JP6826307B2 - Laminated film - Google Patents

Description

The present invention relates to a laminated film in which a resin layer containing inorganic particles and / or organic particles is laminated on at least one surface of a base material layer.

In recent years, with the expansion of smartphones and tablets, the integration of circuits has led to the advancement of high precision and high density of printed wiring boards. In the process of manufacturing a printed wiring board, a circuit is provided on the surface of an insulating base material (polyimide resin, polyphenylene sulfide resin, etc.), and then a coverlay, which is a heat-resistant resin film having an adhesive layer, is coated for the purpose of insulation and circuit protection. Then, the molding is performed by press laminating through the release film. At this time, the release film is required to have a printed wiring board material, releasability from a press plate, shape followability, and uniform moldability. In recent years, the printed wiring board is also required to have a design, and the need for a printed wiring board having a matte appearance is increasing. A matte appearance can be achieved by roughening the surface shape and reducing specularly reflected light. Therefore, the printed wiring board having a matte appearance can be obtained by forming the printed wiring board on the release film having a roughened surface shape and transferring the surface shape of the release film to the printed wiring board. Therefore, there is a demand for a release film having a matte appearance with a roughened surface shape.

Further, there is an increasing need for a matte film having excellent appearance and releasability as a base material for transferring a functional layer such as an insulating layer or an electromagnetic wave shielding layer onto the surface of a circuit board by a heating press. In the use as these transfer films, there is an increasing need for a highly matte appearance having a lower glossiness than the conventional requirements, and it has been difficult to apply the existing films.

As a matte transfer base material, a polyester film containing inorganic particles or organic particles at a high concentration has been proposed (for example, Patent Documents 1 and 2). Further, as a film having a highly matte appearance, a film having a particle layer coated on the surface has been proposed (for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 2013-129076 Japanese Unexamined Patent Publication No. 2006-31263 Japanese Unexamined Patent Publication No. 2001-341264

However, although the film described in Patent Document 1 is excellent in low glossiness on the surface due to the formation of irregularities on the film surface, the adhesion is enhanced by the anchor effect due to the irregularities on the film surface, and the releasability is inferior. There was a problem. In addition, as a result of increasing the adhesion due to the anchor effect due to the unevenness of the film surface, cohesive fracture may occur in the vicinity of the particles in the film, and it is difficult to maintain process stability in the circuit manufacturing process due to film tearing or adhesion. It was.
Further, the film described in Patent Document 2 is a film having excellent heat resistance, being applicable to high-temperature and high-load processing conditions, and having an excellent matte feeling when viewed from the front (small glossiness of 0 degrees). However, there was a problem that the matte feeling when viewed from the lick was inferior (high glossiness of 85 degrees) and the design was not sufficient. The film described in Patent Document 3 has a very low glossiness and is excellent in good appearance, but when it is used for transfer purposes, there is a problem that problems such as deterioration of the quality of the transfer surface and adhesion of particles occur due to the dropout of particles. was there.
An object of the present invention is to solve the above-mentioned problems of the prior art. That is, it is an object of the present invention to provide a laminated film having both excellent matte appearance and transferability and high process compatibility.

In order to solve the above problems, the present invention has the following configuration. That is, it is a laminated film in which a resin layer containing inorganic particles and / or organic particles is laminated on at least one surface of the base material layer, and the resin layer is on at least one surface layer and is measured at 85 degrees on the surface of the resin layer. The in-plane average value Gb of the glossiness is 25 or less, and the ratio (S / A) of the projected area A (μm ² ) of the resin layer to the actual surface area S (μm ² ) per projected area is 1.15 or more. It is a laminated film of 1.80 or less.

According to the present invention, it is possible to provide a laminated film having both excellent matte appearance and transferability and high process compatibility. Such a laminated film can be suitably used as a release film.

The laminated film of the present invention is formed by laminating a resin layer containing inorganic particles and / or organic particles on at least one surface of a base material layer. Hereinafter, specific modes of the base material layer and the resin layer in the laminated film of the present invention will be described.

[Base layer]
The base material layer of the laminated film of the present invention contains polyester as a main component. Here, the main constituent component means that 50% by weight or more is applied to the entire resin constituting the film.

The base material layer of the laminated film of the present invention may be a single layer or may have a laminated structure of two or more layers. In order to achieve an excellent matte appearance on the laminated film, the substrate layer preferably contains inorganic particles and / or organic particles. More preferably, the base material layer has a laminated structure of two or more layers, and it is preferable that at least one outermost layer contains inorganic particles and / or organic particles (note that the inorganic particles and / or organic particles). The outermost layer of the base material layer containing particles may be referred to as layer A). In the case of a three-layer structure, it is preferable that the compositions of both surface layers are the same from the viewpoint of productivity. Further, in order to improve productivity, it is preferable that the laminated thicknesses of both surface layers are equal. When the base material layer of the present invention is a laminated film having two or more layers and the concentrations of the inorganic particles and / or the organic particles of the polyester layer laminated on the outermost layer of the base film are different, the most inorganic particles and / Or the layer with a high concentration of organic particles is called the A layer.

Here, the inorganic particles and / or organic particles used are not particularly limited, and examples of the inorganic particles include wet and dry silica, colloidal silica, aluminum silicate, calcium carbonate, calcium phosphate, and aluminum oxide. Bengala, Molybdenum Red, Cadmium Red, Red Mouth Yellow Lead, Chrome Permillion, Ultramarine Blue, Navy Blue, Cobalt Blue, Cerulean Blue and other blue pigments, Chromium Oxide, Pyridian, Emerald Green, Cobalt Green, Yellow Lead, Cadmium Yellow, Yellow Iron Oxide , Titanium yellow, manganese violet, mineral violet, titanium dioxide, barium sulfate, zinc white, zinc sulfate, carbon black, black iron oxide, etc. Organic particles include styrene, silicone, acrylic acids, methacrylic acids, polyesters, and divinyl compounds. , Condensed azo, phthalocyanine, quinacridone, dioxazine, isoindolinone, quinophthalone, anthraquinone and the like can be used as constituents. Among them, it is preferable to use heat-resistant wet and dry silica, colloidal silica, inorganic particles such as aluminum silicate, and particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituents. From the viewpoint of matt appearance and economy, wet and dry silica, colloidal silica, and aluminum silicate are particularly preferably used. Two or more kinds of these externally added particles may be used in combination.

