TWI811302B - Polyester Film for Dry Film Resist Substrates - Google Patents

Abstract

The present invention provides a polyester film for a dry film resist base material that can be used as a base material film in a step of producing a dry film resist for a flexible printed wiring board or the like. The polyester film for a dry film resist base material of the present invention is characterized in that it has a coating layer on at least one side of the polyester film, and the content of the antistatic agent in the coating layer is 45% by mass or less. The coating layer The layer contains particles, and the area ratio of particles AS with a particle diameter of 30 to 80 nm is 60 to 99.9% relative to the total area of particles occupying the surface of the coating layer when the surface of the coating layer is observed. Within the range, the area ratio of particles AL with particle diameters of 100 to 400 nm is within the range of 0.1 to 15%, and does not substantially contain particles with particle diameters exceeding 1 μm.

Description

Polyester film for dry film resist substrates

The present invention relates to a film that can be suitably used, for example, as a film for a base material in a step of producing a dry film resist for a flexible printed circuit board or the like.

Previously, polyester films represented by polyethylene terephthalate and polyethylene naphthalate had excellent properties such as mechanical strength, dimensional stability, flatness, heat resistance, chemical resistance, and optical properties. Because of its excellent cost performance, it is used in various applications.

An example of use of a polyester film is a film used in a dry film resist step when manufacturing a flexible printed wiring board. The dry film resist includes, for example, a three-layer structure of base film/photosensitive resin layer/protective film. As the base film, a polyester film excellent in mechanical properties, optical properties, chemical resistance, heat resistance, dimensional stability, planarity, etc. is used. To briefly describe the use example, first the protective film is peeled off, and the exposed photosensitive resin layer is brought into close contact with the conductive base material attached to the substrate. Next, a glass plate or film (called a photomask) on which a circuit is printed is brought into close contact with the base film side, and light is irradiated from the photomask side. Ultraviolet rays are usually used for this irradiation light. Light passes through the transparent part of the circuit printed on the photomask, and the photosensitive resin is only exposed to ultraviolet rays and undergoes a partial reaction during exposure. Remove the glass plate and base film, and use an appropriate solvent to remove the unexposed portion of the photosensitive resin layer that has not been exposed to ultraviolet rays. Furthermore, if etching is performed using acid or the like, the photosensitive resin layer is removed and a conductive base material layer is formed as a circuit.

In recent years, due to the miniaturization of electronic equipment, high-definition flexible printed wiring boards have been required, and further thinning of circuit patterns formed on the surface of insulating substrates has become an urgent task. urgent. Therefore, the polyester film used as a base film is also required to have high quality. In the photoresist film, when the photosensitive resin layer is exposed, light passes through the base film as described above. Therefore, if the transparency of the base film is low, problems such as insufficient exposure of the photosensitive resin layer or deterioration of resolution due to light scattering may occur. Therefore, it is important that the polyester film used as a base film has low haze and has high transparency. Furthermore, when there is damage on the film surface, problems such as scattering of transmitted light and deterioration of resolution may occur. Therefore, it is required that there be no damage on the film surface.

A polyester film with a smooth surface, high transparency, and low film haze has poor operability in the film manufacturing process, winding process, etc. If this type of film roll is used, there are problems such as the surface being easily damaged, and the air entrained between the films during the winding step being difficult to escape, causing wrinkles.

In order to improve the handleability of such a film or to improve the handleability and winding characteristics of the dry film resist itself, a method of containing particles in the polyester film to form fine protrusions on the surface is generally used. However, if particles are contained in the polyester film, although the workability and winding characteristics are improved, the level of transparency required for high definition cannot be obtained. Therefore, no method has yet been found to obtain a polyester film that satisfies transparency, damage resistance, and smoothness at the same time.

As a method of maintaining the transparency of the film and improving the smoothness, a method of containing particles only in a thin surface layer of a polyester film and suppressing the content to a low level has been proposed (Patent Documents 1 and 2). However, in this method, there is a concern that the damage resistance during the processing step is poor because there is no coating layer.

Regarding prevention of damage during the coiling step and processing step, a method of adding a wax agent to the coating layer has been proposed (Patent Document 3). However, it is considered that the performance imparted by the wax agent alone to provide anti-damage properties is not sufficient. In addition, this method uses a surfactant-type antistatic agent, and there is a concern of contamination in the substrate film manufacturing step and the photoresist film manufacturing step due to the bleeding of the antistatic agent.

[Prior technical literature] [Patent Document]

Patent Document 1: Japanese Patent Application Laid-Open No. 2000-221688

Patent Document 2: Japanese Patent Application Laid-Open No. 2001-117237

Patent Document 3: Japanese Patent Application Publication No. 2006-327158

The present invention was made in view of the above-mentioned actual situation, and its problem to be solved is to provide a dry film resist base material that can be suitably used as a base film in the dry film resist production step of a flexible printed wiring board or the like. Polyester film (hereinafter also referred to as "film for DFR base material").

The present inventors conducted diligent research in view of the above-mentioned actual situation, and as a result found that the above-mentioned problems can be easily solved by using a laminated polyester film having a specific structure, and thus completed the present invention.

That is, the gist of the present invention is a polyester film for a dry film resist base material, which is characterized in that: a coating layer is provided on at least one side of the polyester film, and the content of the antistatic agent in the coating layer is 45 Mass % or less, the coating layer contains particles, and the area of particles AS with a particle diameter of 30 to 80 nm relative to the total area of particles occupying the surface of the coating layer when the surface of the coating layer is observed The ratio is in the range of 60 to 99.9%, the area ratio of particles AL with a particle diameter of 100 to 400 nm is in the range of 0.1 to 15%, and does not substantially contain particles with a particle diameter of more than 1 μm.

The main purpose of the present invention is a polyester film for a dry film resist substrate, which is characterized in that: there is a coating layer on at least one side of the polyester film, and the coating layer contains a surfactant, The coating layer contains particles, and relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed, the area ratio of particles AS with a particle diameter of 30 to 80 nm is 60 to 60 Within the range of 99.9%, the area ratio of particles AL with a particle size of 100 to 400 nm is within a range of 0.1 to 15%, and does not substantially contain particles with a particle size exceeding 1 μm.

The main purpose of the present invention is a polyester film for a dry film resist substrate, which is characterized in that: a coating layer is provided on at least one side of the polyester film, and the coating layer does not substantially contain inorganic salts. The coating layer Contains particles, and relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed, the area ratio of particles AS with a particle diameter of 30 to 80 nm is in the range of 60 to 99.9% Within, the area ratio of particles AL with a particle size of 100 to 400 nm is in the range of 0.1 to 15%, and does not substantially contain particles with a particle size exceeding 1 μm.

The main purpose of the present invention is a polyester film for a dry film resist substrate, which is characterized in that: a coating layer is provided on at least one side of the polyester film, and the coating layer does not substantially contain a polyether compound. The cloth layer contains particles, and relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed, the area ratio of particles AS with a particle diameter of 30 to 80 nm is 60 to 99.9%. Within the range, the area ratio of particles AL with particle diameters of 100 to 400 nm is within the range of 0.1 to 15%, and does not substantially contain particles with particle diameters exceeding 1 μm.

According to the present invention, as the base film in the dry film resist step, circuit formation of extremely fine lines can be performed by simultaneously satisfying transparency, damage resistance, grinding resistance, air escape properties, and smoothness. Furthermore, according to the present invention, it is possible to provide a film for a DFR base material that has good smoothness and damage resistance, so that the air leakage index can be reduced, and that has good air escape properties, so that it can be rolled When the film is wound into a roll, the inhaled gas can easily escape, allowing the films to be in close contact with each other and rolled tightly, thus preventing the film from deflecting toward the roll core during storage and transportation. Damage and grinding caused by offset make surface wrinkles less likely to occur. According to the present invention, a film for DFR substrates with higher quality can be provided, and its industrial value is high.

Hereinafter, an example of an embodiment of the present invention will be described in detail. However, the present invention is not limited to the embodiment examples described below, and can be implemented with any modification within the scope that does not deviate from the gist of the present invention.

The film for DFR base material according to the embodiment of the present invention has a coating layer on at least one side of the polyester film. The content of the antistatic agent in the coating layer is 45% by mass or less. The coating layer contains particles. When the surface of the coating layer is observed, the total area of the particles occupying the surface of the coating layer, the area ratio of particles AS with a particle diameter of 30 to 80 nm is in the range of 60 to 99.9%, and the particle diameter is The area ratio of particles AL between 100 and 400 nm is in the range of 0.1 to 15%, and does not substantially contain particles with a particle size exceeding 1 μm.

The DFR base film according to the embodiment of the present invention has a coating layer containing particles and optionally an antistatic agent on at least one side of the polyester film. Therefore, the coating layer can be used to maintain the base film. While being transparent, it also meets the requirements of damage resistance, grinding resistance, air escape, and smoothness. Furthermore, when the coating layer of the DFR substrate film according to the embodiment of the present invention contains an antistatic agent, by reducing the content of the antistatic agent in the coating layer to 45% by mass or less, it is possible to suppress The exudation of antistatic agents prevents contamination of the DFR substrate film caused by exudation, and prevents damage caused by the adsorption of dust, etc.

The film for DFR base material according to the embodiment of the present invention has a coating layer on at least one side of the polyester film, the coating layer contains a surfactant, and the coating layer contains particles. When the surface is observed, the total area of the particles occupied by the surface of the coating layer, the area ratio of particles AS with a particle diameter of 30 to 80 nm is in the range of 60 to 99.9%, and the particle diameter is 100 The area ratio of ~400nm particles AL is in the range of 0.1~15%, and does not substantially contain particles with a particle size exceeding 1 μm.

The film for DFR base material according to the embodiment of the present invention has a coating layer on at least one side of the polyester film, and the coating layer contains a surfactant and particles. Therefore, the coating layer can be used to maintain the base material. While the material film is transparent, it also meets the requirements of damage resistance, anti-abrasion, air escape, and smoothness. In addition, the film for DFR substrates according to the embodiment of the present invention contains a surfactant in the coating layer. The surfactant can improve the wettability of the coating liquid to the polyester film and suppress uneven coating or coating The shrinkage of the liquid makes the appearance of the coating layer good.

The film for DFR base material according to the embodiment of the present invention has a coating layer on at least one side of the polyester film. The coating layer does not substantially contain inorganic salts. The coating layer contains particles. Compared with coating the When the surface of the layer is observed, the total area of the particles occupying the surface of the coating layer, the area ratio of particles AS with a particle diameter of 30~80nm is in the range of 60~99.9%, and the area ratio of particles with a particle diameter of 100~400nm The area ratio of AL is in the range of 0.1~15%, and does not substantially contain particles with a particle size exceeding 1 μm.

The DFR base film according to the embodiment of the present invention has a coating layer containing particles on at least one side of the polyester film. Therefore, the coating layer can satisfy the requirements while maintaining the transparency of the base film through the coating layer. Damage resistance, grinding resistance, air escape, and smoothness. In addition, since the coating layer of the film for DFR base material according to the embodiment of the present invention does not substantially contain inorganic salts, the emulsion formed from the cross-linking agent etc. contained in the coating liquid will not be destroyed by the inorganic salts and can be It suppresses the uneven coating of the polyester film with the coating liquid and improves the appearance of the coating layer.

The film for DFR base material according to the embodiment of the present invention has a coating layer on at least one side of the polyester film. The coating layer does not substantially contain a polyether compound, and the coating layer contains particles. Compared with the coating layer, The total area of the particles occupying the surface of the coating layer when the surface of the cloth layer is observed According to the calculation, the area ratio of particles AS with a particle diameter of 30~80nm is in the range of 60~99.9%, and the area ratio of particles AL with a particle diameter of 100~400nm is in the range of 0.1~15%, and does not substantially contain particles. Particles with a diameter exceeding 1 μm.

The DFR base film according to the embodiment of the present invention has a coating layer on at least one side of the polyester film. Therefore, the coating layer can maintain the transparency of the base film and at the same time satisfy the requirements of damage prevention. properties, anti-grinding properties, air escape properties, and smoothness. In addition, since the coating layer of the DFR substrate film according to the embodiment of the present invention contains substantially no polyether compound, it has excellent water resistance and moisture resistance and can improve the damage resistance over time.

The film for a DFR base material according to the embodiment of the present invention contains particles AS with a particle diameter of 30 to 80 nm in the coating layer in the range of 60 to 99.9% based on the area ratio of the coating layer surface, so it can be maintained Improves damage resistance with transparency. In addition, since the film for DFR base material according to the embodiment of the present invention contains particles AL with a particle diameter of 100 to 400 nm in the range of 0.1 to 15% based on the area ratio of the coating layer surface, it can be Improves grinding resistance, air escape and smoothness while maintaining damage resistance. Furthermore, since the coating layer of the film for DFR base material according to the embodiment of the present invention does not substantially contain particles having a particle diameter exceeding 1 μm, the anti-wear properties are improved. In this specification, the particles contained in the coating layer of the film for DFR base materials are also referred to as particles A. Particle A refers to the particles contained in the coating layer. Particle A includes particle AS with a particle diameter of 30 to 80 nm and particle AL with a particle diameter of 100 to 400 nm. It may also include particles other than particle AS and particle AL with a particle diameter of less than 1 μm (hereinafter also referred to as "other particles"). AE").

polyester film

The polyester film in the present invention can be an unstretched film (sheet) or a stretched film. Among them, a stretched film extending in a uniaxial direction or a biaxial direction is preferred. Among them, in terms of the balance and balance of mechanical properties In terms of excellent surface properties, a biaxially stretched film is preferred.

The polyester film in the present invention can be composed of a single layer or a multi-layer structure of two or more layers, and is not particularly limited. When adding particles to the polyester layer, three or more layers are preferred from the viewpoint of effectively imparting transparency and smoothness, and three layers are preferred from the viewpoint of cost. In addition, when forming three layers, from the viewpoint of effectively imparting transparency and smoothness, it is preferable to use two types of three layers in which both surface layers contain particles and the middle layer does not contain particles, and at least one surface layer contains particles and The middle layer and the other surface layer are 3 types of 3 layers that do not contain particles.

The polyester in the present invention includes, for example, the dicarboxylic acid component constituting the polyester: terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, 4, 4'-diphenyldicarboxylic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, etc. In particular, in terms of the mechanical properties of the film, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferred. Examples of the glycol component constituting the polyester include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol. alcohol, cyclohexanedimethanol, polyethylene glycol, etc. Especially in terms of the rigidity of the film, ethylene glycol is preferred.

The polyester may be a copolyester obtained by copolymerizing the dicarboxylic acid component or diol component as the third component, or may contain a trifunctional or higher polycarboxylic acid component or a trifunctional or higher polyol component. The polyester obtained may be a polyester copolymerized in a small amount within a substantially linear range (for example, 5 mol% or less). As the polyester used in the present invention, polyethylene terephthalate or polyethylene naphthalate is particularly preferred. The polyester can be produced by conventional methods. If the inherent viscosity of the polyester (phenol/tetrachloroethane = 50/50 (weight ratio), 30°C) is 0.45 or above, the tearability and rigidity of the film will be greater. etc. and have good mechanical properties, so they are preferred.

