 80 wt% / 10 wt%), melt-extruded from the slit, rapidly cooled and solidified on a chill roll with a surface temperature of 30-40 ° C. An amorphous unstretched sheet was obtained. And after extending the obtained unstretched sheet in the longitudinal (machine) direction at a predetermined temperature and a predetermined magnification with respect to the glass transition temperature in the longitudinal direction between the heating roll and the cooling roll, The coating liquid A shown is applied to one side of the film by a roll coating method, dried at 130 ° C. for 3 seconds, and then stretched in a transverse direction (perpendicular to the machine direction) at a predetermined temperature and a predetermined magnification. Next, relaxation is performed by 3 to 5% based on a temperature range of −10 to −35 ° C. with respect to the melting temperature to obtain release films having thicknesses of 15 μm, 25 μm, 100 μm, and 125 μm, and measurement and evaluation The method was carried out.

Table 3 shows Examples 4 to 5 described above.

  In Examples 4 and 5, the resin constituting the base material with an ideal coat is different, but the thickness is changed within a predetermined range. Even if the resins are different, there is no problem as a base material, and the resin composition layer works effectively.

(Coating solution B)
It mixes so that a melamine compound (Becamine M-3 solid content concentration 60% by DIC) may be 20 mass parts with respect to 100 mass parts of copolymer polyester resin (a1) obtained above, and copolymer polyester resin. A mixed solvent of water / isopropyl alcohol so that 25% by mass of polymethyl methacrylate particles having a total resin solid content concentration of 2.8% by mass and an average particle size of 0.04 μm as particles is contained with respect to the total resin. The coating liquid B was obtained by diluting with (= 65/35; mass ratio).

(Coating liquid C)
A coating liquid C was obtained by preparing in the same manner as the coating liquid B except that 10 mass% of silica particles having an average particle size of 0.06 µm was contained with respect to the total resin.

(Coating liquid D)
Instead of containing 0.05% by mass of styrene / divinylbenzene crosslinked particles having an average particle size of 0.8 μm with respect to the total resin, 1.7% by mass of silica particles having an average particle size of 1.0 μm with respect to the total resin is used. The coating liquid D was obtained by preparing similarly to the coating liquid A except containing.

(Coating liquid E)
Instead of containing 0.05% by mass of styrene / divinylbenzene crosslinked particles having an average particle diameter of 0.8 μm based on the total resin, styrene / divinylbenzene crosslinked particles having an average particle diameter of 2.0 μm based on the total resin. The coating liquid E was obtained by preparing similarly to the coating liquid A except containing 0.02 mass%.

(Coating fluid F)
Instead of containing 0.05% by mass of styrene / divinylbenzene crosslinked particles having an average particle diameter of 0.8 μm based on the total resin, 1.0% by mass of silica particles having an average particle diameter of 0.1 μm based on the total resin is used. A coating solution F was obtained by preparing in the same manner as the coating solution A, except that the content was%.

(Coating liquid G)
Instead of containing 0.05% by mass of styrene / divinylbenzene crosslinked particles having an average particle diameter of 0.8 μm with respect to the total resin, 1 melamine / formaldehyde crosslinked particles having an average particle diameter of 0.9 μm is added to the total resin. The coating liquid G was obtained by preparing like the coating liquid A except containing 0.0 mass%.

(Coating liquid H)
The melamine compound (DIC's Becamine M-3 solid content concentration 60%) is 20 parts by mass with respect to 100 parts by mass of the copolymerized polyester resin (a1) obtained above and the copolymerized polyester resin. The coating liquid H was obtained by preparing similarly to the coating liquid A except that the total resin solid content concentration in the mixture was 5.6% by mass.

(Coating liquid I)
The melamine compound (DIC's Becamine M-3 solid content concentration 60%) is 20 parts by mass with respect to 100 parts by mass of the copolymerized polyester resin (a1) obtained above and the copolymerized polyester resin. In the mixture, coating liquid I was obtained by preparing in the same manner as coating liquid A except that the total resin solid content concentration was 0.56% by mass.

(Coating liquid J)
Instead of containing 0.05% by mass of styrene / divinylbenzene crosslinked particles having an average particle diameter of 0.8 μm based on the total resin, styrene / divinylbenzene crosslinked particles having an average particle diameter of 0.8 μm based on the total resin. The coating liquid J was obtained by preparing like the coating liquid A except containing 0.02 mass%.