Further, the content of the inorganic particles and / or the organic particles contained in the base material layer of the laminated film of the present invention is 0.1% by mass or more with the entire base material layer as 100% by mass in order to achieve a matte appearance. It is preferably contained in an amount of 5% by mass or less, but from the viewpoint of a matte appearance and prevention of film tearing during peeling, it is preferable to contain 0.5% by mass or more and 4% by mass or less with the entire base material layer as 100% by mass. .. When the base material layer has a laminated structure of two or more layers, the A layer of the base material layer is 1% by mass or more and 10% by mass with the entire A layer of inorganic particles and / or organic particles as 100% by mass. It is preferably contained below, more preferably 2% by mass or more and 8% by mass or less, and further preferably 3% by mass or more and 6% by mass or less.

In addition, the inorganic particles and / or organic particles used in the base material layer of the laminated film of the present invention have a large wavy shape on the surface, so that the matte appearance is particularly good when viewed from the plane direction of the film. For the purpose of swelling, the average particle size is preferably 2 μm or more and 10 μm or less, more preferably 3 μm or more and 9 μm or less, and most preferably 4 μm or more and 8 μm or less. The average particle size in the present invention refers to a number average diameter D represented by D = ΣDi / N (Di: equivalent circle diameter of particles, N: number of particles).
Further, in the base material layer of the laminated film of the present invention, it is preferable that the layer containing the particles contains a hydrophobic polyester resin together with the particles from the viewpoint of suppressing streaks in the mouthpiece generated during film formation. The hydrophobic polyester resin referred to here is defined as a polyester resin in which the surface energy of the particle layer surface of the resin film is 38 mN / mm or more and 44 mN / mm or less by adding an appropriate amount. When a polyester resin containing a large amount of particles is melt-extruded, particles may be deposited on the base and streaks may be generated. When this base streak is generated, the surface quality may be deteriorated, or the film may be embrittled during heating due to the crystallized spots that occur in the streak portion and other portions. To solve this problem, it was found that the base streaks can be reduced by simultaneously melting and extruding the hydrophobic resin together with the particles. As the hydrophobic polyester resin, polybutylene terephthalate, polyoxyalkylene glycol copolymerized polyester and the like are preferably used. The content of the hydrophobic polyester resin is preferably 5% by weight or more and 25% by weight or less with respect to the entire layer containing the particles of the base material layer for the purpose of improving the heat resistance of the laminated film. It is more preferably 20% by weight or more by weight.

The base material layer of the laminated film of the present invention is preferably a biaxially oriented polyester film from the viewpoint of heat resistance and dimensional stability. The biaxially oriented polyester film is obtained by a sequential biaxial stretching method in which an unstretched film is stretched in the longitudinal direction and then stretched in the width direction, or stretched in the width direction and then stretched in the longitudinal direction, or the length of the film. It can be obtained by stretching by a simultaneous biaxial stretching method in which the directions and the width directions are stretched almost simultaneously.

The draw ratio of biaxial stretching is preferably 3.0 to 4.2 times, more preferably 3.1 to 4.0 times, and even more preferably 3 in each of the longitudinal direction and the width direction. It is .3 to 3.8 times. In this case, the stretching ratios in the longitudinal direction and the width direction may be increased, or may be the same. The stretching speed is preferably 1,000% / min to 200,000% / min. More preferably, it is 1,500% / min to 50,000% / min, and even more preferably 2,000% / min to 30,000% / min. By setting the stretching speed in the above range, the productivity can be improved and the orientation can be easily controlled.
In the case of the sequential biaxial stretching method in which stretching is performed in the longitudinal direction and then in the width direction, it is preferable to perform stretching under the following conditions because the difference in physical properties between the longitudinal direction and the width direction can be reduced. The stretching ratio in the longitudinal direction is 3 to 4.2 times, the stretching ratio in the width direction is 3 to 4.2 times, preferably the stretching ratio in the longitudinal direction is 3.3 to 3.8 times, and the stretching ratio is in the width direction. The stretching ratio of the above is 3.3 to 3.8 times, and the difference between the stretching ratios in the longitudinal direction and the width direction is 0.5 times or less, more preferably 0.2 times or less. Further, the preheating temperature for stretching in the longitudinal direction (hereinafter sometimes referred to as longitudinal stretching) is preferably 80 to 100 ° C, more preferably 85 to 95 ° C. The longitudinal stretching temperature is preferably 80 ° C. or higher and 110 ° C. or lower, more preferably 85 ° C. or higher and 100 ° C. or lower, and most preferably 85 ° C. or higher and 95 ° C. or lower. The preheating temperature for stretching in the width direction (hereinafter sometimes referred to as transverse stretching) is preferably 70 to 120 ° C, more preferably 75 to 110 ° C. The transverse stretching temperature is preferably 80 ° C. or higher and 165 ° C. or lower, more preferably 80 ° C. or higher and 150 ° C. or lower, and most preferably 80 ° C. or higher and 145 ° C. or lower. When the preheating temperature is equal to or higher than the above temperature range, thermal crystallization of the amorphous portion in the film proceeds, and tearing may easily occur during stretching. Further, when the preheating temperature is not more than the above temperature range, the film is stretched at a cold temperature, the thickness unevenness becomes large, and the degree of orientation of the film decreases, so that the mechanical strength may deteriorate. If the stretching temperature exceeds the above range, process troubles such as roll adhesion and clip adhesion may occur. Further, when the stretching temperature is lower than the above range, the stretching tension rises sharply, causing tearing, clip detachment, and the like, which may significantly reduce productivity.

The base material layer of the laminated film of the present invention is preferably obtained by biaxially stretching an unstretched sheet and then performing a heat treatment. This heat treatment can be performed by any conventionally known method, such as in an oven or on a heated roll. The heat treatment can be performed at any temperature such that the temperature of the film is 120 ° C. or higher and 240 ° C. or lower, but is preferably 200 to 240 ° C. More preferably, it is 225 ° C to 240 ° C. The heat treatment time can be any time, but it is preferably performed for 1 to 60 seconds. More preferably, it takes 1 to 30 seconds. The heat treatment may be performed while relaxing the film in the longitudinal direction and / or the width direction. Further, re-stretching may be performed once or more in each direction, and then heat treatment may be performed.