The polymerization catalyst for polyester is not particularly limited, and previously known catalysts can be used. Examples of the compound include antimony compounds, titanium compounds, germanium compounds, manganese compounds, aluminum compounds, magnesium compounds, calcium compounds, and the like. Among them, titanium compounds and germanium compounds are preferred because they have high catalytic activity, can polymerize in small amounts, and have a small amount of metal elements remaining in the film, thereby improving the transparency of the film.

When the polyester film is composed of two layers, the thickness of at least one layer is preferably one-eighth or less of the thickness of the other layer, more preferably one-tenth or less, and still more preferably one-twelfth or less. Especially preferably, it is less than one sixteenth. When the polyester film is composed of three or more layers, the thickness of at least one surface layer (outermost layer) is preferably less than one-eighth of the thickness of the layers other than the surface layer (the total thickness of the intermediate layers), and more preferably One-tenth or less, more preferably one-twelfth or less, particularly preferably one-sixteenth or less. When the polyester film is composed of two or more layers, if the thickness of at least one surface layer is within the range of one-eighth or less of the thickness of layers other than the surface layer, then at least one surface layer contains the following: In the case of particle B, high transparency and good smoothness can also be achieved at the same time.

Particle B

In the polyester film, it is preferable to contain particles for the main purpose of imparting slipperiness and damage prevention in each step. In this specification, the particles contained in the polyester film are called particles B. When the polyester film has a multilayer structure, the particles B are preferably contained in at least one layer. When the polyester film has a two-layer structure, the particles B are preferably contained in at least one layer. When the polyester film has a multilayer structure of three or more layers, the particles B are preferably contained in at least one surface layer, and may also be contained in both surface layers.

樹脂等有機粒子等。進而，於聚酯膜之製造步驟中，亦可使用使觸媒等金屬化合物之一部分沈澱並微分散之析出粒子。 The type of particles B contained in the polyester film is not particularly limited as long as it can impart slipperiness. Specific examples include inorganic particles such as silica, alumina, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, zirconium oxide, and titanium oxide; acrylic resin and styrene resin. , Urea resin, phenolic resin, epoxy resin, benzene guanidine

Resin and other organic particles, etc. Furthermore, in the production process of the polyester film, precipitated particles in which a part of a metal compound such as a catalyst is precipitated and finely dispersed may be used.

If the particles B are added to the polyester film to form protrusions on the surface of the polyester film, poor exposure to ultraviolet rays due to the protrusions or depressions on the resist surface may occur during the manufacture of wiring boards, which is a problem for recent years. The formation of circuits with extremely fine lines required may result in reduced resolution or defects, or may result in reduced transparency of the film. Among them, by using alumina particles, organic particles, and silicon dioxide particles as particles B, high transparency and damage prevention properties of the polyester film can be obtained and circuit defects can be reduced.

The average particle diameter of the particles B is usually 1.5 μm or less, preferably 1.0 μm or less, more preferably 0.001 to 0.5 μm, and further preferably 0.001 to 0.3 μm. When the average particle diameter exceeds 1.5 μm, the surface roughness of the polyester film becomes rough, so the unevenness of the polyester film may be transferred to the resist. If the resist has unevenness, when the resist is removed by acid etching, it may affect the etching process and cause defects in the circuit. Regarding the average particle size of the particles, when the particles are powder, the equivalent spherical distribution obtained by measuring the powder using a centrifugal sedimentation particle size distribution measuring device (model SA-CP3, manufactured by Shimadzu Corporation) can be considered The particle diameter (d50) with a cumulative volume fraction of 50% is set as the average particle diameter. Regarding the average particle size of the film or the particles in the film, for example, a scanning electron microscope (manufactured by Hitachi High-Technology Co., Ltd., "S3400N") can be used to observe the powder or polyester film, and from the image data obtained The size of one particle is measured, and the average value of 10 points (10 particles) is taken as the average particle diameter.

The smaller the average particle size of the particles B, the higher the transparency of the polyester film, which can reduce circuit defects and can therefore be applied to circuits that require thinner ultra-thin wires. Average particle size relative to The average particle diameter of the smaller particles B (hereinafter, sometimes referred to as "particles B-1") is usually in the range of 0.001 to 0.1 μm, preferably 0.001 to 0.08 μm, and more preferably 0.001 to 0.06 μm. In order to maintain the smoothness of the polyester film and prevent damage during the film-making step due to the decrease in smoothness, particles B (hereinafter sometimes referred to as "particles") whose average particle diameter is slightly larger than particles B-1 can also be used. B-2"). By using particles B-2, smoothness can also be imparted to the polyester film. The average particle diameter of the particles B-2 is usually in the range of 0.1 to 1.5 μm, preferably 0.1 to 1.0 μm, more preferably 0.1 to 0.5 μm, and further preferably 0.1 to 0.3 μm. Furthermore, two or more types of particles B including particles B-1 included in the range of average particle diameters of 0.001 to 0.1 μm and particles B-2 included in the range of average particle diameters of 0.1 to 1.5 μm may be used together. , and can also be used together to achieve high transparency and good smoothness at the same time.

The content of the particles B in the polyester film is preferably 10,000 ppm by mass or less, more preferably 8,000 ppm by mass or less, more preferably 6,000 ppm by mass or less, and even more preferably 4,000 ppm by mass or less. When using particles B-2 with an average particle diameter of 0.1 to 1.5 μm, since smoothness can be effectively imparted in a small amount, the content of particles B in the polyester film is preferably 1000 ppm by mass or less. More preferably, it is 800 mass ppm or less, and still more preferably, it is the range of 500 mass ppm or less. The lower limit is not particularly limited, but it is 1 mass ppm or more or 2 mass ppm or more excluding particle B. When the content of particle B in the polyester film is high, the haze may increase, and the exposure of ultraviolet rays in the high-resolution dry film resist may become insufficient, resulting in circuit defects or a reduction in resolution. The danger.

The shape of the particles used is not particularly limited, and any shape such as spherical, lumpy, rod-like, and flat shapes can be used. In addition, its hardness, specific gravity, color, etc. are not particularly limited.

These series of particles may be used in combination of two or more types as necessary.

There is no particular limitation on the method of adding particles to the polyester film, and conventionally known methods can be used. For example, it can be added at any stage of producing the polyester constituting the film, but is preferably added after the completion of the esterification or transesterification reaction.

Furthermore, in addition to the above-mentioned particles, the polyester film in the present invention may also contain previously known antioxidants, antistatic agents, heat stabilizers, ultraviolet absorbers, lubricants, dyes, pigments, etc., if necessary.

The thickness of the polyester film in the present invention is not particularly limited as long as it is within the range that can be formed as a film. In terms of mechanical strength, operability, productivity, etc., it is preferably 1 to 300 μm, and more preferably 1 to 300 μm. The range is 5~50μm, and more preferably 8~25μm.

As a method of forming a polyester film, a generally known film forming method can be used and is not particularly limited. For example, the following method can be cited: when producing a biaxially stretched polyester film, first use an extruder to melt and extrude the polyester raw material described above from a die nozzle, and use a cooling roller to cool and solidify the molten sheet. An unstretched sheet is obtained. In this case, in order to improve the planarity of the sheet, it is better to improve the adhesion between the sheet and the rotating cooling cylinder. An electrostatic application adhesion method or a liquid coating adhesion method can be preferably used.

Then, the obtained unstretched sheet is stretched in one direction by a rolling or tenter stretching machine. The extension temperature is usually 70~150°C, preferably 80~140°C, and the extension ratio is usually 2.5~7 times, preferably 3.0~6 times. Then, the film is extended in a direction orthogonal to the extending direction of the first stage at a temperature of usually 70 to 170° C. with an extension ratio of usually 2.5 to 7 times, preferably 3.0 to 6 times. Next, heat treatment is performed at a temperature of 180 to 270°C under stretching or relaxation within 30% to obtain a biaxial alignment film. It is also possible to adopt a method of extending in one direction in two or more stages in the above-mentioned extending. In this case, it is preferable to proceed so that the final stretch ratios in both directions fall into the above ranges.

Formation of coating layer

The formation of the coating layer in the present invention will be described, and then the coating liquid forming the coating layer and the structure of the coating layer will be described. Regarding the formation of the coating layer, the coating layer can be formed by applying the coating liquid within the line on the film surface during the film-making step of the polyester film, or by temporarily applying the coating liquid outside the system. Off-line coating on the produced polyester film forms a coating layer. In terms of ease of processing, the coating layer is preferably formed by in-line coating.

In-line coating is a method of applying a coating liquid to form a coating layer during the polyester film manufacturing process. Specifically, in-line coating is based on melting and extruding the polyester, stretching it, and then heat-setting it. And the method of applying the coating liquid at any stage before rolling up. The coating liquid is usually applied to any polyester film obtained by melting and quenching the unstretched sheet, the stretched uniaxially stretched film, the biaxially stretched film before heat setting, or the film before winding after heat setting.

As a method of applying the coating liquid, for example, air knife coating, blade coating, bar coating, bar coating, blade coating, extrusion coating, dip coating, reverse roll coating, transfer roll Coating, gravure coating, contact roller coating, polishing coating, spray coating, curtain coating, calendar coating, extrusion coating and other previously known coating methods.

It is not limited to the following. For example, in the sequential biaxial stretching, a uniaxially stretched film extending especially along the length direction (longitudinal direction) is coated with a coating liquid and then stretched laterally to form a DFR base material with a coating layer on the polyester film. The method of using membrane is excellent. According to this method, the polyester film can be formed and the coating layer can be formed at the same time, so it is advantageous in terms of manufacturing cost. In addition, since the stretching is performed after coating, the coating can also be made by stretching the magnification. The thickness of the layer changes, making thin film coating easier than offline coating. Furthermore, the thickness of the coating layer can be made more uniform.

Furthermore, by providing a coating layer on the polyester film before stretching, the coating layer can be The polyester film is stretched together, whereby the coating layer and the polyester film can be tightly adhered to each other. Furthermore, in the production of biaxially stretched polyester films, the ends of the film are held and stretched by clamps, etc., thereby constraining the film in the longitudinal and transverse directions, and in the heat fixing step, wrinkles, etc. can be prevented. High temperature is applied while maintaining flatness.

Therefore, the heat treatment performed after coating can be carried out to a high temperature that cannot be achieved by other methods, so that the coating layer and the polyester film can be more closely adhered, and a strong coating layer can be produced.

In addition, whether the coating layer is formed by off-line coating or in-line coating, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination as necessary. In order to improve the coating properties and adhesion of the coating liquid forming the coating layer to the polyester film, the polyester film can also be subjected to chemical treatment or corona discharge treatment, plasma treatment, ozone treatment, chemicals before coating. Treatment, solvent treatment and other surface treatments.

Coating liquid

The coating liquid used to form the coating layer is not limited by the solvent used. Among them, an aqueous coating liquid using water as a solvent is preferably used, and may contain a small amount of organic solvent. Examples of organic solvents include: alcohols such as ethanol, isopropyl alcohol, ethylene glycol, and glycerol; ethers such as ethyl cellosolve, tert-butyl cellosolve, propylene glycol monomethyl ether, and tetrahydrofuran; acetone, methylethyl Ketones such as ketones; esters such as ethyl acetate; amines such as dimethylethanolamine, etc. These can be used individually or in combination of plural types. There may be cases where the stability and coating properties of the coating liquid can be improved by appropriately selecting these organic solvents and including the organic solvents in the aqueous coating liquid as necessary.

The coating liquid contains the particles A so as to be included in the coating layer formed from the coating liquid. Preferably, the coating liquid contains a compound selected from a compound having a long-chain alkyl group, wax, fluorinated At least one release agent from the group consisting of compounds and polysiloxane compounds. In addition, the coating liquid may contain various polymers described below in addition to the polymer cross-linked by a cross-linking agent. The coating liquid may also contain a surfactant if necessary.

Cross-linking agent

唑啉化合物、環氧化合物、異氰酸酯系化合物、碳二醯亞胺系化合物、矽烷偶合劑化合物等；該等之中，就耐久性之觀點而言，交聯劑較佳為三聚氰胺化合物或

唑啉化合物，就防受損性之觀點而言，較佳為三聚氰胺化合物。又，該等交聯劑亦可將2種以上併用。再者，亦可使塗佈液中含有任意聚合性單體作為與該等交聯劑一起硬化之成分。 The coating liquid forming the coating layer may also contain a cross-linking agent. When the coating liquid constituting the coating layer contains a cross-linking agent, the coating layer can form a dense coating layer with a higher cross-linking density, which can provide more suitable protection during the dry film resist step. Damage. The cross-linking agent is not particularly limited, and conventionally known cross-linking agents can be used. Examples of the crosslinking agent include: melamine compounds,

oxazoline compounds, epoxy compounds, isocyanate compounds, carbodiimide compounds, silane coupling agent compounds, etc.; among these, from the viewpoint of durability, the cross-linking agent is preferably a melamine compound or

From the viewpoint of damage prevention properties, the oxazoline compound is preferably a melamine compound. Moreover, these cross-linking agents can also be used in combination of 2 or more types. Furthermore, the coating liquid may contain any polymerizable monomer as a component that hardens together with the cross-linking agent.

The coating liquid for forming the coating layer may contain a cross-linking agent to form a curable coating layer. Especially when applied to a dry film resist capable of forming circuits with extremely fine lines, if the coating liquid contains a cross-linking agent, it can impart more excellent surface smoothness. Furthermore, as mentioned above, this effect becomes more remarkable by using a specific crosslinking agent.

The melamine compound refers to a compound having a melamine skeleton among the compounds. For example, a compound obtained by reacting an alcohol with a hydroxyalkylated melamine derivative, a hydroxyalkylated melamine derivative and partially or completely etherified, and a mixture thereof can be used. Examples of hydroxyalkylation include hydroxymethylation, hydroxyethylation, isohydroxybutylation, n-hydroxybutylation, isohydroxybutylation, and the like. Among these, hydroxymethylation is preferred from the viewpoint of reactivity. Also, as the alcohol used for etherification, it is appropriate to Use methanol, ethanol, isopropanol, n-butanol, isobutanol, etc. From the viewpoint of improving the strength of the coating film and thereby improving the adhesion between the coating layer and the base material, a hydroxyalkylated melamine derivative obtained by partial etherification is preferred, and an alcohol obtained by etherification with methanol is more preferred. Therefore, a more preferable form is a partially etherified melamine having a hydroxymethyl group and a methoxymethyl group. The etherified hydroxyalkyl group is preferably 0.5 to 5 equivalents, and more preferably 0.7 to 3 equivalents relative to the non-etherified hydroxyalkyl group. In addition, the melamine compound may be a monomer or a polymer of a dimer or higher, or a mixture thereof may be used. Furthermore, what is obtained by co-condensing urea etc. with a part of melamine can also be used. In order to improve the reactivity of a melamine compound, a crosslinking catalyst can also be used.

The so-called melamine cross-linking catalyst is used to increase the reactivity of thermosetting resins. Various well-known catalysts can be used, for example, amine compounds, salts of amine compounds, aromatic sulfonic acid compounds such as p-toluenesulfonic acid, organic acids such as phosphoric acid compounds, and their salts, imine compounds, amidine compounds, Guanidine compounds, organic metal compounds, metal salts such as zinc stearate or zinc myristate, aluminum stearate or calcium stearate, etc. Among these, an amine compound, a salt of an amine compound, or p-toluenesulfonic acid is preferable, and an amine compound or a salt of an amine compound is more preferable.