(Coating liquid K)
Instead of containing 0.05% by mass of styrene / divinylbenzene crosslinked particles having an average particle diameter of 0.8 μm based on the total resin, styrene / divinylbenzene crosslinked particles having an average particle diameter of 0.8 μm based on the total resin. The coating liquid K was obtained by preparing like the coating liquid A except containing 3.0 mass%.

(Coating liquid L)
Instead of containing 0.05% by mass of styrene / divinylbenzene crosslinked particles having an average particle size of 0.8 μm based on the total resin, styrene / divinylbenzene crosslinked particles having an average particle size of 0.5 μm based on the total resin. The coating liquid L was obtained by preparing like the coating liquid A except containing 1.0 mass%.

(Coating liquid M)
Instead of the copolymerized polyester resin (a1) obtained above and 100 parts by mass of the copolymerized polyester resin, 100 parts by mass of urethane resin (manufactured by Mitsui Chemicals, Inc .: trade name Takelac W511) is used as a reference. The coating liquid M was obtained by preparing like the coating liquid A except having been.

(Coating liquid N)
Instead of the copolyester resin (a1) obtained above and 100 parts by mass of the copolyester resin, a water-dispersible acrylic resin (manufactured by Nippon Shokubai Kagaku Co., Ltd .: trade name Acre Reset 270E) is the standard. The coating liquid N was obtained by preparing in the same manner as the coating liquid A except that the amount was 100 parts by mass.

(Coating solution O)
The melamine compound (DIC's Becamine M-3 solid content concentration 60%) is 20 parts by mass with respect to 100 parts by mass of the copolymerized polyester resin (a1) obtained above and the copolymerized polyester resin. Instead of mixing, the coating solution except that the blocked isocyanate compound is mixed in an amount of 20 parts by mass with respect to 100 parts by mass of the copolyester resin (a1) obtained above and the copolyester resin. A coating solution O was obtained by preparing in the same manner as A.

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

(Preparation of water-dispersed polyester-based graft copolymer)
In a reactor equipped with a stirrer, thermometer, refluxing device and quantitative dropping device, 75 parts by mass of hydrophobic copolymer polyester, 56 parts by mass of methyl ethyl ketone and 19 parts by mass of isopropyl alcohol are heated and stirred at 65 ° C. Dissolved. After the resin was completely dissolved, 15 parts by mass of maleic anhydride was added to the polyester solution. Subsequently, a solution prepared by dissolving 10 parts by mass of styrene and 1.5 parts by mass of azobisdimethylvaleronitrile in 12 parts by mass of methyl ethyl ketone was dropped into the polyester solution at 0.1 ml / min, and stirring was further continued for 2 hours. After sampling for analysis from the reaction solution, 5 parts by mass of methanol was added. Next, 300 parts by mass of ion-exchanged water and 15 parts by mass of triethylamine were added to the reaction solution and stirred for 1.5 hours. Thereafter, the reactor internal temperature was raised to 100 ° C., and methyl ethyl ketone, isopropyl alcohol, and excess triethylamine were distilled off to obtain a water-dispersed polyester graft copolymer. The obtained polyester-based graft copolymer was light yellow and transparent, and the glass transition point was 40 ° C. This resin was designated as a polyester-based graft copolymer (a2).

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

  In the coating liquid O, the polyester-based graft copolymer (a2) and the polycarbonate-based urethane resin (b1) are contained in a mass ratio of 95: 5 instead of the copolymerized polyester resin (a1). Similarly, a coating liquid P was obtained.

<Examples 6 to 17 and Comparative Examples 2 to 4>
In the same manner as in Example 1, resin A, resin B, and resin E, which are polyester-based resins for base materials, were dry blended at a predetermined blending ratio, and kneaded and extruded using an extruder, and then the skin layer / core layer / It is melt-extruded from a slit so as to be a skin layer (ratio 10% by weight / 80% by weight / 10% by weight), and rapidly cooled and solidified on a chill roll having a surface temperature of 30 to 40 ° C. A regular unstretched sheet was obtained. And after extending the obtained unstretched sheet in the longitudinal (machine) direction at a predetermined temperature and a predetermined magnification with respect to the glass transition temperature in the longitudinal direction between the heating roll and the cooling roll, The coating liquids B to P shown are each applied to one side of the film by a roll coating method, dried at 130 ° C. for 3 seconds, and then at a predetermined temperature and a predetermined magnification in the transverse direction (perpendicular to the machine direction). Next, relaxation is performed by 3 to 5% based on the temperature range of −10 to −35 ° C. with respect to the melting temperature, and a release film having a thickness of 25 μm constituted by each resin ratio is obtained. It obtained as Examples 6-17 and Comparative Examples 2-4 for every coating liquid, and implemented the measurement and evaluation method.