[Resin layer]
The resin layer of the laminated film of the present invention needs to contain inorganic particles and / or organic particles. The inorganic particles and / or organic particles contained in the resin layer are not particularly limited, but are not particularly limited, but are silica, alumina, kaolin, calcium carbonate, titanium oxide, calcium phosphate, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, and talc. , Clay, mica, zirconia, aluminosilicate particles and other inorganic particles, and organic particles such as crosslinked polystyrene particles, acrylic particles and polyester particles. It is preferable to use crosslinked polystyrene particles for the purpose of achieving both transferability and a highly matte appearance in the circuit manufacturing process.

As a method of laminating the resin layer of the laminated film of the present invention, a method of forming an unstretched sheet in which the base resin and the above-mentioned inorganic particles and / organic particles are co-extruded at the same time as the base material layer, or a resin layer composition solution is applied to the base material layer. Examples include a coating method. These are not particularly limited, but it is preferable to use a method of providing the substrate layer by coating for the purpose of forming the surface shape characteristic of the present invention.

The resin layer of the laminated film of the present invention preferably contains a binder resin and a cross-linking agent as components constituting the resin layer for the purpose of uniformly and firmly supporting the above-mentioned particles on the surface of the base material. When the binder resin is contained, the particles can be fixed on the base material layer to prevent them from falling off, and the aggregated state of the particles can be changed to control the size of the unevenness due to the resin layer. Specific examples of the binder resin include polyester resin, acrylic resin, urethane resin, polyvinyl, polyalkylene glycol, polyalkyleneimine, celluloses, starches, etc., and acrylic resin from the viewpoint of stretch followability and peeling force control. Is preferably used. Further, by containing a cross-linking agent in addition to the binder resin, a restraint structure can be formed between the molecular chains and the strength of the resin layer can be increased. The cross-linking agent is preferably an oxazoline resin, a melamine resin, an epoxy resin, a carbodiimide resin, or an isocyanate resin. A melamine resin is more preferably used from the viewpoint of solvent durability of the resin layer. The cross-linking agent can be mixed and used in an arbitrary ratio, but it is preferable to add 5 to 50 parts by weight of the cross-linking agent with respect to 100 parts by weight of the binder resin in terms of improving durability, and more preferably 10 to 40 parts by weight. It is an addition. If the amount of the cross-linking agent added is less than 5 parts by weight, the effect of adding the cross-linking agent may be insufficient, the resistance to the solvent used during processing may be lowered, or scratches may occur during roll transportation. On the other hand, if it exceeds 50 parts by weight, spots are likely to occur during application.

In the resin layer of the laminated film of the present invention, the binder resin and the cross-linking agent are used as the main agent of the resin layer, and the particle concentration is preferably 4% by weight or more and 15% by weight or less with respect to the solid content of the main agent. Since the surface shape characteristic of the present invention, which will be described later, strongly depends on the particle concentration of the resin layer, the particle concentration is preferably in the above-mentioned specific range, and when it is higher than 15% by weight, the particles are likely to fall off. In some cases. It is preferably 6% by weight or more and 14% by weight or less, and most preferably 8% by weight or more and 12% by weight or less.

In the present invention, it is preferable that the resin composition forming the resin layer contains an additive suitable for the purpose of imparting peelability in addition to the binder resin and the cross-linking agent. When the sum of the masses of the binder resin and the cross-linking agent is 100 parts by mass, the additive is preferably 3 parts by mass or more and 30 parts by mass or less. By making the mass of the additive 3 parts by mass or more, peelability at the time of transfer can be imparted, and when it is 30 parts by mass or less, appropriate adhesion is maintained, and during transportation or punching process. Peeling can be suppressed. The additive used here is preferably a compound having a peeling property (that is, lowering the surface energy of the resin or lowering the coefficient of static friction of the resin) on the surface of the resin when added to the resin. ..

Examples of the additive that can be used in the present invention include silicone-containing compounds, waxes such as fluorine compounds, paraffin wax, polyethylene wax, and carnauba wax, long-chain alkyl group-containing compounds, and resins. Among them, the long-chain alkyl chain-containing compound is preferable in that it forms a desired surface shape and achieves both peelability and suppression of zipping. The long-chain alkyl compound referred to in the present invention refers to a compound having a long-chain alkyl group, and is not particularly limited as long as it is a compound containing a long-chain alkyl group, but a compound having a long-chain alkyl group in the side chain of the main chain polymer. Can be mentioned.

Among compounds having a long-chain alkyl group in the side chain of the main-chain polymer, the main-chain polymer includes an acrylate-based polymer or copolymer, polyvinyl alcohol (including a partially saponified product of polyvinyl acetate), and ethylene-vinyl alcohol. Copolymers (including partially saponified ethylene-vinyl acetate copolymers), vinyl alcohol-acrylic acid copolymers (including partially saponified vinyl acetate-acrylic acid copolymers), polyethylimine, polyvinylamine , Styrene-maleic anhydride copolymer, polyurethane and the like.

The fluorine compound in the present invention is a compound containing a fluorine atom in the compound. For example, a perfluoroalkyl group-containing compound, a polymer of an olefin compound containing a fluorine atom, an aromatic fluorine compound such as fluorobenzene, and the like can be mentioned. When the laminated film of the present invention is used for simultaneous molding transfer foil, a high heat load is applied during transfer. Therefore, considering heat resistance and stain resistance, the fluorine compound is preferably a polymer compound.

The wax in the present invention is a wax selected from natural waxes, synthetic waxes, and waxes containing them. Natural waxes are plant waxes, animal waxes, mineral waxes, and petroleum waxes. Examples of the plant wax include candelilla wax, carnauba wax, rice wax, wood wax and jojoba oil. Examples of animal waxes include mitsuro, lanolin, and whale wax. Examples of mineral waxes include montan wax, ozokerite, and selecin. Examples of petroleum wax include paraffin wax, microcrystalline wax, and petrolatum. Examples of synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, acid amides, amines, imides, esters and ketones. Fisher Tropsch wax (also known as Sazoir wax) and polyethylene wax are well-known synthetic hydrocarbons, but other low molecular weight polymers (specifically, polymers with a viscosity average molecular weight of 500 to 20000). The following polymers are also included. That is, there are polypropylene, ethylene / acrylic acid copolymers, polyethylene glycol, polypropylene glycol, block or graft conjugates of polyethylene glycol and polypropylene glycol. Examples of the modified wax include a montan wax derivative, a paraffin wax derivative, and a microcrystalline wax derivative. The derivative here is a compound obtained by any treatment of purification, oxidation, esterification, saponification, or a combination thereof. Examples of the hydrogenated wax include hardened castor oil and hardened castor oil derivatives.