唑啉化合物，係分子內具有

唑啉基之化合物，尤佳為含有

唑啉基之聚合物，可藉由含有加成聚合性

唑啉基之單體單獨製作或者藉由與其他單體之聚合製作。含有加成聚合性

唑啉基之單體可列舉：2-乙烯基-2-

唑啉、2-乙烯基-4-甲基-2-

唑啉、2-乙烯基-5-甲基-2-

唑啉、2-異丙烯基-2-

唑啉、2-異丙烯基-4-甲基-2-

唑啉、2-異丙烯基-5-乙基-2-

唑啉等；可使用該等之1種或2種以上之混合物。該等之中，2-異丙烯基-2-

唑啉於工業上亦容易獲取而較佳。其他單體只要為可與含有加成聚合性

唑啉基之單體共聚之單體，則並無限制，例如可列舉：(甲基)丙烯酸烷基酯(作為烷基，為甲基、乙基、正丙基、異丙基、 正丁基、異丁基、第三丁基、2-乙基己基、環己基)等(甲基)丙烯酸酯類；丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸、苯乙烯磺酸及其鹽(鈉鹽、鉀鹽、銨鹽、三級胺鹽等)等不飽和羧酸類；丙烯腈、甲基丙烯腈等不飽和腈類；(甲基)丙烯醯胺、N-烷基(甲基)丙烯醯胺、N,N-二烷基(甲基)丙烯醯胺(作為烷基，為甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、2-乙基己基、環己基等)等不飽和醯胺類；乙酸乙烯酯、丙酸乙烯酯等乙烯酯類；甲基乙烯醚、乙基乙烯醚等乙烯醚類；乙烯、丙烯等α-烯烴類；氯乙烯、偏二氯乙烯、氟乙烯等含鹵素α,β-不飽和單體類；苯乙烯、α-甲基苯乙烯等α,β-不飽和芳香族單體等、可使用該等之1種或2種以上之單體。 so-called

Oxazoline compounds have in the molecule

Compounds of oxazoline base, especially those containing

Oxazoline-based polymers can be obtained by containing addition polymerizability

The oxazoline-based monomer is produced alone or by polymerization with other monomers. Contains addition polymerizability

Examples of oxazolinyl monomers include: 2-vinyl-2-

Oxazoline, 2-vinyl-4-methyl-2-

Oxazoline, 2-vinyl-5-methyl-2-

Oxazoline, 2-isopropenyl-2-

Oxazoline, 2-isopropenyl-4-methyl-2-

Oxazoline, 2-isopropenyl-5-ethyl-2-

Oxazoline, etc.; one type or a mixture of two or more types of these can be used. Among these, 2-isopropenyl-2-

Oxazoline is also easy to obtain industrially and is preferred. Other monomers can be used as long as they contain addition polymerizability

The monomer for copolymerization of the oxazoline group monomer is not limited, and examples thereof include: (meth)acrylic acid alkyl ester (the alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl). base, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl) and other (meth)acrylates; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid , crotonic acid, styrenesulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) and other unsaturated carboxylic acids; unsaturated nitriles such as acrylonitrile and methacrylonitrile; (methyl ) Acrylamide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide (the alkyl group is methyl, ethyl, n-propyl, isopropyl , n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, etc.) and other unsaturated amides; vinyl esters such as vinyl acetate, vinyl propionate; methyl vinyl ether, ethyl vinyl ether, etc. Vinyl ethers such as vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride and other halogen-containing α,β-unsaturated monomers; styrene, α-methylstyrene, etc. α,β-unsaturated aromatic monomers, etc., one or more of these monomers can be used.

The so-called epoxy compound refers to a compound having an epoxy group in the molecule, for example, the condensate of epichlorohydrin and hydroxyl or amine groups of ethylene glycol, polyethylene glycol, glycerol, polyglycerol, bisphenol A, etc.; Polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, etc. Examples of the polyepoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, and triglycidyl tris(2-hydroxyethyl). Isocyanate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether; examples of diepoxy compounds include: neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, m Diphenol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly1,4-butylene glycol diglycidyl ether ; Examples of monoepoxy compounds include: allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether; examples of glycidyl amine compounds include: N, N, N', N '-Tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamine)cyclohexane, etc.

The so-called isocyanate compound refers to a compound having an isocyanate derivative structure represented by isocyanate or blocked isocyanate. Examples of the isocyanate include aromatic isocyanates such as toluene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; α, α, α', α' - Tetramethylxylylene diisocyanate and other aliphatic isocyanates with aromatic rings; methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene Aliphatic isocyanates such as methyl diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropyl dicyclohexyl diisocyanate, etc. Alicyclic isocyanates, etc. In addition, polymers or derivatives such as biuret compounds, isocyanurate compounds, uretdione compounds, and carbodiimide-modified products of these isocyanates can also be cited. These can be used individually or in combination. Among the above isocyanates, in order to avoid yellowing caused by ultraviolet rays, aliphatic isocyanates or alicyclic isocyanates are more preferred than aromatic isocyanates.

When used in the state of blocked isocyanate, examples of the blocking agent include: bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol; propylene glycol monomethyl ether, ethylene glycol, Alcohol compounds such as benzyl alcohol, methanol, and ethanol; active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetyl acetate, ethyl acetate, and acetyl acetone; butyl Thiol-based compounds such as mercaptans and dodecylmercaptan; lactam-based compounds such as ε-caprolactam and δ-valerolactam; amine-based compounds such as diphenylaniline, aniline, and ethylideneimine ; Acetyl aniline, acetamide acid amide compounds, formaldehyde, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime and other oxime compounds; these can be used alone, or two types can be combined Use the above together. Among these, active methylene-based compounds are preferred especially from the viewpoint that peeling properties are not easily changed even after heating.

In addition, the isocyanate-based compound can be used in a monomer form or as a mixture or combination with various polymers. In order to improve the dispersibility and crosslinkability of the isocyanate-based compound, it is preferable to use a mixture or combination with a polyester resin or a urethane resin.

The so-called carbodiimide compound is a compound having a carbodiimide structure and is used to improve the heat and moisture resistance of the coating layer. Carbodiimide compounds can be synthesized using previously known techniques, generally using the condensation reaction of diisocyanate compounds. The diisocyanate compound is not particularly limited, and either aromatic or aliphatic compounds can be used. Specific examples include toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, and phenylene diisocyanate. Isocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, diisocyanate Cyclohexylmethane diisocyanate, etc.

The silane coupling agent compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule. Examples include: 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Epoxy group-containing compounds such as glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethyl Oxysilane and other vinyl-containing compounds; p-styryltrimethoxysilane, p-styryltriethoxysilane and other styryl-containing compounds; 3-(meth)acryloxypropyltrimethoxy Silane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxysilane Compounds containing (meth)acrylic acid groups such as methylpropylmethyldiethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(amine ethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3- Aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-amino Propylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-3-aminopropyltrimethoxy Silane, N-phenyl-3-aminopropyltriethoxysilane and other amine-containing compounds; tris(trimethoxysilylpropyl)isocyanurate, tris(triethoxysilylpropyl) base) isocyanurate and other compounds containing isocyanurate groups; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-Mercaptopropylmethyldiethoxysilane and other thiol-containing compounds.

Among the above-mentioned compounds, from the viewpoint of maintaining the strength of the coating layer, more preferred are silane coupling agent compounds containing epoxy groups, silane coupling agent compounds containing double bonds such as vinyl groups or (meth)acrylic acid groups, and Amino-based silane coupling agent compound.

The cross-linking agent contained in the coating liquid can react during the drying process and film-making process when forming the coating layer to improve the performance of the coating layer. It is presumed that unreacted products of these cross-linking agents, reacted compounds, or mixtures thereof exist in the coating layer formed from the coating liquid.

The content of the cross-linking agent in the coating liquid is preferably 5 to 85 mass %, more preferably 15 to 80 mass %, and further preferably 25 to 70 mass %, based on all non-volatile components in the coating liquid. Particularly preferred is 30 to 50% by mass. When the content of the cross-linking agent is 5 to 85% by mass relative to the total non-volatile components in the coating liquid, the strength of the coating layer formed from the coating liquid is increased, the damage resistance can be further improved, and the coating layer can be while satisfying smoothness. Furthermore, when the coating layer optionally contains an antistatic agent, the antistatic agent can be suppressed from seeping out of the coating layer, thereby preventing film contamination caused by seepage. When the content of the cross-linking agent is less than 5% by mass relative to the total non-volatile components in the coating liquid, sufficient damage prevention performance may not be obtained.

When the coating liquid contains a cross-linking catalyst as necessary, the content of the cross-linking catalyst The amount is usually 0.4 to 10% by mass, preferably 0.6 to 8% by mass, and more preferably 0.8 to 5% by mass relative to the non-volatile components in the coating liquid. If the content of the cross-linking catalyst is 0.4 to 10% by mass, a coating film with ideal damage prevention properties tends to be obtained.

The coating liquid contains particles, and the particles contained in the coating liquid and included in the coating layer composed of the coating liquid are also referred to as particles A. The particles A contained in the coating liquid include particles AS with a particle diameter of 30 to 80 nm (hereinafter, referred to as "particles AS") and particles AL with a particle diameter of 100 to 400 nm (hereinafter, referred to as "particles"). AL" situation). In the coating liquid, the area ratio of the particles AS is 60 to 99.9% relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer formed by the coating liquid is observed. The particle AS and the particle AL are included so that the area ratio of the particle AL is within the range of 0.1 to 15%.

The particles A contained in the coating liquid may also include particles other than particles AS and particles AL having a particle diameter of less than 1 μm. It is preferable that the coating liquid contains at least one release agent selected from the group consisting of compounds having long-chain alkyl groups, waxes, fluorine compounds, and polysiloxane compounds. Furthermore, when the coating liquid contains a cross-linking agent, the following various polymers may be included in addition to the cross-linked polymer.

The coating liquid may also contain the antistatic agent in the coating layer formed from the coating liquid. If necessary, the antistatic agent may be contained in the coating layer in an amount of 45% by mass or less. Moreover, the coating liquid may contain a surfactant.

coating layer

The coating layer of the film for DFR base material of the present invention is preferably a coating layer formed from a coating liquid by the above method.

When the polyester film has a multi-layer structure, the coating layer of the film for DFR base material may be a coating layer formed by coating a coating liquid on a surface layer containing particles, or it may be a coating layer coated on a surface layer that does not contain particles. The coating layer formed by the coating liquid on the surface layer. A DFR base film in which one of the surface layers of a multi-layered polyester film contains particles B and has a coating layer in contact with the surface layer containing the particles B has excellent damage resistance and smoothness due to the coating layer. It is easy to operate in the processing step, and in the dry film resist step, it is easy to form a resist layer on the side of the layer that does not contain particles B. A DFR base film in which one surface layer of a multi-layered polyester film contains particles B and has a coating layer connected to another surface layer that does not contain particles B has excellent damage prevention and smoothness due to the coating layer , so it is easy to operate in the processing step and the resist layer is easy to form in the dry film resist step.

The thickness of the coating layer of the DFR base material film (hereinafter also referred to as the "film thickness of the coating layer") is usually 0.001 to 1 μm, preferably 0.002 to 0.5 μm, more preferably 0.005 to 0.2 μm, and further preferably Preferably, it is 0.008~0.15μm, particularly preferably 0.01~0.1μm, and most preferably 0.01~0.08μm. If the thickness of the coating layer is 0.001~1μm, when used as a film for DFR substrates, the appearance of the coating film will be good, sufficient exposure can be obtained, and sufficient damage prevention performance can be obtained. The film thickness of the coating layer can be measured by the method for measuring the film thickness of the coating layer described in the following examples. If the film thickness of the coating layer of the DFR base material film is 0.001~1 μm, in the coating layer including particle AS and particle AL, transparency can be maintained by particle AS and sufficient damage prevention performance can be obtained , thereby further improving the anti-grinding property, and the air escape and smoothness can be further improved through the particles AL. A coating layer of this thickness can preferably be provided by in-line coating in particular.

antistatic agent

The coating layer of the film for DFR base material optionally contains an antistatic agent. to obtain the necessary protection In the case of a damaged and smooth coating layer, the coating layer may not contain an antistatic agent. The content of the antistatic agent in the coating layer is not limited, but is usually less than 45 mass%, preferably 1 to 45 mass%, more preferably 5 to 40 mass%, and more preferably 10 to 35 mass%, especially Preferably, it is 15~30% by mass. If the content of the antistatic agent in the coating layer is 45% by mass or less, bleeding of the antistatic agent from the coating layer can be suppressed. In addition, if the content of the antistatic agent in the coating layer is 1% by mass or more, the surface resistance of the coating layer can be reduced and contamination of the DFR base film caused by the antistatic agent bleeding out from the coating layer can be prevented. , and can inhibit the adsorption of dust, etc. The content of the antistatic agent in the coating layer can be measured, for example, by elemental analysis, fluorescent X-rays, NMR (nuclear magnetic resonance, nuclear magnetic resonance), and the like. The content of the antistatic agent in the coating liquid is not limited. It is usually 45 mass% or less, preferably 1 to 45 mass%, and more preferably 5 to 40 mass% relative to the non-volatile components in the coating liquid. Furthermore, 10-35 mass % is more preferable, and 15-30 mass % is especially preferable.

Since the coating layer of the DFR substrate film of the present invention contains an antistatic agent if necessary, the surface resistance value of the coating layer is preferably 1×10 ¹⁰ Ω or more, and more preferably 5×10 ¹⁰ ~1×10 ¹⁵ Ω, and more preferably 1×10 ¹¹ ~1×10 ¹⁵ Ω. When the surface resistance value of the coating layer of the DFR substrate film does not reach 1×10 ¹⁰ Ω, a large amount of antistatic agent is necessary, which may cause the antistatic agent to bleed out or the content of the cross-linking agent in the coating liquid. Relatively reduced, so damage resistance may be reduced.

Examples of antistatic agents include quaternary ammonium salts, pyridinium salts, cationic antistatic agents having cationic functional groups such as primary to tertiary amine groups, sulfonic acid bases, sulfate ester bases, and phosphate esters. Anionic antistatic agents with anionic functional groups such as bases and phosphonic acid bases, amphoteric antistatic agents such as amino acid-based and amino sulfate-based antistatic agents, polyol-based, polyglycerol-based, polyethylene glycol-based antistatic agents, etc. Various polymer antistatic agents such as antistatic agents with non-ionic functional groups. In addition, monomers or oligomers that have tertiary amine groups or quaternary ammonium groups and can be polymerized by ionizing radiation, such as N,N-dialkyl (meth)acrylic acid aminoalkyl ester monomers, can also be used. The fourth level of body, etc. Polymeric antistatic agents such as compounds, and conductive polymers such as polyaniline, polypyrrole, and polythiophene. Among these, a polymer-type antistatic agent having a tertiary amine group or a quaternary ammonium group is preferred.

surfactant

The coating layer of the DFR substrate film may also contain surfactants. The coating layer can use the surfactant contained in the coating liquid that forms the coating layer to improve the wettability of the coating liquid to the polyester film and suppress uneven coating (unevenness of the coating layer) or coating The shrinkage of the cloth liquid makes the coating layer have a good appearance. The content of the surfactant in the coating layer is usually 0.01% by mass or more, preferably 0.01~10% by mass, more preferably 0.05~5.0% by mass, further preferably 0.10~3.0% by mass, especially 0.10~ 1.0% by mass, optimally 0.30~1.0% by mass. If the content of the surfactant in the coating layer is 0.01% by mass or more, the transparency, damage resistance and smoothness of the coating layer can be maintained, and the wettability of the polyester film can be improved, inhibiting Uneven coating or shrinkage of the coating liquid will make the appearance of the coating layer better. If the surfactant content in the coating layer is less than 0.01% by mass, it will be difficult to improve the wettability. If it exceeds 10% by mass, the transparency of the coating layer will decrease and the haze value of the DFR base film will increase. Big situation. It is estimated that the content of the surfactant in the coating layer is approximately equal to the content of the surfactant relative to the non-volatile components in the coating liquid. The content of the surfactant in the coating liquid relative to the non-volatile components in the coating liquid is preferably 0.01 to 10 mass %, more preferably 0.05 to 5.0 mass %, and further preferably 0.10 to 3.0 mass %, especially The preferred range is 0.10~1.0% by mass, and the optimum range is 0.30~1.0% by mass.