Table 4 shows Examples 6 to 15 and Comparative Examples 2 to 4 described above.

<Examples 18 to 29 and Comparative Examples 5 to 7>
In the same manner as in Example 2, the resin A, resin B, and resin E of the base polyester resin were dry blended at a predetermined blending ratio, and kneaded and extruded using an extruder, and the skin layer / core layer / It is melt-extruded from a slit so as to be a skin layer (ratio 10% by weight / 80% by weight / 10% by weight), and rapidly cooled and solidified on a chill roll having a surface temperature of 30 to 40 ° C. A regular unstretched sheet was obtained. And after extending the obtained unstretched sheet in the longitudinal (machine) direction at a predetermined temperature and a predetermined magnification with respect to the glass transition temperature in the longitudinal direction between the heating roll and the cooling roll, The coating liquids B to P shown are each applied to one side of the film by a roll coating method, dried at 130 ° C. for 3 seconds, and then at a predetermined temperature and a predetermined magnification in the transverse direction (perpendicular to the machine direction). Next, relaxation is performed by 3 to 5% based on the temperature range of −10 to −35 ° C. with respect to the melting temperature, and a release film having a thickness of 25 μm constituted by each resin ratio is obtained. It obtained as Examples 18-29 and Comparative Examples 5-7 for every coating liquid, and implemented the measurement and evaluation method.

In addition, said Examples 18-29 and Comparative Examples 5-7 are shown in Table 5.

  The polyester resin film for mold release of the present invention is a thin and flexible substrate made of a polyester resin having transparency, and has a good appearance suitable for giving a mirror surface design by transfer. And to maintain it. Therefore, as a base material for transfer films applied to decoration for automobile interior and exterior members, household electrical appliance membrane switches, mobile phone members, building material members, etc. It can be suitably used as a base material for a transfer film for simultaneous molding transfer suitable for decoration.

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

Claims (7)

Having a resin composition layer containing particles on at least one surface of the film substrate;
The film substrate is substantially free of particles,
In the resin composition layer
The content of particles A is 0.1 to 30% by mass,
The content of the particles B is 0 to 10% by mass,
The average particle diameter dA of the particles A is 0.01-2 μm,
The average particle diameter dB of the particles B is 0.01 to 0.2 μm,
The average particle diameter dA of the particles A, the average particle diameter dB of the particles B, and the thickness t of the resin composition layer satisfy the following relationships (1) and (2):
The elastic modulus is 1000 MPa or more at 30 ° C., 2200 MPa or less at 100 ° C.,
Haze is 2.0% or less,
A polyester-based resin film for mold release, wherein the surface reflection intensity (Wa) of a resin composition layer in a wavelength region of 0.1 mm to 0.3 mm measured using a wave scanning device is 4.0 or less.
(1) dA> dB
(2) dA> t   After laminating 50 sheets of the film and applying a pressure of 10 MPa for 24 hours, the surface reflection intensity (Wa) in the wavelength region of 0.1 mm to 0.3 mm measured using a wave scanning device is 4.0 or less. The polyester-type resin film for mold release of Claim 1 characterized by the above-mentioned. The average particle diameter dA of the particles A is 0.1 to 1.2 μm,
The polyester resin film for mold release according to claim 1 or 2, wherein the particle size distribution (dA75 / dA25) is 1.1 to 1.5. The polyester resin film for mold release according to any one of claims 1 to 3, wherein a thickness t of the resin composition layer is 0.06 µm or less. The average particle diameter dB of the particles B is 0.02 to 0.15 μm,
The ratio (dB / t) to the thickness t of the resin composition layer is 0.1 to 1.5,
The polyester resin film for mold release according to any one of claims 1 to 4 , wherein the following relationship (3) is satisfied.
(3) dA>t> dB A release film comprising a release layer on at least one surface of the polyester resin film for release according to any one of claims 1 to 5 . The transfer film which has a decoration layer in the mold release layer surface of the mold release film of Claim 6 .