Further, as long as the gist of the present invention is not impaired, the resin layer may contain a defoaming agent, a coatability improver, a thickener, an organic lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, as necessary. It may contain a foaming agent, a dye and the like.

When the resin layer of the present invention is formed by coating, a solvent may be used when the resin composition is provided on the base material layer. That is, the resin composition may be dissolved or dispersed in a solvent to prepare a coating liquid, which may be applied to the base material layer. After the coating, the solvent is dried and heated to obtain a film on which the resin layer is laminated. In the present invention, it is preferable to use an aqueous solvent as the solvent. By using an aqueous solvent, rapid evaporation of the solvent in the heating step can be suppressed, a uniform resin layer can be formed, and the environmental load is excellent.

Here, the aqueous solvent is soluble in water, 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. It refers to a mixture of an organic solvent in an arbitrary ratio.

The resin layer of the present invention can be laminated on one side or both sides of the base material layer. When the resin layer is laminated on one side, the antistatic layer may be laminated on the opposite surface. The antistatic layer can contain, for example, an antistatic agent such as carbon black, tin oxide, tin oxide antimony doping, polythiophene and polyaniline. Considering transparency, tin oxide-based antistatic agents are preferable.

When the resin layer of the present invention is provided by coating, it is preferable that the resin composition forming the resin layer is applied to at least one surface of the base material layer and then heated to form the resin layer. The method for applying the resin composition to the base material layer can be either an in-line coating method or an off-coating method, but the in-line coating method is preferable. The in-line coating method is a method of applying in the process of manufacturing a polyester film. Specifically, it refers to a method in which the resin constituting the base material layer is melt-extruded, then biaxially stretched, then heat-treated and wound up at any stage, and is usually obtained by melt-extruding and then quenching. A substantially amorphous unstretched (unaligned) film, followed by a longitudinally stretched (uniaxially oriented) film, or a further widthwise biaxially stretched (biaxially oriented) film before heat treatment. ) Apply to any of the films.

In the present invention, the resin composition is applied to at least one surface of either the unaligned polyester film or the uniaxially oriented polyester film before the crystal orientation is completed, the solvent is evaporated, and then the base material layer is uniaxially oriented. Alternatively, it is preferable to adopt a method of stretching in the biaxial direction and heating to complete the crystal orientation of the base material layer and providing a resin layer. When the base material layer contains particles, it is difficult to apply the resin layer composition solution uniformly because large irregularities are distributed on the surface of the base material layer, and the orientation seen in the glossiness of the resulting film. And angle spots may occur. On the other hand, in the polyester film that has not been stretched or uniaxially stretched, the resin layer composition solution can be uniformly applied because the formation of irregularities and the progress of crystallization by stretching are in the middle, and the subsequent stretching process. The resin layer can be cured inside, and at the same time, the surface shape of the base material can be made into a desired shape. Further, since the film formation of the base material layer, the application of the resin composition, 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 an advantage in terms of manufacturing cost. Above all, a method of applying the resin composition to the film uniaxially stretched in the longitudinal direction, drying the solvent, then stretching in the width direction and heating is preferable. Compared with the method of biaxially stretching after coating on an unstretched film, since the stretching step is one less, it is possible to suppress the occurrence of defects and cracks in the resin layer due to stretching.

On the other hand, the offline coating method is a film forming step on a film after the unstretched film is stretched uniaxially or biaxially and heat-treated to complete the crystal orientation of the base material layer, or the unstretched film. This is a method of applying the resin composition in a separate process. In the present invention, it is preferable that the in-line coating method is used because of the various advantages described above.

Therefore, the best method for forming the resin layer in the present invention is to apply a resin composition using an aqueous solvent on at least one surface of the base material layer by an in-line coating method, and dry and heat the aqueous solvent. It is a method of forming by.

As a method for applying the resin composition to the base material layer, any known application method such as a bar coating method, a reverse coating method, a gravure coating method, a die coating method, or a blade coating method can be used. A biaxially oriented film is preferable from the viewpoint of heat resistance and dimensional stability. Examples of the biaxial orientation method include a sequential biaxial stretching method and a simultaneous biaxial stretching method, but from the viewpoint of productivity, the sequential biaxial stretching method is more preferably used.

[Laminated film]
In the laminated film of the present invention, in order to give the appearance of the transfer target a highly matte appearance, the in-plane average value of the glossiness Gb at an incident angle of 85 degrees measured on the surface on the resin layer side needs to be 25 or less. .. The glossiness is an index showing the amount of specular reflection with respect to the incident light, and the lower this value is, the more the matte appearance is shown. When measuring the glossiness, the deeper the angle, that is, the larger the angle of incidence from the direction perpendicular to the film plane (the angle of incidence is closer to 90 °), the lower the diffusivity due to the unevenness of the film surface. However, the value increases. Since this tendency is more remarkable at deep angles, the effect of reducing the glossiness at deep angles is very large for the purpose of improving the uniformity of the matte appearance. The in-plane average value of the glossiness Gb at an incident angle of 85 degrees measured on the surface on the resin layer side is more preferably 22 or less, and most preferably 20 or less. Examples of the method of setting the in-plane average value of the 85-degree gloss Gb to 25 or less include a method of forming the above-mentioned resin layer on the base material layer by an in-line coating method in the manufacturing process of the laminated film. The in-plane average value of the glossiness Gb at an incident angle of 85 degrees is a value obtained by a measurement method described later, and the glossiness at an incident angle of 85 degrees is measured at an arbitrary measurement position and centered on the measurement position. The sheet is rotated 360 degrees in increments of 30 degrees, measured in each direction, and the average of the obtained measured values in all directions is taken as the in-plane average value of the glossiness Gb at an incident angle of 85 degrees.