As the surfactant, anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants can be used. Among these, from the viewpoint of compatibility with various resins, anionic surfactants and nonionic surfactants are preferred, and anionic surfactants are particularly preferred.

Examples of anionic surfactants include sulfonic acid types such as alkyl sulfonates, alkylaryl sulfonates, and ester sulfonates; alkyl phosphates or salts thereof, and polyoxyalkylene alkyl ethers. Phosphoric acid type such as phosphate ester or its salt; sulfate type such as alkyl sulfate ester salt, alkyl ether sulfate ester salt; carboxylate type such as alkyl fatty acid salt, etc. Among these, the sulfonic acid type is preferable from the viewpoint of excellent antistatic properties.

Examples of sulfonic acid-type anionic surfactants include: decyl sulfonate, dodecyl sulfonate, tetradecyl sulfonate, hexadecyl sulfonate, and octadecyl sulfonate. Salts and other alkyl sulfonates; butyl benzene sulfonate, hexyl benzene sulfonate, octyl benzene sulfonate, decyl benzene sulfonate, dodecyl benzene sulfonate, tetradecyl benzene sulfonate Alkyl aryl sulfonates such as cetyl benzene sulfonate, octadecyl benzene sulfonate, dibutyl naphthalene sulfonate, triisopropyl naphthalene sulfonate; dibutyl sulfonate Ester sulfonates such as dioctyl sulfosuccinate salt, dioctyl sulfosuccinate salt, dodecyl sulfoacetate salt, nonylphenoxy polyethylene glycol sulfoacetate salt, etc. Among these, from the viewpoint of excellent antistatic properties, the number of carbon atoms in the alkyl group is 8 or more, preferably 10 to 22, and further preferably 12 to 18. Moreover, as a salt, a metal salt is preferable, an alkali metal salt such as lithium, sodium, and potassium is especially more preferable, and a sodium salt is even more preferable. As a type, from the viewpoint of antistatic properties, alkyl sulfonates are preferred.

Examples of the phosphoric acid-type anionic surfactant include butyl phosphate, butyl phosphate, hexyl phosphate, hexyl phosphate, octyl phosphate, octyl phosphate, decyl phosphate, and decyl phosphate. Salt, lauryl phosphate, lauryl phosphate, myristyl phosphate, myristyl phosphate, cetyl phosphate, cetyl phosphate, stearyl phosphate, stearyl phosphate Phosphate alkyl esters such as base phosphate ester salts or their salts; polyoxyethylene butyl ether phosphate ester, polyoxyethylene butyl ether phosphate ester salt, polyoxyethylene hexyl ether phosphate ester, polyoxyethylene hexyl ether phosphate ester salt, polyoxyethylene hexyl ether phosphate ester salt, Oxyethylene octyl ether phosphate, polyoxyethylene octyl ether phosphate, polyoxyethylene Decyl ether phosphate, polyoxyethylene decyl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene tetradecyl ether phosphate, polyoxyethylene tetradecane Polyoxyethylene cetyl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene stearyl ether phosphate, polyoxyethylene stearyl ether phosphate, Polyoxypropylene octyl ether phosphate, polyoxypropylene octyl ether phosphate, polyoxypropylene decyl ether phosphate, polyoxypropylene decyl ether phosphate, polyoxypropylene lauryl ether phosphate, polyoxypropylene laurel Polyoxyalkylene alkyl ether phosphates such as ether phosphate ester salts or their salts, etc.

Among these, from the viewpoint of performance as a surfactant and antistatic performance, an alkyl phosphate ester salt or a polyoxyalkylene alkyl ether phosphate or a salt thereof is preferred.

Furthermore, regarding the alkyl phosphate ester salt, the carbon number of the alkyl group is 4 or more, preferably 4 to 22, and further preferably 6 to 12. Regarding the polyoxyalkylene alkyl ether phosphate ester or its salt, The number of carbon atoms in the alkyl group is 4 or more, preferably 6 to 22, and further preferably 8 to 18. Furthermore, as the salt, a metal salt or an amine salt is preferred, an alkali metal salt such as lithium, sodium, and potassium, an alkylamine salt, or an alcoholamine salt is particularly preferred, and a sodium salt or a monoethanolamine salt is further preferred.

Examples of the nonionic surfactant include ester type in which polyhydric alcohols such as glycerin or sugar are bonded to fatty acid esters, ether types such as polyoxyethylene alkyl ether or polyoxyethylene alkylphenyl ether, etc. The ester-ether type formed by adding alkylene oxide to fatty acid or polyhydric alcohol fatty acid ester, and the amide type such as fatty acid alkanol amide in which the hydrophobic group and the hydrophilic group are bonded through amide. Among these, when heat resistance is taken into consideration, ester type, ether type, and ester-ether type are preferable, and when antistatic performance is taken into consideration, ether type is preferable.

Examples of ester type or ester-ether type nonionic surfactants include: glycerol mono(di)laurate, glycerol mono(di)stearate, glycerol, glycerol mono(di)oleate, di-oleate, Glyceryl fatty acid esters such as glyceryl mono(di)stearate and triglyceryl mono(di)stearate; polyoxyethylene Glyceryl mono(di)laurate, polyoxyethylene glyceryl mono(di)stearate, polyoxypropylene glyceryl mono(di)laurate, polyoxyethylene glyceryl mono(di)stearate, polyoxybutylene Polyoxyalkylene glycerol fatty acid esters such as glycerol mono(di)laurate and polyoxybutylene glycerol mono(di)stearate; polyoxyethylene mono(di)laurate, polyoxyethylene mono(di)laurate 2) Polyoxyalkylene fatty acid esters such as stearate, polyoxyethylene mono(di)oleate, polyoxypropylene mono(di)laurate, polyoxypropylene mono(di)stearate; Sorbitan fatty acids such as sorbitan mono(di)laurate, sorbitan mono(di)palmitate, sorbitan mono(di)stearate, sorbitan mono(di)oleate, etc. Esters; polyoxyethylene sorbitan monocinnamate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan tristearate, Polyoxyalkylene sorbitol such as ethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxypropylene sorbitan monolaurate, polyoxypropylene sorbitan monostearate, etc. Anhydride fatty acid esters, etc.

Among these, from the viewpoint of compatibility with polyester and antistatic properties, glycerin fatty acid ester, polyoxyalkylene glycerin fatty acid ester, and polyoxyalkylene fatty acid ester are preferred, and more preferred It is a glycerin fatty acid ester or a polyoxyalkyleneglycerol fatty acid ester which is a fatty acid ester having a glycerin skeleton.

Moreover, among these, from the viewpoint of excellent antistatic properties and compatibility, those having the carbon number of the alkyl group are preferably 8 or more, preferably 10 to 22, and further preferably 12 to 18.

Examples of ether-type nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene isodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. , polyoxyethylene octyl lauryl ether, polyoxypropylene lauryl ether, polyoxypropylene cetyl ether, polyoxypropylene stearyl ether, polyoxypropylene oleyl ether, polyoxybutylene lauryl ether, polyoxyethylene Butylene cetyl ether, polyoxybutylene stearyl ether, polyoxybutylene oleyl ether, etc. Oxyalkylene alkyl ether; polyoxyethylene triphenyl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene stilbene phenyl ether and other polyoxyalkylene phenyl ethers.

Among these, from the viewpoint of antistatic properties, polyoxyalkylene alkyl ether is preferred. Furthermore, from the viewpoint of excellent antistatic properties and compatibility, the number of carbon atoms in the alkyl group is 8 or more, preferably 10 to 22, and further preferably 12 to 18.

Examples of cationic surfactants include quaternary ammonium salt types such as alkylammonium salts and alkyl benzylammonium salts; amine salt types such as N-methylbishydroxyethylamine fatty acid ester-hydrochloride; and the like. . Among these, the quaternary ammonium salt type is preferable from the viewpoint of excellent antistatic properties.

Examples of the quaternary ammonium salt type cationic surfactant include: octyltrimethylammonium salt, decyltrimethylammonium salt, lauryltrimethylammonium salt, tetradecyltrimethylammonium salt, Cetyltrimethylammonium salt, stearyltrimethylammonium salt, octyldimethylethylammonium salt, decyldimethylethylammonium salt, lauryldimethylethylammonium salt, ten Tetraalkyldimethylethylammonium salt, cetyltriethylammonium salt, octyltriethylammonium salt, lauryltriethylammonium salt, cetyltriethylammonium salt, Alkylammonium salts such as dialkyldimethylammonium salt; octyldimethylbenzylammonium salt, decyldimethylbenzylammonium salt, lauryldimethylbenzylammonium salt, tetradecyldimethyl Alkyl benzylammonium salts such as cetyl benzyl ammonium salt, cetyl dimethyl benzylammonium salt, stearyl dimethyl benzylammonium salt, tributyl benzylammonium salt, trihexyl benzylammonium salt, etc. wait.

Among these, from the viewpoint of performance as a surfactant and antistatic performance, an alkylammonium salt is preferred.

In addition, the alkyl group has the longest carbon number, which is usually 4 or more, preferably 6 to 22, and further preferably 8 to 18. In addition, examples of counter ions of the ammonium group include: halogen ions, sulfonates, sulfates, phosphates, nitrates, carboxylates and other ions; among these, from the viewpoint of good antistatic properties Specifically, chloride, sulfonate, and sulfate are preferred.

Examples of amphoteric surfactants include betaine type surfactants such as alkyl betaines, amino acid types such as alkyl amino fatty acid salts, and amine oxide types such as alkyl amine oxides. Among these, the betaine type is preferable from the viewpoint of excellent antistatic properties.

Examples of betaine-type zwitterionic surfactants include: octyldimethylaminoacetate betaine, decyldimethylaminoacetate betaine, lauryldimethylaminoacetate betaine, tetradecane Alkyl dimethylaminoacetate betaine, cetyldimethylaminoacetate betaine, stearyldimethylaminoacetate betaine, octylamide propyl betaine, decylamide propyl betaine Alkali, laurylamide propyl betaine, tetradecylamine propyl betaine, cetylamide propyl betaine, stearylamine propyl betaine, etc.

An aspect of the coating layer of the film for DFR base material of the present invention includes an aspect that does not substantially contain inorganic salts. Here, the term "the coating layer does not substantially contain inorganic salts" means that inorganic salts may be included within a range that does not impair the effects of the present invention. For example, inorganic salts may also be inevitably included in water used as a solvent for the coating liquid. situation. In the present invention, the term "substantially no inorganic salt" in the coating layer means that the content of the inorganic salt in the coating layer is preferably 500 ppm by mass or less, more preferably 300 ppm by mass or less, and even more preferably on a mass basis. It is 200 mass ppm or less, more preferably 100 mass ppm or less. The lower limit is not particularly limited, but if the inevitable mixing of inorganic salts is taken into consideration, it is actually 10 mass ppm or more. The content of the inorganic salt in the coating layer can be measured, for example, by elemental analysis, fluorescence X-ray analysis, or the like.

Here, as the inorganic salt, the cross-linking catalyst of the above-mentioned metal salt is not included, and the particle A corresponds to the inorganic salt. Examples include: sodium chloride, sodium bromide, sodium nitrate, potassium chloride, potassium nitrate, strontium chloride, strontium nitrate, cesium chloride, magnesium chloride, magnesium nitrate, calcium chloride, calcium nitrate, ferric chloride (II ), iron(II) bromide, ferric nitrate, potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), cobalt(II) chloride, cobalt(II) bromide, cobalt(II) chloride , cobalt(II) nitrate, cobalt(II) sulfate, nickel(II) chloride, bromide Nickel(II), nickel(II) nitrate, nickel(II) sulfate, sodium palladium(II) chloride, copper(II) chloride, copper(II) bromide, copper(II) nitrate, copper(II) sulfate , silver nitrate, zinc chloride, zinc nitrate, aluminum chloride, aluminum nitrate, indium (III) chloride, indium (III) nitrate, etc.

One aspect of the coating layer of the film for DFR base material of the present invention is an aspect that does not substantially contain a polyether compound. Here, the term "the coating layer does not substantially contain a polyether compound" means that the polyether compound may be included in the range that does not impair the effects of the present invention and is present in the drying process and preparation process when the coating layer is formed from the coating liquid. The situation in which polyether compounds are included in unreacted substances, compounds after reaction, or mixtures thereof that remain unreacted during the membrane process. In this specification, a polyether compound refers to a compound having two or more ether bonds in a linear chain. If the coating layer contains a polyether compound, the coating layer will become soft and damage resistance will be deteriorated.

In the present invention, the term "substantially no polyether compound" in the coating layer means that the content of the polyether compound in the coating layer is preferably 3,000 mass ppm or less, more preferably 1,000 mass ppm or less on a mass basis, and further It is preferably 800 ppm by mass or less, more preferably 500 ppm by mass or less. The lower limit is not particularly limited, but if the inevitable mixing of the polyether compound is taken into consideration, it is 10 ppm by mass or more.

Here, the polyether compound is a compound having two or more ether bonds in a linear chain, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and poly1,4-butylene glycol; 15 -Crown ethers such as crown ether-5, 18-crown ether-6, etc.

Here, the polyether compound does not include the polyol-based antistatic agent, ester-ether type surfactant and ether type surfactant mentioned above.

Particle A

In order to maintain the transparency of the DFR substrate film, while improving the smoothness and further improving the anti- Damage resistance, anti-grinding property and air escape property, the coating layer contains particles A. The particles A are not particularly limited, and previously known particles can be used. Specific examples of the particles A include inorganic particles such as colloidal silica, porous silica, alumina, calcium carbonate, zirconium oxide, and titanium oxide; organic particles such as acrylic resin and styrene resin. Particle A includes particle AS with a particle diameter of 30 to 80 nm and particle AL with a particle diameter of 100 to 400 nm. It may also include particles other than particle AS and particle AL with a particle diameter of less than 1 μm.

In order to maintain the transparency of the coating layer while further improving the smoothness, damage resistance, abrasion resistance and air escape properties, relative to the proportion of the surface of the coating layer when observing the surface of the coating layer The coating layer contains particles AS and particles AL such that the area ratio of particles AS falls within the range of 60 to 99.9%, and the area ratio of particles AL falls within the range of 0.1 to 15%. Here, when the particle B contained in the polyester film is observed when the surface of the coating layer is observed, it is considered that the particle B is not included.

Among the particles A contained in the coating layer, the particles AS, the particles AL, and the other particles AE may be the same type of particles or different types of particles. Particle AS, particle AL and other particles AE may be components constituting each particle size range in one peak in the particle size distribution, or may be components constituting each particle size range in different peaks in the particle size distribution. In addition, the particles AS, the particles AL, and the other particles AE may be the same type of particles as the particle B contained in the polyester film, or they may be different types of particles from the particle B. From the viewpoint of heat resistance when forming the coating layer and availability at low cost, colloidal silica, porous silica, and organic particles are preferred.

Particle AS

The coating is applied in such a manner that the area ratio of the particles AS is within the range of 60 to 99.9% relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed. The cloth layer contains particles, which can maintain the transparency of the coating layer and further improve the smoothness during the dry film resist step, thereby improving damage resistance and grinding resistance. The particle AS preferably has the above-mentioned area ratio within the range of 65 to 99.5%, more preferably within the range of 70 to 99.0%.

Regarding the particle diameters of the particles AS and the particles AL, when the particles AS and the particles AL are powders, the powder can be measured by using a centrifugal sedimentation particle size distribution measuring device (model SA-CP3, manufactured by Shimadzu Corporation). The obtained equivalent spherical distribution was measured. The particle diameters of the particles AS and AL contained in the coating layer can be observed on the surface of the coating layer using, for example, a scanning electron microscope (SEM, manufactured by Japan FEI Co., Ltd., "NovaNanoSEM"). The obtained image data was used to measure the particle size of each particle using image analysis software ("Image-Pro Premier" manufactured by Japan Roper Co., Ltd.). When the particles in the image data are not circular, measure the area of the particle, convert it into a circle with the same area, and then measure the particle diameter.

Particle AL

The particles are contained in the coating layer so that the area ratio of the particles AL is within the range of 0.1 to 15% relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed. , can maintain the transparency of the coating layer and improve air escape during the dry film resist step, thereby further improving smoothness and maintaining anti-grinding properties. The particle AL preferably has the above-mentioned area ratio within the range of 0.2 to 15%, more preferably within the range of 1.0 to 10%.

The coating layer substantially does not contain particles with a particle size exceeding 1 μm. Here, "the coating layer does not substantially contain particles with a particle diameter exceeding 1 μm" specifically refers to the area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed. The total particle size exceeds 1 The area ratio of μm particles does not reach 0.01%. Whether or not particles having a particle size exceeding 1 μm is substantially included can be determined by the same method as Particle AS. If the coating layer contains particles with a particle size exceeding 1 μm, the transparency of the coating layer may be hindered, and since the particle size relative to the film thickness increases, there may be problems due to coating during the coiling and processing steps. The particles will easily fall off when the coating is wiped, which may cause contamination due to peeling off of the coating.

The coating layer may also contain other particles AE having a size other than the particles AS and the particles AL and having a particle diameter of 1 μm or less. Specifically, the other particles AE may be, for example, particles with a particle diameter of 5 nm or more and less than 30 nm, particles with a particle diameter of more than 80 nm and less than 100 nm, or particles with a particle diameter of more than 400 nm and less than 100 nm. Particles in the range of 1000nm. When the coating layer contains particles AE other than particles AS and particles AL, the total area occupied by the particles in the surface of the coating layer when observing the surface of the coating layer can be compared with the other particles AE. The coating layer contains other particles AE so that the area ratio falls within the range of 0.1~25%.

In order to prevent damage and contamination of the DFR substrate film, the average particle diameter of the particles A contained in the coating layer is preferably in the range of 0.5 times to 5 times the film thickness of the coating layer, and more preferably The film thickness of the fabric layer is within the range of 0.7 times to 3.5 times. Furthermore, the range of 1.0 times or more and 3.0 times or less of the film thickness of the coating layer is more preferable. In the coating layer of a polyester film, if the average particle size of the particles relative to the film thickness is large, there is a concern that the particles may easily fall off due to the coating layer being wiped during the winding and processing steps, resulting in the occurrence of Damage or contamination caused by grinding of the coating film. When the average particle diameter of the particles A contained in the coating layer is in the range of 0.5 times to 5 times the film thickness of the coating layer, the transparency and good protection of the DFR base film can be maintained. Damage resistance and grinding resistance, while providing air escape and smoothness.

For example, a polyester film with an average surface roughness (Ra) in the range of 1 to 3 nm When forming a coating layer, in order to provide damage prevention and smoothness while maintaining transparency, it is preferable to use two or more types of particles A with different average particle diameters. When using two or more sizes of particles A with different average particle diameters, it is preferable that the particle size of the particle A with the largest average particle diameter is within the range of 0.5 to 5 times the film thickness of the coating layer. .

The smaller the average particle size of Particle A, the higher the transparency of the polyester film, which can reduce defects in circuits and thus can be applied to circuits requiring finer wires. On the other hand, the average particle size of Particle A is as large as a certain This degree can impart smoothness. The average particle diameter of the particles A satisfies the range of 0.5 to 5 times the film thickness of the coating layer, and is usually 0.001 to 1.0 μm, preferably 0.005 to 0.5 μm, and more preferably 0.01 to 0.1 μm. If the average particle diameter of the particles A is in the range of 0.001 to 1.0 μm, damage and contamination of the DFR substrate film can be prevented and smoothness can be imparted. Regarding the average particle size, when the particle A is a powder, the cumulative equivalent spherical distribution obtained by measuring the powder using a centrifugal sedimentation particle size distribution measuring device (model SA-CP3, manufactured by Shimadzu Corporation) can be The particle diameter (d50) with a volume fraction of 50% is set as the average particle diameter. The average particle diameter of the particles A contained in the coating layer can be observed on the surface of the coating layer using, for example, a scanning electron microscope (SEM, manufactured by Japan FEI Co., Ltd., "NovaNanoSEM"). Image data and use image analysis software ("Image-Pro Premier" manufactured by Japan Ropper Co., Ltd.) to measure the particle size of each particle, randomly select 2000 particles, and calculate the particle size distribution based on the particle size data of the selected particles ( Volume basis), and the particle diameter (d50) with a cumulative volume fraction of 50% is set as the average particle diameter.

As the particles A, two or more types of particles A having different average particle diameters may be used. When two or more types of particles A are used, the average particle diameter of one type of particle A (hereinafter, also referred to as "particle A-1") is usually 0.001~0.06 μm, preferably 0.005~0.06 μm, and more preferably 0.01~ 0.06μm range. Particle A-1 may include particle AS or particle AL. The average particle diameter of the other particle A (hereinafter also referred to as "particle A-2") is usually 0.06~1.0 μm, preferably 0.06~0.5 μm, more preferably 0.06~0.3 μm, and still more preferably 0.06~ 0.1μm range. Particle A-2 may include particle AS or particle AL. Furthermore, by using two or more types of particles A, namely particles A-1 with an average particle diameter in the range of 0.001 to 0.06 μm and particles A-2 with an average particle diameter in the range of 0.06 to 1.0 μm, higher-level results can be achieved simultaneously. Transparency and good smoothness.

The content of particle A in the coating layer is preferably 1 to 10 mass%, more preferably 1 to 8 mass%, further preferably 2 to 7 mass%, and particularly preferably 2 to 5 mass%. If the content of particle A in the coating layer is in the range of 1 to 10% by mass, the transparency of the DFR base film can be maintained while providing damage prevention and better smoothness. The content of particles A in the coating layer can be determined, for example, by using elemental analysis to identify the elements constituting the particles in the coating layer, and then using a transmission electron microscope (TEM: Transmission Electron Microscope) to measure the size and frequency of the particles. Measured by observation. The content of particle A in the coating liquid relative to the non-volatile components in the coating liquid is preferably 1 to 10 mass %, more preferably 1 to 8 mass %, further preferably 2 to 7 mass %, and particularly preferably It is 2~5% by mass.

Release agent

In order to further improve the smoothness of the DFR substrate film, the coating layer preferably contains a release agent. The release agent is preferably at least one release agent selected from the group consisting of compounds having long-chain alkyl groups, waxes, fluorine compounds, and polysiloxane compounds. Among them, the release agent is preferably a compound or wax having a long-chain alkyl group from the viewpoint of excellent stain resistance. Moreover, from the viewpoint of preventing damage, the release agent is preferably wax. These release agents can be used individually or in plural types. Preferably in the coating layer Contains wax.

The content of the release agent in the coating layer is usually 1 to 10 mass%, preferably 2 to 9 mass%, and more preferably 3 to 8 mass%. If the content of the release agent in the coating layer is 1 to 10% by mass, the smoothness of the DFR base film can be further improved. It is estimated that the content of the release agent in the coating layer is approximately equal to the content of the release agent relative to the non-volatile components in the coating liquid. The content of the release agent in the coating liquid used to form the coating layer is usually 1 to 10 mass %, preferably 2 to 9 mass %, and more preferably 3 to 3 mass % relative to the non-volatile components in the coating liquid. 8% by mass.

The wax is at least one selected from the group consisting of natural waxes, synthetic waxes, and waxes formulated with them.

The so-called natural wax refers to plant wax, animal wax, mineral wax, and petroleum wax. Examples of plant-based waxes include candelilla wax, carnauba wax, rice bran wax, wood wax, and jojoba oil. Examples of animal-based waxes include beeswax, lanolin, and spermaceti. Examples of mineral wax include montan wax, ozokerite, and ozokerite. Examples of petroleum waxes include paraffin wax, microcrystalline wax, and paraffin wax.

Examples of synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, acid amides, amines, imines, esters, and ketones. As synthetic hydrocarbons, Fischer-Tropsch wax (also known as Sasol Wax) and polyethylene wax are well-known. In addition, low molecular weight polymers (specifically, polymers with a viscosity number average molecular weight of 500 to 20,000) and less are also included. of polymers. That is, there are polypropylene, ethylene-acrylic acid copolymer, polyethylene glycol, polypropylene glycol, and end-capped or grafted combinations of polyethylene glycol and polypropylene glycol. Examples of modified waxes include montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives. The derivative here refers to a compound obtained by any treatment of purification, oxidation, esterification, saponification, or a combination thereof. Examples of hydrogenated wax include hydrogenated castor oil and hydrogenated castor oil derivatives.

From the viewpoint that smoothness can be imparted effectively in a small amount, polyethylene wax is preferred.

The compound having a long-chain alkyl group refers to a compound having a linear or branched alkyl group having a carbon number of usually 6 or more, preferably 8 or more, and further preferably 12 or more. Examples of the alkyl group include hexyl, octyl, decyl, lauryl, octadecyl, behenyl, and the like. The so-called compounds having alkyl groups include, for example: various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. wait. In consideration of heat resistance and contamination resistance, a polymer compound having a long-chain alkyl group in the side chain is preferred.

The polymer compound having a long-chain alkyl group in the side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group that can react with the reactive group. Examples of the reactive group include a hydroxyl group, an amine group, a carboxyl group, an acid anhydride, and the like.

Examples of compounds having such reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, reactive group-containing polyester resin, reactive group-containing poly(meth)acrylic resin, and the like. Among these, polyvinyl alcohol is preferred in consideration of mold releasability and ease of handling.

Examples of the compound having an alkyl group that can react with the above reactive group include: hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, and stearyl isocyanate. , behenyl isocyanate and other isocyanates containing long-chain alkyl groups; hexyl chloride, octyl chloride, decyl chloride, lauryl chloride, octadecyl chloride, behenyl chloride and other long-chain alkyl chlorides ; Amines containing long-chain alkyl groups, alcohols containing long-chain alkyl groups, etc. Among these, in consideration of mold releasability and ease of handling, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred.

In addition, the polymer compound with a long-chain alkyl group in the side chain can also be produced by a polymer of a long-chain alkyl (meth)acrylate or a combination of a long-chain alkyl (meth)acrylate and other vinyl-containing monomers. Obtained by gathering together. Examples of long-chain (meth)acrylic acid alkyl esters include: (methyl) Hexyl acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, etc.

The so-called polysilicone compounds are compounds with a polysilicone structure in the molecule. Examples include: polysilicone emulsion, acrylic acid-grafted polysiloxane, polysilicone-grafted acrylic acid, amine-modified polysiloxane, and perfluoroalkane modified polysiloxane, alkyl modified polysiloxane, etc. In consideration of heat resistance, it is preferable to contain a hardened polysiloxane resin. As the type of curable polysilicone resin, any curing reaction type such as addition type, condensation type, ultraviolet curing type, electron beam curing type, etc. can be used.

The fluorine compound is a compound containing a fluorine atom. In terms of the coating appearance of in-line coating, organic fluorine compounds can be suitably used. Examples include perfluoroalkyl group-containing compounds, polymers of olefin compounds containing fluorine atoms, and aromatic compounds such as fluorobenzene. Fluorine compounds, etc. From the viewpoint of mold releasability, compounds having a perfluoroalkyl group are preferred. Furthermore, a compound containing a long-chain alkyl compound as described below among the fluorine compounds may also be used.

Examples of the compound having a perfluoroalkyl group include: (meth)acrylic acid perfluoroalkyl ester, (meth)acrylic acid perfluoroalkyl methyl ester, (meth)acrylic acid 2-perfluoroalkylethyl ester, 3-Perfluoroalkylpropyl (meth)acrylate, 3-Perfluoroalkyl-1-methylpropyl (meth)acrylate, 3-Perfluoroalkyl-2-propenyl (meth)acrylate, etc. (Meth)acrylates or their polymers containing perfluoroalkyl groups; perfluoroalkyl methyl vinyl ether, 2-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-Perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenyl vinyl ether and other perfluoroalkyl-containing vinyl ethers or their polymers, etc. In consideration of heat resistance and contamination resistance, polymers are preferred. The polymer may be a single compound or a polymer of multiple compounds. Furthermore, from the viewpoint of mold releasability, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Furthermore, a polymer with a compound having a long-chain alkyl compound as described below may also be used. Furthermore, from the viewpoint of adhesion to the base material, a polymer with vinyl chloride is preferred.

various polymers

In order to improve the appearance of the coating layer and the transparency of the DFR base film, the coating layer may also contain various polymers other than polymers cross-linked by a cross-linking agent.

The content of various polymers other than the polymer cross-linked with the cross-linking agent in the coating layer is usually 10 to 70 mass %, preferably 20 to 65 mass %, more preferably 30 to 60 mass %. If the content of various polymers in the coating layer other than the polymer cross-linked with the cross-linking agent is 10 to 70% by mass, the appearance and transparency of the coating layer of the DFR base film can be further improved. It is estimated that the content of various polymers other than the polymer cross-linked with the cross-linking agent in the coating layer and the various polymers other than the polymer cross-linked with the cross-linking agent relative to the non-volatile components in the coating liquid are estimated. The polymer contents are approximately equal. The content of various polymers other than the polymer obtained by cross-linking the cross-linking agent contained in the coating liquid used to form the coating layer is usually 10 to 70 mass % relative to the non-volatile components in the coating liquid. , preferably 20 to 65 mass%, more preferably 30 to 60 mass%.

Specific examples of various polymers include acrylic resin, polyvinyl alcohol, polyester resin, urethane resin, polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxyl Cellulose, starch, etc. Among these, acrylic resin and polyester resin are preferred from the viewpoint of improving damage prevention performance.