In the laminated film of the present invention, when the projected area of the resin layer is A (μm ² ) and the actual surface area per projected area of the resin layer is S (μm ² ), the ratio of the surface area of the resin layer to the projected area (resin layer). The actual surface area (S / A) of the resin layer per unit projected area measured on the side surface must be 1.15 or more and 1.80 or less. The projected area A of the resin layer represents a horizontal projected area when the laminated film is viewed from a direction perpendicular to the film surface. The actual surface area S per unit projected area of the resin layer represents the actual surface area of the film surface within the range of the horizontal projected area when the film is viewed from the direction perpendicular to the film surface. When many large irregularities are present on the surface of the resin layer of the laminated film, the actual surface area S of the resin layer becomes large and the S / A value becomes large. If the S / A is less than 1.15, the matte tone of the transferred product is insufficient. When the S / A is larger than 1.80, the coatability of the solution deteriorates when the functional layer is formed on the resin layer, and the surface shape of the laminated film is not sufficiently transferred, resulting in a matte finish of the transferred product. Insufficient or excessively increases the adhesion area, and particles and resin on the surface of the resin layer fall off during peeling, causing process contamination. The S / A is preferably 1.20 or more and 1.70 or less, and most preferably 1.30 or more and 1.60 or less. The method of setting the S / A in the specific range is not particularly limited, but the base material layer has a laminated structure of two or more layers, and the layer on the side in contact with the resin layer contains inorganic particles and / or organic particles to form a resin. The ratio (rb / rc) of the number average particle size rc (μm) of the number of particles contained in the layer to the number average particle size rb (μm) of the number of particles contained in the layer in contact with the resin layer of the base material layer is 4 or more and 10 The following methods can be mentioned. By setting the ratio of the number average particle diameters of the particles attracted to each layer to the above-mentioned specific range, the large undulations on the surface of the base material layer and the arrangement of the fine particles of the resin layer are controlled, so that the S / A can be adjusted. Can be a range.

In the laminated film of the present invention, the average value (Wa) of the surface waviness of the surface of the resin layer is preferably 0.05 to 0.5 μm. When the surface waviness is in the above range, the diffusing ability of light at a deep incident angle can be made good (the glossiness is low) due to the large unevenness on the surface of the resin layer. Wa is preferably 0.07 to 0.45 μm, and more preferably 0.1 to 0.4 μm. As a method of setting the surface waviness in the above preferable range, the particle concentration contained in the layer in contact with the resin layer of the base material layer is set to a specific range, and the area magnification of biaxial stretching is set to 8.0 times or more and 13.0 times or less. The method can be given.

The laminated film of the present invention preferably has a surface peak count (Pc) of 100 to 1000 pieces / mm. If Pc is larger than 1000, particle shedding may occur in the peeling step during transfer, and if Pc is smaller than 100, the appearance unevenness may be deteriorated due to an increase in specular reflectance in a minute region of the surface. .. Examples of the method in which Pc is in a preferable range include a method in which the average particle size of the particles contained in the resin layer is 0.4 μm or more and 0.8 μm or less in a composition in which the surface area ratio is in a preferable range. The Pc is preferably 150 to 900, and most preferably 200 to 700.

The laminated film of the present invention preferably has a surface roughness (Ra) of 0.4 to 1.0 μm from the viewpoint of transferability of a matte appearance. If the surface roughness exceeds 1.0 μm, uniform coating may be difficult in the coating process of the functional layer, and the transferability of glossiness may be insufficient. If the surface roughness is less than 0.4 μm, the adhesion is weak. It may peel off during the transportation process before use. The method of setting the surface roughness within the above range is not particularly limited, and examples thereof include a method of controlling the content and particle size of the particles contained in the resin layer. When these surface parameters are within the above-mentioned specific range, it is possible to achieve both a high matte appearance and transferability.

In the laminated film of the present invention, the ratio (Gbmin / Gbmax) of the maximum value Gbmax and the minimum value Gbmin of 85 degree glossiness measured on the surface on the resin layer side is preferably 0.85 or more and 0.97 or less. The ratio (Gbmin / Gbmax) of the maximum value Gbmax and the minimum value Gbmin of the 85-degree glossiness measured on the surface on the resin layer side indicates that the glossiness is not anisotropic when the value is 1. As a result of diligent studies by the present inventors, it has been found that by forming a surface shape in which Gbmin / Gbmax brings anisotropy to the above range, that is, glossiness, it becomes easy to create a peeling start point and the peelability becomes good. I found it. In-plane anisotropy should normally be suppressed from the viewpoint of uniformity of characteristics, but it is presumed that controlling it within the above range makes it easier to peel off in the direction of weak adhesion. When Gbmin / Gbmax is less than 0.85, the glossiness changes depending on the direction, and the transfer appearance may deteriorate. Further, when Gbmin / Gbmax exceeds 0.97, the effect of improving the peelability cannot be sufficiently obtained. Gbmin / Gbmax is more preferably 0.88 or more and 0.96 or less, and further preferably 0.90 or more and 0.95 or less. As a method of setting Gbmin / Gbmax in the above-mentioned preferable range, when the resin layer is provided on the base material layer, the resin layer is formed on at least one side surface of the uniaxially oriented polyester film in which the base material layer is stretched in the uniaxial direction. After applying the coating liquid containing the resin composition to be used, the solvent of the coating liquid is evaporated by heating to form a resin layer, and then the resin layer is stretched in the uniaxial direction. By forming the resin layer and then stretching it only in the uniaxial direction, the particles contained in the resin layer exist in an anisotropy form, and the surface of the resin layer has an anisotropy shape. In the step of applying the coating solution containing the resin composition forming the resin layer, the time until the heating and drying step is started after application is controlled, and the time to reach the boiling point of the solvent of the resin layer composition solution is set long. , The fluidity of the particles existing in the resin layer composition solution can be increased, and a resin layer having more anisotropy can be formed. When the coating liquid of the resin composition forming the resin layer is an aqueous solvent, the time from applying the coating liquid to entering the heat-drying step is preferably 3 seconds or more and less than 20 seconds. The maximum value Gbmax and the minimum value Gbmin of the 85 degree glossiness measured on the surface on the resin layer side are values obtained by the measurement method described later, and the glossiness at an incident angle of 85 degrees can be measured at an arbitrary measurement position. Then, the sheet was rotated 360 degrees around the measurement position in 30 degree increments, and measurements were taken in each direction. Of the obtained measured values in all directions, the largest value was Gbmax and the smallest value was Gbmin. To do.

Specific examples of the method for producing a laminated film of the present invention will be described, but the present invention is not construed as being limited to such examples.