Acrylic resin refers to a polymer including polymerizable monomers containing acrylic and methacrylic monomers. These may be any of homopolymers, copolymers, and copolymers with polymerizable monomers other than acrylic and methacrylic monomers. In addition, copolymers of these polymers and other polymers (such as polyester, polyurethane, etc.) are also included. For example, they are blocked copolymers and graft copolymers. Alternatively, a polymer obtained by polymerizing a polymerizable monomer in a polyester solution or polyester dispersion (optionally a mixture of polymers) is included. Likewise, it also includes A polymer obtained by polymerizing a polymerizable monomer in a polyurethane solution or polyurethane dispersion (optionally a mixture of polymers). Similarly, polymers obtained by polymerizing polymerizable monomers in other polymer solutions or dispersions (polymer mixtures as the case may be) are also included. In addition, in order to further improve the adhesiveness with the base material, a hydroxyl group or an amine group may be included.

The polymerizable monomer is not particularly limited, and representative compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and maleic acid. , various carboxyl-containing monomers of citraconic acid, and their salts; such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Various hydroxyl-containing monomers such as ester, monobutyl hydroxy fumarate, and monobutyl hydroxy itaconate; such as (meth)acrylic acid methyl ester, (meth)ethyl acrylate, (methyl) Various (meth)acrylate esters such as propyl acrylate, (meth)butyl acrylate, and lauryl (meth)acrylate; such as (meth)acrylamide, diacetone acrylamide, and N-hydroxymethylacrylamide Various nitrogen-containing compounds such as amide or (meth)acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; various vinyl esters such as vinyl propionate ; Various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, etc.; Phosphorus-containing vinyl monomers; such as vinyl chloride, vinylidene chloride Various halogenated ethylenes; various conjugated dienes such as butadiene.

The polyester resin includes, for example, the following polycarboxylic acid and polyhydric hydroxyl compound as main structural components. That is, as the polycarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, phthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1 ,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfo-m- Phthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimellitic acid, pyromellitic acid, Trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, trimellitic acid monopotassium salt and their ester-forming derivatives, etc.; as polyvalent hydroxyl compounds, ethylene glycol, 1,2- Propylene glycol, 1,3-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1, 4-Cyclohexane dimethanol, terephthalenedimethanol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene Glycol, poly(tetramethylene oxide) glycol, dimethylol propionate, glycerin, trimethylol propane, sodium dimethylol ethyl sulfonate, potassium dimethylol propionate, etc. It is sufficient to appropriately select one or more types of each of these compounds and synthesize the polyester resin through a polycondensation reaction using a conventional method.

Polyvinyl alcohol refers to a compound having a polyvinyl alcohol moiety, and includes, for example, a denatured compound that is partially acetalized or butyralized with polyvinyl alcohol. Conventionally known polyvinyl alcohol can be used. The degree of polymerization of polyvinyl alcohol is not particularly limited, but is usually 100 or more, preferably in the range of 300 to 40,000. When the degree of polymerization is less than 100, the water resistance of the coating layer may decrease. In addition, the saponification degree of polyvinyl alcohol is not particularly limited. In fact, it is usually 70 mol% or more, preferably in the range of 70 to 99.9 mol%, more preferably 80 to 97 mol%, and particularly preferably 86 to 86 mol%. 95 mol% polyvinyl acetate saponified product.

The so-called urethane resin is a polymer compound having a urethane resin in the molecule. Usually urethane resin is produced by the reaction of polyol and isocyanate. Examples of polyols include polycarbonate polyols, polyester polyols, polyether polyols, polyolefin polyols, and acrylic polyols; these compounds may be used alone or in plural types.

Polyester film for dry film resist substrates

The DFR base material film of the present invention has a coating layer on at least one side of the polyester film, and the DFR The average surface roughness (Ra) of the base film is preferably 1 to 10 nm, more preferably 1 to 8 nm, and still more preferably 1 to 5 nm. By setting the average surface roughness (Ra) of the DFR substrate film in the range of 1 to 10 nm, transparency can be maintained. When the average surface roughness (Ra) exceeds 10nm, the transparency of the DFR base film decreases and ultraviolet exposure becomes insufficient, which may cause circuit defects and lower resolution. On the other hand, when the average surface roughness (Ra) is less than 1 nm, the smoothness becomes poor, so the film surface is prone to damage during precise steps, especially during the film formation step, and the resist coated on the surface Surface damage may have a greater impact in high-resolution dry film resists where the resist thickness is thin. The average surface roughness (Ra) of the DFR substrate film can be measured by the measurement method in the following examples.

The maximum surface height (Rt) of the film for DFR substrate is preferably 10~200nm, more preferably 10~180nm. When the maximum surface height of the DFR substrate film exceeds 200nm, dents will occur in the dry film resist, and the dents may cause circuit defects and lower resolution. By setting the maximum surface height (Rt) within this range, a film with fewer circuit defects and good resolution can be obtained. The maximum surface height (Rt) of the DFR substrate film can be measured by the measurement method in the following examples.

The haze of the film for DFR substrates of the present invention is preferably 1.0% or less, more preferably 0.7% or less. By setting the haze of the film for the DFR base material to 1.0% or less and fully exposing the ultraviolet rays to the high-resolution dry film resist, a dry film resist base material that is less likely to cause circuit defects and lower resolution can be obtained. Use polyester film. The smaller the haze value of the DFR substrate film, the better, usually above 0.1%. The haze of the film for DFR substrates can be measured by the measurement method in the following examples.

The friction coefficient of the film for DFR base material of the present invention is preferably 0.8 or less, more preferably 0.7 or less. By setting the friction coefficient to 0.8 or less, it is possible to obtain a material that is less likely to be damaged during the coiling step. DFR substrate film. Regarding the friction coefficient, by adding particles to the coating layer, smoothness can be imparted while maintaining transparency. The smaller the friction coefficient, the better. The friction coefficient of the DFR base film is usually above 0.1. The friction coefficient can be measured by the measurement method in the following examples.

The air leakage index measured according to JIS P8119 of the DFR substrate film of the present invention is preferably 400,000 seconds or less. The air leakage index of the DFR substrate film is more preferably 350,000 seconds or less, further preferably 300,000 seconds or less, particularly preferably 250,000 seconds or less, most preferably 200,000 seconds or less. If the air leakage index of the film for DFR base material is 400,000 seconds or less, the inhaled gas can easily escape when the film is rolled into a roll, and the films can be brought into close contact with each other and rolled tightly, which can prevent storage and transportation, for example. The deflection in the direction of the winding core can prevent damage caused by deflection, etc. Furthermore, if the air leakage index of the film for DFR base materials is 400,000 seconds or less, a film for DFR base materials that has good winding characteristics and is less prone to surface wrinkles when the film is rolled into a roll can be obtained. The smaller the air leakage index of the film for DFR substrates, the better. If it is too small, the adhesiveness of the rolled film may become too high and the processability may decrease. The air leakage index of the DFR substrate film is usually 8,000 seconds or more, preferably 10,000 seconds or more, and more preferably 30,000 seconds or more.

In this manual, the air leakage index is based on JIS P8119, for example, using a Digi-Bekk smoothness testing machine (DB-2, manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a temperature of 23°C and a relative humidity of 50% RH. For a vacuum container with a pressure of 100 kPa and a volume of 38 mL, measure the time it takes for 1 mL of air to flow through, that is, the time (seconds) until the pressure in the container changes from 50.7 kPa to 48.0 kPa. Multiply the obtained number of seconds by 10 times. Set to air leakage index. The size of the sample for measurement is set to 70mm x 70mm. 20 pieces can be laminated in such a way that the coating layer of one DFR base film sample is overlapped with the polyester film of another DFR base film sample, and allow air to escape. In order to make the film uniform, a hole with a diameter of 5 mm was made in the center of the laminated film and measured.

Furthermore, within the scope that does not detract from the gist of the present invention, the coating layer may optionally contain a defoaming agent, a coating property improver, a tackifier, an organic lubricant, an ultraviolet absorber, an antioxidant, a foaming agent, and a dye. , pigments, etc.

The film for DFR base material of the present invention may also have a coating layer on at least one side of the polyester film, and a functional layer on the other side of the polyester film. The functional layer is not particularly limited, and examples thereof include anti-pollution layers, anti-adhesion layers, and the like.

The film for DFR substrates of the present invention can form circuits with extremely fine lines by simultaneously satisfying transparency, damage resistance, grinding resistance, air escape properties, and smoothness. Therefore, it can be applied to high-definition printed wiring boards. Specifically, it can also be suitably used in circuit boards with a minimum wiring pitch of 80 μm or less. Furthermore, it can also be suitably used in circuit boards with a wiring pitch of 50 μm or less, especially the above-mentioned ones. A circuit board with wiring spacing of 15 μm or less. The lower limit of the narrowest wiring interval is not limited, but is usually 0.1 μm or more. In addition, the same is true when the above "narrowest wiring interval" is changed to "the narrowest wiring (land) width". The film for DFR base materials of the present invention can achieve further remarkable effects on printed wiring boards as described above.

dry film resist

The dry film resist of the present invention has a coating layer on at least one side of the polyester film for a DFR base material of the present invention, and has a photosensitive resin layer on the opposite side to the coating layer side. The dry film resist (hereinafter also referred to as "DFR") can form a photosensitive resin layer by coating a photosensitive resin on one side of the film for DFR base material of the present invention on the side opposite to the coating layer side. The DFR base material of the present invention is laminated with a polyester film under pressure and bonded to the surface of the photosensitive resin layer. Specifically, the photosensitive resin layer can be brought into contact with the side of the two DFR base material polyester films opposite to the coating layer side to be sandwiched between the two DFR base material polyester films, and the two DFR base material polyester films can be sandwiched between the two DFR base material polyester films. A film for DFR substrate is used as a photosensitive resin layer protective film. The DFR of the present invention has a coating layer on at least one side of the DFR base film. The coating layer maintains transparency and improves smoothness, damage prevention and grinding resistance in the dry film resist step. Therefore, it can suppress the particle falling off or the grinding of the coating film caused by the coating layer being wiped during the rolling and processing steps, thereby forming a more refined conductive pattern on the photosensitive resin layer.

Furthermore, the DFR of the present invention may have a photosensitive resin layer on the side of the DFR base film opposite to the coating layer side, and a DFR base film different from that of the present invention may be bonded to the photosensitive resin layer. Examples of films for DFR base materials that are different from the present invention include polyester films for DFR base materials that do not have the coating layer of the present invention, and films for DFR base materials that have a layer different from the coating layer of the present invention. For example, the DFR film for a DFR base material of the present invention may have a photosensitive resin layer on the side opposite to the coating layer side, and the DFR base material film may have a functional layer different from that of the coating layer of the present invention. The polyester film side of the base material or the functional layer side different from the coating layer of the present invention is press-laminated and bonded to the photosensitive resin layer.

As the photosensitive resin, a conventional composition can be used. Usually, as a photosensitive resin used in a dry film resist, a negative photosensitive resin is used, which mainly contains a composition containing a monomer, a polymer, a photopolymerization initiator, etc. having a polymerizable unsaturated group. Photosensitive resin generally has alkali water solubility. In the dry film resist processing step, the exposed part is developed to form a circuit, and the unexposed part is removed by using a developer.

The monomer having a polymerizable unsaturated group is not particularly limited, and examples thereof include monomers having one polymerizable unsaturated group, monomers having two polymerizable unsaturated groups, and monomers having three or more polymerizable unsaturated groups. Unsaturated monomers; these can be used alone or in appropriate combination.

Examples of the monomer having one polymerizable unsaturated group include: (meth)acrylic acid methyl ester, (meth)ethyl acrylate, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid Propyl acid, 2-hydroxypropyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate , 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, 2-(meth)acrylate acrylic acid acetate phosphate, phthalic acid derivatives of hemi(meth)acrylate, N-hydroxymethyl(meth)acrylamide, etc.

Examples of the monomer having two polymerizable unsaturated groups include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. ester, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate Meth)acrylate, ethylene oxide modified bisphenol A type epoxy resin di(meth)acrylate, propylene oxide modified bisphenol A type epoxy resin di(meth)acrylate, ethylene oxide Alkane-propylene oxide modified bisphenol A type epoxy resin di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, propylene glycol diglycidyl di(meth)acrylate, ortho Diglycidyl phthalate di(meth)acrylate, hydroxypivalic acid modified neopentyl glycol di(meth)acrylate, etc. Among these, ethylene oxide-modified bisphenol A-type epoxy resin di(meth)acrylate or ethylene oxide-propylene oxide-modified bisphenol A-type epoxy resin di(meth)acrylate can be particularly preferably used. Meth)acrylate.

Examples of the monomer having three or more polymerizable unsaturated groups include trimethylolpropane tri(meth)acrylate, trimethylolpropane tricarboxy(meth)acrylate, and neopentylerythritol. Tri(meth)acrylate, dineopenterythritol penta(meth)acrylate, tri(meth)acryloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylic acid Ester etc.

In addition to the above, a (meth)acrylic epoxy compound, a (meth)acrylic urethane compound, a polymerizable compound containing a phosphorus element, etc. can also be used.

As the monomer having a polymerizable unsaturated group, one having two polymerizable unsaturated groups and a weight average molecular weight of 1,500 or less, preferably 300 to 1,200 is preferred. Among them, ethylene oxide modified bis(ethylene oxide) is particularly suitable. Phenol A type epoxy resin di(meth)acrylate, ethylene oxide-propylene oxide modified bisphenol A type epoxy resin di(meth)acrylate. If the weight average molecular weight exceeds 1,500, the distance between crosslinks may become long and sufficient hardening may not be achieved, resulting in a decrease in resolution and thin wire adhesion.

The polymer contained in the photosensitive resin composition is not particularly limited, and examples thereof include polymers containing acrylic or methacrylic polymerizable monomers. It may be a homopolymer, a copolymer, or a copolymer with a polymerizable monomer other than an acrylic or methacrylic monomer. Examples of polymerizable monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, or anhydrides or half-esters thereof; (methane Methyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylate (meth)acrylates such as glycidyl acrylate; acrylamide, methacrylic acid amide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, alkylvinyl Ether etc.

The weight average molecular weight of the above-mentioned polymer is preferably in the range of 5,000 to 250,000, more preferably in the range of 10,000 to 200,000. If the weight average molecular weight is less than 5,000, the resin may become too soft and may bleed out when the photoresist film is processed into a roll form. If the weight average molecular weight exceeds 250,000, the resolution may decrease.

The glass transition temperature (Tg) of the above-mentioned polymer is preferably in the range of 30 to 150°C. If the glass transition temperature is less than 30°C, the resin may become too soft and the resin may bleed out when processed into a roll form as a photoresist film. If it exceeds 150°C, it may not be used as a photoresist film. The ability to follow irregularities on the substrate surface may be reduced.