In the case of a laminated polyester film having two or more base layers, first, as the polyester A used for the A layer, the polyethylene terephthalate resin (a) and the polyethylene terephthalate resin (a) are made to contain silica particles having an average particle size of 5 μm. The particle-containing polyethylene terephthalate resin (a') is weighed at a predetermined ratio. Further, as the polyester B used for the layer (B layer) other than the A layer, the polyethylene terephthalate resin (a) is used. These raw material resins are vacuum-dried, mixed, and then supplied to a single-screw extruder for melt extrusion. At this time, it is preferable to control the resin temperature to 265 ° C to 295 ° C. Then, it is cooled and solidified to prepare an unstretched (unoriented) PET film. This film is stretched 3 to 4.2 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially oriented PET film. A coating liquid having a resin composition prepared to a predetermined concentration is applied to one side of this film. At this time, the coated surface of the PET film may be subjected to surface treatment such as corona discharge treatment before coating. By performing surface treatment such as corona discharge treatment, the coatability of the resin composition on the PET film is improved, so that the wettability is improved, the resin composition is prevented from repelling, and a uniform coating thickness is achieved. be able to. After coating, the end of the PET film is gripped with a clip and led to a preheating zone at 80 to 130 ° C. to dry the solvent of the coating liquid. After drying, it is stretched 3 to 4.2 times in the width direction at a temperature of 100 ° C. to 160 ° C. Subsequently, the heat treatment is carried out for 1 to 60 seconds by leading to a heat treatment zone at 150 to 240 ° C. At this time, it is preferable to perform a relaxation treatment of 3 to 15% in the width direction or the longitudinal direction in the heating step (heat treatment step) because the dimensional change in the heating step when the film is used can be suppressed.

The laminated film of the present invention has a resin layer containing inorganic particles and / or organic particles laminated on at least one surface of the base material layer, and the surface area of the resin layer is significantly increased as compared with the conventional film. In a circuit forming process in which a matte finish is required, it can be suitably used as a heat-resistant transfer film having high process compatibility that achieves both an excellent matte appearance and transferability.

(1) Polyester composition Polyester resin and film can be dissolved in hexafluoroisopropanol (HFIP), and the content of each monomer residue component and by-product diethylene glycol can be quantified using ¹ H-NMR and ¹³ C-NMR. it can. In the case of a laminated film, by scraping off each layer of the film according to the laminated thickness, the components constituting each layer alone can be collected and evaluated. The composition of the film of the present invention was calculated from the mixing ratio at the time of film production.

(2) Gloss The surface of the resin layer of the laminated film is JIS with an incident angle of 85 degrees and a light receiving angle of 85 degrees (85 degrees gloss) using a digital variable angle gloss meter UGV-5B manufactured by Suga Testing Machine Co., Ltd. It was measured according to Z8741. The sample was cut into 50 mm squares, and light was incident on the resin layer side. The measurement is first performed at an arbitrary measurement position, the sheet is rotated 360 degrees in 30 degree increments around the measurement position, measurements are taken in each direction, and the average of the obtained measured values in all directions is defined as Gb. .. The maximum value in the plane was Gbmax and the minimum value was Gbmin. When resin layers were provided on both surface layers of the film, measurements were performed on both sides of the film.

(3) Ratio of surface area of resin layer to projected area A (S / A), surface waviness Wa
According to JIS B 0601, the measurement was performed using VertScan2.0 R5300GL-Lite-AC manufactured by Ryoka System Co., Ltd. The measurement was performed with N = 3 on the surface on the resin layer side, and the average value was adopted. When resin layers were provided on both surface layers of the film, measurements were performed on both sides of the film. The details of the measurement conditions are as follows.
Manufacturer: Ryoka System Co., Ltd.
Device name: VertScan2.0 R5300GL-Lite-AC
Measurement conditions: CCD camera SONY HR-57 1/2 inch objective lens 5x
Intermediate lens 0.5x
Wavelength filter 530nm white
Measurement mode Focus
Measurement software: VS-Measure Version 5.5.1
Analysis software: VS-Viewer Version 5.5.1
Measurement area (= projected area): 1.252 x 0.939 mm ²
(4) Surface peak count Pc, surface roughness Ra
JIS-B0601 (1) using a high-definition fine shape measuring instrument (three-dimensional surface roughness meter) of the stylus method
The surface morphology of the polyester film is measured under the following conditions in accordance with (994).
-Measuring device: 3D fine shape measuring device (model ET-4000A) manufactured by Kosaka Laboratory Co., Ltd.-Analyzing device: 3D surface roughness analysis system (model TDA-31)
・ Stylus: Tip radius 0.5 μmR, diameter 2 μm, made of diamond ・ Needle pressure: 100 μN
・ Measurement direction: Average after measuring the film longitudinal direction and film width direction once each ・ X measurement length: 1.0 mm
・ X feed speed: 0.1 mm / s (measurement speed)
・ Y feed pitch: 5 μm (measurement interval)
・ Number of Y lines: 81 (number of measurements)
・ Z magnification: 20 times (vertical magnification)
・ Low frequency cutoff: 0.20 mm (waviness cutoff value)
-High frequency cutoff: R + Wmm (roughness cutoff value) R + W means no cutoff.
・ Filter method: Gaussian spatial type ・ Leveling: Yes (tilt correction)
-Reference area: 1 mm ² .
The measurement was performed under the above conditions, and then the surface peak count Pc and the surface roughness Ra were calculated using an analysis system.
(Peak count Pc analysis conditions)
・ Slice level condition setting; fixed vertical spacing ・ Center pitch level 0.05 μm
・ Upper and lower level spacing 0.025 μm
-The SPc values of the lower limit of 375 nm, the center level of 400 nm, and the upper limit of 425 nm are adopted as the peak count Pc.

(5) Number of Particles The film was obtained from a cross-sectional photograph obtained by observing the cross section of the film at a magnification of 3,000 to 200,000 times using a transmission electron microscope HU-12 (manufactured by Hitachi, Ltd.). That is, the particle portion of the cross-sectional photograph is marked, and the particle portion is image-processed using the high-definition image analysis processing device PIAS-IV (manufactured by Pierce Co., Ltd.) to obtain a total of 100 particles in the measurement field. The average diameter when converted to a circle was calculated and used as the average particle size of the particles.