、2-甲基9-氧硫

、2,4-二乙基9-氧硫

等9-氧硫

衍生物；二氯苯乙酮、2,2-二乙氧基苯乙酮、2,2-二氯-4-苯氧基苯乙酮等苯乙酮衍生物；乙醛酸苯酯、α-羥基異丁基苯酮、二苯并環庚酮、1-(4-異丙基苯基)-2-羥基-2-甲基-1-丙酮、2-甲基-[4-(甲硫基)苯基]-2-嗎啉基-1-丙酮等丙酮衍生物；三溴苯基碸、三溴甲基苯基碸等碸衍生物；2,4,6-[三(三氯甲基)]-1,3,5-三

、2,4-[雙(三氯甲基)]-6-(4'-甲氧基苯基)-1,3,5-三

、2,4-[雙(三氯甲基)]-6-(4'-甲氧基萘基)-1,3,5-三

、2,4-[雙(三氯甲基)]-6-(向日葵基)-1,3,5-三

、2,4-[雙(三氯甲基)]-6-(4'-甲氧基苯乙烯基)-1,3,5-三

等三

衍生物；吖啶及9-苯基吖啶等吖啶衍生物；2,2'-雙(鄰氯苯基)-4,5,4',5'-四苯基-1,2'-聯咪唑、2,2'-雙(鄰氯苯基)-4,5,4',5'-四苯基-1,1'-聯咪唑、2,2'-雙(鄰氟苯基)-4,5,4',5'-四苯基-1,1'-聯咪唑、2,2'-雙(鄰甲氧基苯基)-4,5,4',5'-四苯基-1,1'-聯咪唑、2,2'-雙(對甲氧基苯基)-4,5,4',5'-四苯基-1,1'-聯咪唑、2,4,2',4'-雙[雙(對甲氧基苯基)]-5,5'-二苯基-1,1'-聯咪唑、2,2'-雙(2,4-二 甲氧基苯基)-4,5,4',5'-二苯基-1,1'-聯咪唑、2,2'-雙(對甲硫基苯基)-4,5,4',5'-二苯基-1,1'-聯咪唑、雙(2,4,5-三苯基)-1,1'-聯咪唑等或日本專利特公昭45-37377號公報所揭示之於1,2'-、1,4'-、2,4'-共價鍵結之互變異構物等六芳基聯咪唑衍生物等；又，此外可列舉：苯甲醯苯甲酸、苯甲醯苯甲酸甲酯、苯偶醯二苯基二硫醚、苯偶醯二甲基縮酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉丙烷-1-酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、1-羥基-環己基-苯基-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦等。該等可單獨使用或將2種以上併用。該等之中，較佳為2,2-二甲氧基-1,2-二苯乙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1。 As the photopolymerization initiator contained in the photosensitive resin composition, a conventionally known one is used. Examples include: benzophenone, P,P'-bis(dimethylamino)benzophenone, P,P'-bis(diethylamino)benzophenone, P,P'- Benzophenone derivatives such as bis(dibutylamino)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isophenone Benzoin derivatives such as propyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzoin isobutyl ether, etc.; quinone derivatives such as anthraquinone and naphthoquinone; 2-chloro-9-oxosulfide

, 2-Methyl 9-oxosulfide

, 2,4-diethyl 9-oxosulfide

Etc. 9-oxysulfur

Derivatives; dichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dichloro-4-phenoxyacetophenone and other acetophenone derivatives; phenyl glyoxylate, α -Hydroxyisobutylphenone, dibenzocycloheptanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methyl Thio)phenyl]-2-morpholinyl-1-propanone and other acetone derivatives; tribromophenyl terine, tribromomethylphenyl terine and other terine derivatives; 2,4,6-[tris(trichloro Methyl]-1,3,5-tri

,2,4-[Bis(trichloromethyl)]-6-(4'-methoxyphenyl)-1,3,5-tri

, 2,4-[bis(trichloromethyl)]-6-(4'-methoxynaphthyl)-1,3,5-tri

, 2,4-[bis(trichloromethyl)]-6-(sunfloweryl)-1,3,5-tri

, 2,4-[Bis(trichloromethyl)]-6-(4'-methoxystyryl)-1,3,5-tri

Wait three

Derivatives; acridine derivatives such as acridine and 9-phenylacridine; 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'- Biimidazole, 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis(o-fluorophenyl) -4,5,4',5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis(o-methoxyphenyl)-4,5,4',5'-tetraphenyl 1,1'-biimidazole, 2,2'-bis(p-methoxyphenyl)-4,5,4',5'-tetraphenyl-1,1'-biimidazole, 2,4 ,2',4'-bis[bis(p-methoxyphenyl)]-5,5'-diphenyl-1,1'-biimidazole, 2,2'-bis(2,4-dimethyl Oxyphenyl)-4,5,4',5'-diphenyl-1,1'-biimidazole, 2,2'-bis(p-methylthiophenyl)-4,5,4', 5'-diphenyl-1,1'-biimidazole, bis(2,4,5-triphenyl)-1,1'-biimidazole, etc. or those disclosed in Japanese Patent Publication No. Sho 45-37377 1,2'-, 1,4'-, 2,4'- covalently bonded tautomers and other hexaarylbiimidazole derivatives; and, in addition, benzoyl benzoic acid, benzyl Methyl benzoate, benzyl diphenyl disulfide, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-benzene Propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-benzyl-2-di Methylamino-1-(4-morpholinylphenyl)-butanone-1, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6- Dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(eta5-2, 4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, etc. These can be used individually or in combination of 2 or more types. Among these, 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholine phenyl)-butanone-1.

In addition, the photosensitive resin composition may be added with amine-based resins such as melamine or thermal cross-linking agents such as isocyanate compounds, crystal violet, malachite green, malachite green lake, brilliant green, patent blue, methyl violet, Victoria blue, rose aniline, Colored dyes such as fuchsin and ethylene violet, adhesion imparting agents, plasticizers, antioxidants, thermal polymerization inhibitors, solvents, surface tension modifying materials, stabilizers, chain transfer agents, defoaming agents, flame retardants, etc. Additives.

When a photosensitive resin composition is provided on a base film to form a photosensitive resin layer, an organic solvent may be mixed with the photosensitive resin composition to a specific concentration and used. Examples of the organic solvent include acetone, methyl ethyl ketone, methanol, ethanol, isopropyl alcohol, toluene, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, and the like. These may be used individually or in combination of 2 or more types. Utilize roller The coating liquid containing the mixture of the photosensitive resin composition is evenly coated on one side of the carrier film by a method such as a formula coating method or a rod coating method, and the temperature is usually 50 to 130°C or as the temperature increases. It is dried in an oven to form a photosensitive resin layer, and is rolled into a roll to produce a photosensitive resin laminate (dry film resist).

[Example]

Hereinafter, the present invention will be further described in detail using examples. However, the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. In addition, the measurement method and evaluation method used in the present invention are as follows.

(1) Determination method of ultimate viscosity of polyester

Accurately weigh 1g of polyester with a precision scale after removing other polymer components and pigments that are not compatible with polyester, add 100ml of a mixed solvent of phenol/tetrachloroethane = 50/50 (weight ratio) to dissolve it, and Measurement was performed at 30°C.

(2)Measurement method of particle size and average particle size (d50)

The equivalent spherical distribution of particle A or particle B containing powder was measured using a centrifugal sedimentation particle size distribution analyzer (SA-CP3 model) manufactured by Shimadzu Corporation, and the cumulative volume fraction of each particle size range was calculated. In addition, the particle diameter at which the cumulative volume fraction in the equivalent spherical distribution measured for each particle is 50% is defined as the average particle diameter d50.

(3)Measurement method of average surface roughness (Ra)

The surface roughness measuring machine (SE-3500) manufactured by Kosaka Laboratory Co., Ltd. was used and the surface roughness was determined as follows. That is, the cross-sectional curve of the coating layer surface of the sample film for DFR substrate film When a portion of the reference length L (2.5mm) is cut out along the direction of its average line, the average line of the cut-out portion is taken as the x-axis, the direction of the vertical magnification is taken as the y-axis, and expressed as a roughness curve y=f(x) , the value given by the following formula (1) is expressed in [nm]. Regarding the arithmetic mean roughness, 10 roughness curves were obtained from the surface of the sample film, and expressed as the average of the arithmetic mean roughness of the intercepted portions calculated based on these roughness curves. Furthermore, the tip radius of the stylus is set to 2 μm, the load is set to 30 mg, and the critical value is set to 0.08 mm.

Ra=(1/L)ʃL0｜f(x)｜dx (1)

(4)Measurement method of maximum surface height (Rt)

When measuring the average surface roughness (Ra) of the sample film for DFR substrate film, the intercepted part of the cross-sectional curve is sandwiched between two straight lines parallel to the average line, and the longitudinal magnification of the cross-sectional curve is The distance between the two straight lines is measured in the direction, and the value expressed in micron (μm) units is taken as the maximum surface height (Rt) of the intercepted portion. The maximum surface height is calculated from 10 profile curves on the surface of the sample film, and is expressed by the average value of the maximum surface height of the intercepted portions calculated based on these profile curves.

(5)Measurement method of film thickness of coating layer

The surface of the coating layer of the sample film of the DFR substrate film was dyed with RuO ₄ and embedded in epoxy resin. Thereafter, the sections prepared by the ultrathin sectioning method were stained with RuO ₄ , and a Transmission Electron Microscope (TEM) manufactured by Hitachi High-Technology Co., Ltd. (H-7650, accelerating voltage 100 kV) was used. Measure the cross-section of the coating layer.

(6) Evaluation method of appearance of coating layer

The surface of the coating layer of the sample film for DFR substrate film was irradiated with an LED lamp (GF-006) manufactured by GENTOS Co., Ltd. and visually observed. The case where uneven coating did not occur was regarded as A, and the case where uneven coating did not occur was regarded as A. The case where uneven coating occurs is designated as B, the case where there is slight uneven coating is designated as C, and the case where uneven coating occurs on the entire surface is designated as D.

(7) Evaluation method for shrinkage of coating layer

The surface of the coating layer of the sample film of the DFR base material film was irradiated with an LED lamp (GF-006) manufactured by GENTOS Co., Ltd. and visually observed to confirm whether there were any uncoated parts of the coating layer on the surface of the sample film. Let the uncoated part of the coating layer, that is, no shrinkage, be designated as A. The case where there is slight shrinkage is designated as B. The case where there is slight shrinkage is designated as C. The case where the entire surface shrinks is designated as D. .

(8)Measurement method of film haze

For the sample film of the DFR substrate film, the film haze was measured using a haze meter (HM-150) manufactured by Murakami Color Technology Research Institute Co., Ltd. in accordance with JIS-K7136.

(9)Measurement method of dynamic friction coefficient

Using the coating layer as the upper surface, attach the sample film of the DFR base film to a smooth glass plate with a width of 10mm and a length of 100mm, and cut another sample film of 18mm in width and 120mm in length for coating. The cloth layers are laminated on the coating layer in such a manner that they are connected to each other. Then, a metal needle with a diameter of 8mm is placed on another sample film, and the metal needle is slid along the length direction of the glass plate with a load of 30g and 40mm/min to measure the friction force. The friction coefficient when sliding at 10mm is set to dynamic friction coefficient.

(10) Evaluation method of damage resistance

Use the friction testing machine manufactured by Taiping R&D Co., Ltd. to rub the surface of the coating layer of the test film for DFR base material back and forth 5 times, and irradiate the rubbed area with the LED lamp: GF-006 manufactured by GENTOS Co., Ltd. Make visual observations. The case where there is no damage to the coating layer is designated as A, the case where there is damage but the damaged area is less than 20% of the total area of the test film is designated as B, the case where it exceeds 20% and is less than 50% The situation where it exceeds 50% is set as C, and the situation where it exceeds 50% is set as D.

(11)Measurement method of air leakage index

The Digi-Bekk smoothness testing machine: DB-2 manufactured by Toyo Seiki Co., Ltd. was used to measure according to JIS P8119 in an environment with a temperature of 23°C and a humidity of 50% RH. The pressure of the pressurizing device is 100kPa, and the vacuum container uses a container with a volume of 38ml. Measure the time for 1mL of air to flow through, that is, the time (seconds) until the pressure in the container changes from 50.7kPa to 48.0kPa, and divide the obtained seconds into 10 times is set as the air leakage index. The sample size of the test film for DFR base material film was set to 70 mm square. 20 pieces were laminated in such a way that the front and back sides of the test film (the coating layer side and the polyester film side) were overlapped, and the air was allowed to escape. A hole with a diameter of 5 mm was opened in the center of the film laminated in a uniform manner for measurement. The larger the value of the air leakage index, the longer it takes for air to seep out from the gap between the membranes, indicating that the membranes are more closely connected to each other.

(12) Evaluation method of surface wrinkles

Roll the sample film of the DFR substrate film into a 500m roll, and store it at a temperature of 23°C and a humidity of Leave it in an environment of 50%RH for 16 hours. After 16 hours passed, the surface layer of the film rolled into a roll was observed. The case where no wrinkles are produced on the surface layer is defined as A, and the width of the wrinkles produced on the surface layer in the roll core direction (hereinafter, the width of the wrinkles in the roll core direction is referred to as the "horizontal width") is 1 cm or less. Set it as B, set it as C if the width exceeds 1cm and 5cm or less, and set it as D if the width exceeds 5cm.

(13)Evaluation method of surface resistance value

Using a high resistance tester: UX MCP-HT800 manufactured by Mitsubishi Chemical ANALYTECH Co., Ltd., the sample of the DFR substrate film was humidified for 30 minutes in a measurement environment of 23°C and 50% RH, and then the surface of the coating layer was measured. The surface resistance value.

(14) Area ratio of the coating layer surface of particle AS and particle AL

The particle diameters of particles AS and particles AL are determined by observing the surface of the coating layer using a scanning electron microscope (manufactured by Japan FEI Co., Ltd., "NovaNanoSEM") at 50,000 times or 100,000 times. The choice can be made based on the obtained image. The 2000 particles identified by the image data were used to measure the particle size of each particle using image analysis software ("Image-Pro Premier" manufactured by Japan Ropper Co., Ltd.). The areas of all measured particles were totaled, and the areas of particles AS having a particle diameter of 30 to 80 nm were totaled, and the area ratio of particles AS to 100% of the total area of all measured particles was calculated. Furthermore, the image data is analyzed, the areas of particles AL having a particle size of 100 to 400 nm among the measured particles are totaled, and the area ratio of particles AL to 100% of the total area of all measured particles is calculated.

The polyester used in Examples and Comparative Examples was prepared as follows.

<Polyester(A)>

Polyester (A) with an ultimate viscosity of 0.65 dl/g was obtained by using terephthalic acid as a dicarboxylic acid component and ethylene glycol as a polyol component and using a conventional melt polymerization method.

<Polyester(B)>

Used in the production method of polyester (A), except that 1.5 parts by weight of alumina particles with an average particle diameter of 0.05 μm as particle B are added before melt polymerization, the polyester is obtained by the same method as the production method of polyester (A). Esters (B).

<Polyester(C)>

The method used in the production method of polyester (A) is the same as the production method of polyester (A), except that 0.5 parts by weight of cross-linked styrene resin particles with an average particle diameter of 0.35 μm as particle B are added before melt polymerization. Obtained polyester (C).

<Polyester(D)>

Used in the production method of polyester (A), it is obtained by the same method as the production method of polyester (A), except that 0.2 parts by weight of silica particles with an average particle diameter of 2.0 μm as particle B are added before melt polymerization. Polyester(D).

The compounds contained in the coating liquid for forming the coating layer are as follows.

Cross-linking agent

‧Melamine compound (I): hexamethoxyhydroxymethylmelamine.

Release agent

‧Polyethylene wax (II): The wax emulsion obtained in the following manner: Add oxidized polyethylene with a melting point of 105°C, an acid value of 16mgKOH/g, a density of 0.93g/mL, and an average molecular weight of 5000 into an emulsification equipment with an internal capacity of 1.5L equipped with a mixer, a thermometer, and a temperature controller. 300g of wax, 650g of ion exchange water, 50g of decaglycerol monooleate surfactant, and 10g of 48% potassium hydroxide aqueous solution were replaced with nitrogen and sealed. Stirred at high speed for 1 hour at 150°C and then cooled to 130°C. The homogenizer is passed through at 400 air pressure and cooled to 40°C.