(6) Matte appearance Transferability 1 (peeling property)
A hard coat layer (UF-TCI-1 manufactured by Kyoeisha Chemical Co., Ltd.) was applied to the laminated film of the present invention to a thickness of 40 μm after drying, and dried at 80 ° C. for 10 minutes. Then, a rectangle having a width of 10 mm and a length of 150 mm was cut out and used as a sample. Using the laminate, a press machine heated to a temperature of 160 ° C. for both the upper mold temperature and the lower mold temperature was used, and an aluminum plate with a thickness of 0.2 mm / a polyimide film with a thickness of 0.125 mm (manufactured by Toray DuPont). Capton 500H / V) / Laminated film / HC laminate / Polyimide film with a thickness of 0.125 mm (Kapton 500H / V manufactured by Toray DuPont) / Aluminum plate with a thickness of 0.2 mm under the condition of 1.5 MPa The heat press was performed for 1 hour. After the heating press, the laminated film / HC laminated body was taken out and irradiated with ultraviolet rays having an illuminance of 2000 mJ / cm ² , and the releasability between the laminated film and the HC layer was evaluated according to the following criteria, and B or higher was passed.
S: The mold release test was performed 10 times, and no film tear or adhesion occurred 10 times.

A: The mold release test was performed 10 times, and the film was torn or adhered once.
B: The mold release test was performed 10 times, and the film was torn or adhered in more than 1 test and within 3 times.
C: The mold release test was performed 10 times, and film tearing and / or adhesion occurred more than 3 times.

(7) Matte appearance transferability 2 (peeling property 2)
The laminated film / HC laminate obtained in (6) is placed on a flat plate, and the corners are floated from the 30 mm × 30 mm flat plate. After that, push the tip of the corner to a position where the apex of the corner is perpendicular to the flat plate. The sample was confirmed, the shortest distance from the corner to the position where the transfer film was peeled off was measured, and the ease of triggering the peeling was evaluated according to the following criteria.
S: 10 mm or more A: 5 mm or more and less than 10 mm B: 1 mm or more and less than 5 mm.
C: Less than 1 mm.

(8) Matte appearance transferability 3 (glossiness)
The appearance of the HC layer (peeled surface) after peeling obtained in (6) was observed, and the transferability of the matte appearance was evaluated according to the following criteria. The 85-degree glossiness was measured using a digital variable-angle glossiness meter UGV-5D manufactured by Suga Test Instruments Co., Ltd. according to the method specified in JIS-Z-8741 (1997). The measurement was performed at n = 5, and the average value excluding the maximum value and the minimum value was adopted.
S: 85 degree glossiness is 20 or less.

A: 85 degree glossiness is greater than 20 and 22 or less.

B: 85 degree glossiness is greater than 22 and 25 or less.
C: 85 degree glossiness is greater than 25.

(Manufacturing of polyester)
The polyester resin used for film formation was prepared as follows.

(Polyester A)
Polymerization of terephthalic acid and ethylene glycol using antimony trioxide as a catalyst was carried out by a conventional method to obtain polyester A having an intrinsic viscosity of 0.65.

(Polyester B)
A polyethylene terephthalate particle master having an intrinsic viscosity of 0.65 containing aggregated silica particles having a number average particle diameter of 3.5 μm in polyester A at a particle concentration of 20% by mass.

(Polyester C)
A polyethylene terephthalate particle master having an intrinsic viscosity of 0.65 containing aggregated silica particles having a number average particle diameter of 2.5 μm in polyester A at a particle concentration of 20% by mass.

(Polyester D)
Hytrel 7247 manufactured by Toray DuPont was used.

(Resin layer forming solution (aqueous dispersion)
The binder resin: cross-linking agent: additive: particle: surfactant shown below was adjusted by diluting with pure water so as to have the mass ratio and solid content concentration shown in the table, respectively.
-Binder resin I: Acrylic resin A
(Nippon Carbide Industries "Nikazol" (registered trademark) RX7013ED)
-Binder resin II: Acrylic resin B
Methyl methacrylate (a), hydroxyethyl methacrylate (b), urethane acrylate oligomer (manufactured by Negami Kogyo Co., Ltd., Art Resin (registered trademark) UN-3320HA, number of acryloyl groups 6) (c) in a stainless steel reaction vessel. ) Was charged at a mass ratio of 75:20: 5, and 2 parts by mass of sodium dodecylbenzenesulfonate as an emulsifier was added to a total of 100 parts by mass of (a) to (c) and stirred to prepare a mixed solution 1. did. Next, a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was prepared. 60 parts by weight of the mixed solution 1, 200 parts by weight of isopropyl alcohol, and 5 parts by weight of potassium persulfate as a polymerization initiator were charged into a reactor and heated to 60 ° C. to prepare a mixed solution 2. The mixed solution 2 was kept heated at 60 ° C. for 20 minutes. Next, a mixed solution 3 composed of 40 parts by weight of the mixed solution 1, 50 parts by weight of isopropyl alcohol, and 5 parts by weight of potassium persulfate was prepared. Subsequently, the mixed solution 3 was added dropwise to the mixed solution 2 over 2 hours using a dropping funnel to prepare the mixed solution 4. Then, the mixed solution 4 was kept heated to 60 ° C. for 2 hours. The obtained mixed solution 4 was cooled to 50 ° C. or lower, and then transferred to a container equipped with a stirrer and decompression equipment. 60 parts by weight of 25% ammonia water and 900 parts by weight of pure water were added thereto, and isopropyl alcohol and unreacted monomers were recovered under reduced pressure while heating at 60 ° C., and the resin (A) dispersed in pure water was collected. Binder resin III: Polyester resin B
A dispersion obtained by diluting a mixed polymer of 25 mol% terephthalic acid, 24 mol% isophthalic acid, 1 mol% 5-Na sulfoisophthalic acid, 25 mol% ethylene glycol, and 25 mol% neopentyl glycol with water to 25% by mass.
-Crosslinking agent I: Crosslinked resin of methylated melamine / urea copolymer ("Nicarac" (registered trademark) "MW12LF" manufactured by Sanwa Chemical Co., Ltd.)
-Crosslinking agent II: Carbodiimide compound ("Carbodilite" (registered trademark) "V-04" manufactured by Nisshinbo Chemical Co., Ltd.)
-Additive I: Long-chain alkyl group-containing compound ("Rezem T738" manufactured by Chukyo Yushi Co., Ltd.)
-Additive II: Olefin compound (Mitsui Chemicals, Inc. "Chemipal (registered trademark) XHP400")
500 parts by weight of toluene, 80 parts by weight of stearyl methacrylate (18 carbon atoms of alkyl chain), 15 parts by weight of methacrylic acid, 5 parts by weight of 2-hydroxyethyl methacrylate in a temperature-adjustable reactor equipped with a stirrer, a thermometer and a condenser. A part, azobisisobutyronitrile, was placed in a dropping device and dropped at a reaction temperature of 85 ° C. for 4 hours to carry out a polymerization reaction. Then, it was aged at the same temperature for 2 hours to complete the reaction to obtain a long-chain alkyl group-containing compound A.
Particle I: An aqueous dispersion obtained by diluting crosslinked polystyrene particles (specific gravity: 1.06) having a number average particle size of 500 nm with pure water so that the solid content concentration becomes 15% by weight.
-Particle II: An aqueous dispersion obtained by diluting crosslinked polystyrene particles (specific gravity: 1.06) having a number average particle size of 800 nm with a pure content so as to have a solid content concentration of 25%.
-Particle III: An aqueous dispersion obtained by diluting silica particles (specific gravity: 2.00) having a number average particle diameter of 300 nm with pure water so that the solid content concentration becomes 40% by weight.
-Particle IV: An aqueous dispersion obtained by diluting silica particles (specific gravity: 2.00) having a number average particle diameter of 300 nm with pure water so that the solid content concentration becomes 40% by weight.
-Surfactant: Fluorine-based surfactant (Plus Coat (registered trademark) "RY-2" manufactured by Reciprocal Chemical Co., Ltd.)
(Example 1)
The solution containing the resin composition was prepared with the mass ratio and solid content concentration shown in the table.

The composition is as shown in the table, and the raw materials are supplied to separate single-screw extruders having an oxygen concentration of 0.2% by volume, and melted at a layer A extruder cylinder temperature of 270 ° C. and a layer B extruder cylinder temperature of 270 ° C. Then, after the A layer and B layer merge, the short tube temperature is set to 275 ° C and the base temperature is set to 280 ° C, and the resin temperature is 280 ° C, and the temperature is controlled to 25 ° C from the T die. did. At that time, an unstretched film was obtained by electrostatically applying static electricity using a wire-shaped electrode having a diameter of 0.1 mm and bringing it into close contact with a cooling drum. Next, the film temperature was raised with a heating roll before stretching in the longitudinal direction, the preheating temperature was 90 ° C., the stretching temperature was 95 ° C., and the film was stretched 3.3 times in the longitudinal direction, and the temperature was immediately controlled to 40 ° C. Cooled with a roll. Then, a corona discharge treatment was performed, and a resin layer forming solution (aqueous dispersion) having the composition shown in the table was applied using a metering bar so that the wet thickness was 15 μm. Next, the film was stretched 3.5 times in the width direction at a preheating temperature of 100 ° C. and a stretching temperature of 120 ° C. using a tenter-type transverse stretching machine, and then heat-treated in the tenter at a constant length at a temperature of 240 ° C., and then at the same temperature. A 3% relaxation treatment was performed, and a 2% relaxation treatment was further performed at a temperature of 200 ° C., and a resin layer was laminated on a base material layer having a three-layer structure of A layer / B layer / A layer having a film thickness of 50 μm. A laminated film was obtained. At this time, the time from application of the resin layer composition solution to the preheating zone was 18 seconds.

(Example 2)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Example 3)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Example 4)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Example 5)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Example 6)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Example 7)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the particles of the polyester A layer of the base material were changed as shown in the table.

(Example 8)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Example 9)
Lamination with a film thickness of 50 μm in the same manner as in Example 1 except that the time from application of the resin layer composition solution to the zone of the tenter 100 ° C. or higher was set to 30 seconds by changing the transverse stretching preheating 2 temperature and the first half temperature to 95 ° C. I got a film.

(Example 10)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Example 11)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Example 12)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the particles of the polyester A layer of the base material were changed as shown in the table.

(Example 13)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Example 14)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Example 15)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Comparative Example 1)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

(Comparative Example 2)
As shown in the table, a laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the base material had a single film structure without the polyester A layer.

(Comparative Example 3)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table. When the peelability of the obtained laminated film was evaluated, the matte appearance transferability 3 (glossiness) was rejected because the particles of the laminated film resin layer were attached to the transfer surface although the peelability was possible. ..

(Comparative Example 4)
A laminated film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the composition of the resin layer composition solution was changed as shown in the table.

The laminated film of the present invention is a laminated film in which a resin layer containing inorganic particles and / or organic particles is laminated on at least one surface of a base material layer, and the resin layer is on at least one surface layer, and the surface of the resin layer. The in-plane average value Gb of the 85-degree glossiness measured in 1) is 25 or less, and the ratio (S / A) of the projected area A (μm ² ) of the resin layer to the actual surface area S (μm ² ) per projected area is , 1.15 or more and 1.80 or less, preferably used as a heat-resistant transfer film having high process compatibility that achieves both excellent matte appearance and transferability in a circuit forming process that requires a high degree of matte tone. Can be done.
The laminated film of the present invention is used in a circuit forming process in which a resin layer containing inorganic particles and / or organic particles is laminated and the surface area of the film is significantly increased as compared with a conventional film, so that a high degree of matte tone is required. It can be suitably used as a heat-resistant transfer film having high process compatibility that achieves both an excellent matte appearance and transferability.

Claims (5)

A laminated film in which a resin layer containing inorganic particles and / or organic particles is laminated on at least one surface of a base material layer, wherein the resin layer is on at least one surface layer, and the 85 degree glossiness measured on the surface of the resin layer. The in-plane average value Gb of the resin layer is 25 or less, and the ratio (S / A) of the projected area A (μm ² ) of the resin layer to the actual surface area S (μm ² ) per projected area is 1.15 or more. 80 Ri der hereinafter the resin layer surface, the average value of the surface waviness (Wa) is 0.05 to 0.5 [mu] m, the surface peak count (Pc) is 100 to 1000 / mm, the surface roughness (Ra) of 0.4~1.0μm der Ru laminated film. The lamination according to claim 1 , wherein the ratio ( Gbmin / Gbmax ) of the in-plane maximum value Gbmax and the in-plane minimum value Gbmin measured on the surface of the resin layer is 0.85 or more and 0.97 or less. the film. The laminated film according to claim 1 or 2 , wherein the base material layer is composed of at least two layers, and the layer in contact with the resin layer contains inorganic particles and / or organic particles. The ratio (rb / rc) of the number average particle size rc (μm) of the particles contained in the resin layer to the number average particle size rb (μm) of the particles contained in the layer in contact with the resin layer of the base material layer is 4 The laminated film according to claim 3 , which is 10 or less. The laminated film according to any one of claims 1 to 4 , which is used for mold release applications.