Particle A

‧Silica particles (IIIA): colloidal silica (particle A-1) with an average particle size of 0.02μm.

Measured using a particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., "ELSZ-2000ZS") in the state of a dispersion of silica particles (solid content concentration: 10% by mass) using water as a solvent The calculated particle size indicates that the volume fraction of particles with a particle size less than 30 nm is 77.3%, and the volume fraction of particles AS with a particle size of 30 to 80 nm is 22.0%. Furthermore, the particle size distribution of the silica particles measured in the state of the dispersion liquid and the area ratio of the silica particles relative to the total area of the particles on the surface of the coating layer when the surface of the coating layer is observed are due to The measurement methods are different and therefore inconsistent.

‧Silica particles (IIIB): colloidal silica (particle A-1) with an average particle size of 0.045 μm.

Measured using a particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., "ELSZ-2000ZS") in a dispersion of silica particles (solid content concentration: 10% by mass) using water as a solvent. The calculated volume fraction of particles AS with a particle size of 30 to 80 nm is 92.4%, and the volume fraction of particles AL with a particle size of 100 to 400 nm is 1.4%.

‧Silica particles (IIIC): colloidal silica (particles A-2) with an average particle size of 0.07μm.

Measured using a particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., "ELSZ-2000ZS") in a dispersion of silica particles (solid content concentration: 10% by mass) using water as a solvent. The calculated volume fraction of particles AS with a particle size of 30 to 80 nm is 65.8%, and the volume fraction of particles AL with a particle size of 100 to 400 nm is 16.5%.

‧Silica particles (IIID): colloidal silica (particles A-2) with an average particle size of 0.14μm.

Measured using a particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., "ELSZ-2000ZS") in a dispersion of silica particles (solid content concentration: 10% by mass) using water as a solvent. The volume fraction of particles AL with a particle size of 100~400 nm is 100%.

‧Silica particles (IIIE): colloidal silica (particles A-2) with an average particle size of 0.45μm.

Measured using a particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., "ELSZ-2000ZS") in a dispersion of silica particles (solid content concentration: 10% by mass) using water as a solvent. The volume fraction of particles with a calculated particle diameter of more than 400 nm and less than 1000 nm is 100%.

various polymers

‧Acrylic resin (IVA): Acrylic resin copolymerized with n-butyl acrylate/n-butyl methacrylate/ethyl acrylate/ethyl methacrylate = 20/26/40/14 (mol%).

‧Polyester resin (IVB): With (acid component) terephthalic acid/isophthalic acid/sodium 5-sulfoisophthalate/(diol component) ethylene glycol/1,4-butanediol/diethylene glycol=56/40/ Aqueous polyester resin dispersion formed by copolymerization of 4/70/20/10 (mol%).

Cross-linking catalyst

‧Melamine cross-linking catalyst (V): 2-amino-2-methyl hydrochloride.

antistatic agent

‧Antistatic agent (VI): a polymer with a number average molecular weight of 50,000 of tertiary amine groups that contains the structural unit of the following formula and the counterion is methanesulfonate ion.

surfactant

‧Surfactant (VIIA): polyoxyethylene lauryl ether.

‧Surface active agent (VIIB): sodium lauryl sulfonate.

‧Surfactant (VIIC): glyceryl ether.

Inorganic salt

‧Sodium chloride (VIII): Special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.

polyether compounds

‧Polyether compound (IX): 15-crown ether-5 crown ether.

Example 1:

Mix polyester (A), (B), and (C) at mass ratios of 75%, 20%, and 5% respectively. The resulting mixed raw materials are used as the raw materials for the outermost layer (surface layer). Polyester (A) As the raw material for the middle layer, it is supplied to two extruders respectively. After being melted at 285°C, it is co-extruded into two types of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge amount). The film was transferred to a cooling roller set at 35°C for cooling and solidification to obtain an unstretched sheet. Then, using the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 5 shown in Table 1 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 4 nm. The maximum surface height (Rt) of the surface is 100 nm. The characteristics of this film are shown in Table 2 below. As shown in Table 2, the film haze and dynamic friction coefficient of the DFR substrate film of Example 1 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface resistance, The air leakage index is also good.

Examples 2 and 3:

Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 1 to obtain a film for a DFR base material. As shown in Table 2, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 2 and 3 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface Resistance and air leakage index are also good.

Example 4:

Mix polyester (A) and (B) at a mass ratio of 80% and 20% respectively. The resulting mixed raw material is used as the raw material for the outermost layer (surface layer), and polyester (A) is used as the raw material for the middle layer. Supplied to two extruders, each is melted at 285°C, and then co-extruded to a temperature of 40°C in the form of two layers of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge volume). Cooling and solidification are performed on a cooling roll to obtain an unstretched sheet. Then, using the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 5 shown in Table 1 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 2 nm. The maximum surface height (Rt) of the surface is 70 nm. The characteristics of this film are shown in Table 3 below. As shown in Table 3, the film haze and dynamic friction coefficient of the DFR substrate film of Example 4 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface resistance, The air leakage index is also good.

Embodiments 5~8:

Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 4 to obtain a film for a DFR base material. As shown in Table 3, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 5 to 8 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

Comparative example 1:

Except that the coating layer was not provided, the film was produced in the same manner as in Example 1 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 2, it was a film with poor dynamic friction coefficient or damage resistance.

Comparative examples 2~4:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 1 to obtain a film. The obtained films were evaluated, and the results are shown in Table 2. Since the coating liquids 17 and 18 did not contain a cross-linking agent, the films of Comparative Examples 2 and 3 had good coating appearance. It is a layer of film with poor damage resistance. In addition, in the film of Comparative Example 4, the antistatic agent contained in the coating liquid 19 was more than 45 mass %, which was 64 mass %, so the surface resistance value was less than 1×10 ¹⁰ Ω, and bleeding occurred and the coating was The appearance and film haze are poor. Since the coating liquid 19 does not contain a cross-linking agent, it is a film with poor damage resistance.

Comparative example 5:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 1 to obtain a film. The obtained film was evaluated, and the results are shown in Table 2. Although the coating liquid 23 contains a cross-linking agent, it contains particles with a particle diameter exceeding 1 μm, so grinding may occur. Since the particles The area ratio of AL exceeds 15%, so the damage resistance is poor.

Comparative examples 6~8:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 1 to obtain a film. The obtained films were evaluated, and the results are shown in Table 2. Although the films of Comparative Examples 6 and 8 contained a cross-linking agent in the coating liquids 4 and 16, the area ratio of the particles AL was 0%, so they were not coated. A film with poor appearance and damage resistance. Although the coating liquid 6 of the film of Comparative Example 7 contains a cross-linking agent, the area of particles AS is 0.3% and the area of particles AL is 98.3%, so it is a film with poor coating appearance and damage resistance.

Comparative example 9:

Except that the coating layer was not provided, the film was produced in the same manner as in Example 4 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 3, it was a film with poor dynamic friction coefficient and damage resistance, and thus had surface wrinkles with a large horizontal width.

Comparative Examples 10~11:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 4 to obtain a film. The obtained film was evaluated, and the results are shown in Table 3. The coating liquids 17 and 18 did not contain a cross-linking agent, so although the coating appearance was good, even if it was a film with a coating layer, Damage resistance is also poor.

Comparative example 12:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 4 to obtain a film. The obtained film was evaluated, and the results are shown in Table 3. Although the coating liquid 22 contains a cross-linking agent, the coating liquid 22 contains a cross-linking agent. The area ratio of sub-AL exceeds 15%, so the damage resistance is also poor.

Comparative examples 13~18:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 4 to obtain a film. The obtained films were evaluated, and the results are shown in Table 3. Although the coating liquids 1 to 4 of the film systems of Comparative Examples 13 to 17 contained a cross-linking agent, since the area ratio of the particles AL was 0%, it also produced Films with large surface wrinkles or films with poor coating appearance and damage resistance. Although the coating liquid 6 of Comparative Example 18 contains a cross-linking agent, the coating appearance and damage resistance are poor because the area of particles AS is 0.3% and the area of particles AL is 98.3%.

Example 31:

Mix polyester (A), (B), and (C) at mass ratios of 75%, 20%, and 5% respectively. The resulting mixed raw materials are used as the raw materials for the outermost layer (surface layer). Polyester (A) As the raw material for the middle layer, it is supplied to two extruders respectively. After being melted at 285°C, it is co-extruded into two types of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge amount). Exit to the cooling roller set at 35℃ and enter It is cooled and solidified to obtain an unstretched sheet. Then, using the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 38 shown in Table 4 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 4 nm. The maximum surface height (Rt) of the surface is 170 nm. The characteristics of this film are shown in Table 5 below. As shown in Table 5, the DFR substrate film of Example 31 did not have uneven coating layer or shrinkage of the coating liquid on the entire surface. The film haze and dynamic friction coefficient were low, and the transparency of the coating layer was maintained. , and has good smoothness, coating appearance, damage resistance, surface resistance, and air leakage index.

Examples 32 and 33:

Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 31 to obtain a film for a DFR base material. As shown in Table 5, in the DFR substrate films of Examples 32 and 33, there was no uneven coating layer or shrinkage of the coating liquid on the entire surface. The film haze and dynamic friction coefficient were low, and the coating layer was maintained. It has good transparency and smoothness, as well as good coating appearance, damage resistance, surface resistance, and air leakage index.

Example 34:

Mix polyester (A) and (B) at a mass ratio of 80% and 20% respectively. The resulting mixed raw material is used as the raw material for the outermost layer (surface layer), and polyester (A) is used as the raw material for the middle layer. Supplied to two extruders, each is melted at 285°C, and then co-extruded to a temperature of 40°C in the form of two layers of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge volume). Cooling and solidification on cooling roller to obtain an unstretched sheet. Then, using the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 40 shown in Table 4 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR substrate film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm, and the average surface roughness (Ra) of the coating layer surface is 2 nm. The maximum surface height (Rt) of the cloth layer surface is 40nm for DFR substrate film. The characteristics of this film are shown in Table 6 below. As shown in Table 6, the DFR substrate film of Example 34 did not have uneven coating layer or shrinkage of the coating liquid on the entire surface. The film haze and dynamic friction coefficient were low, and the transparency of the coating layer was maintained. , and has good smoothness, coating appearance, damage resistance, surface resistance, and air leakage index.

Examples 35 and 36:

Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 34 to obtain a film for a DFR base material. As shown in Table 6, in the DFR substrate films of Examples 35 and 36, there was no uneven coating layer or shrinkage of the coating liquid on the entire surface. The film haze and dynamic friction coefficient were low, and the coating layer was maintained. It has good transparency and smoothness, as well as good coating appearance, damage resistance, surface resistance, and air leakage index.

Comparative example 31:

Except that the coating layer was not provided, the film was produced in the same manner as in Example 31 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 5, it was a film with poor dynamic friction coefficient and damage resistance.

Comparative Examples 32 and 33:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 31 to obtain a film. The obtained film was evaluated, and the results are shown in Table 5. Since the coating liquid 44 of the film of Comparative Example 32 does not contain a cross-linking agent and various polymers, even if it does not contain a surfactant, it is not There will be uneven coating layer and shrinkage of the coating liquid. However, since the coating liquid 44 does not contain a cross-linking agent, it is a film with poor damage resistance. Furthermore, as shown in Table 5, the film of Comparative Example 33 contains a cross-linking agent and various polymers. Although unevenness in the coating layer does not occur, since the coating liquid 45 does not contain a surfactant, unevenness appears on the entire surface. Shrinkage of coating fluid.

Comparative example 34:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 31 to obtain a film. The obtained film was evaluated, and the results are shown in Table 5. The coating liquid 49 contains a surfactant, but contains particles with a particle diameter exceeding 1 μm, so grinding may occur. Since the particles The area ratio of AL exceeds 15%, so the damage resistance is poor.

Comparative examples 35~37:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 31 to obtain a film. The obtained film was evaluated, and the results are shown in Table 5. Although the coating liquid 36 or 43 of the film system of Comparative Example 35 or 37 contained a surfactant, the area ratio of the particles AL was 0%, so there was a problem. The unevenness of the coating layer results in a film with poor protection against damage. Although the coating liquid 39 of the film system of Comparative Example 36 contains crosslinking Joint agent, but since the area of particles AS is 0.3% and the area of particles AL is 98.3%, the coating appearance and damage resistance are also poor.

Comparative example 38:

Except that the coating layer was not provided, the film was produced in the same manner as in Example 34 to obtain a film. The obtained film was evaluated, and as a result, since it did not have a coating layer, as shown in Table 6, it was a film with poor dynamic friction coefficient and damage resistance, resulting in surface wrinkles with a large horizontal width.

Comparative Examples 39 and 40:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 34 to obtain a film. The obtained film was evaluated, and the results are shown in Table 6. The film of Comparative Example 39 did not contain a cross-linking agent and various polymers in the coating liquid 44, so even when it did not contain a surfactant, it was not There will be uneven coating layer and shrinkage of the coating liquid. However, since the coating liquid 44 does not contain a cross-linking agent, it is a film with poor damage resistance. In addition, as shown in Table 6, the film of Comparative Example 40 contains a cross-linking agent and various polymers in the coating liquid 45. Although unevenness of the coating layer does not occur, the coating liquid 45 does not contain surfactants. , so the coating liquid shrinks on the entire surface.

Comparative example 41:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 34 to obtain a film. The obtained film was evaluated, and the results are shown in Table 6. Although the coating liquid 48 contained a surfactant and a cross-linking agent, the area ratio of the particles AL exceeded 15%, so the damage prevention property was poor. Also worse.

Comparative examples 42~48:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 34 to obtain a film. The obtained films were evaluated, and the results are shown in Table 6. Although the coating liquids 31 to 35 of the film systems of Comparative Examples 42 to 47 contained surfactants, the area ratio of the particles AL was 0%, so the smoothness was poor. It is also poorer and produces a film with larger horizontal width of the surface wrinkles. Although the coating liquid 39 of the film system of Comparative Example 48 contains a surfactant and a cross-linking agent, the area of the particles AS is 0.3% and the area of the particles AL is 98.3%, so the coating layer is uneven and damaged. Poor membrane.

Example 61:

Mix polyester (A), (B), and (C) at mass ratios of 75%, 20%, and 5% respectively. The resulting mixed raw materials are used as the raw materials for the outermost layer (surface layer). Polyester (A) As the raw material for the middle layer, it is supplied to two extruders respectively. After being melted at 285°C, it is co-extruded into two types of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge amount). The film was transferred to a cooling roller set at 35°C for cooling and solidification to obtain an unstretched sheet. Then, using the roller peripheral speed difference, the film temperature is 85°C in the longitudinal direction. After extending upward 3.2 times, apply the prepared coating liquid 65 shown in Table 7 below on one side of the longitudinally stretched film, introduce it into the tenter, extend it 4.0 times in the transverse direction at 95°C, and heat it at 230°C. After heat treatment, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 4 nm. The maximum surface height (Rt) of the surface is 100 nm. The characteristics of this film are shown in Table 8 below. As shown in Table 8, the film haze and dynamic friction coefficient of the DFR substrate film of Example 61 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface resistance, The air leakage index is also good.

Examples 62 and 63:

Except that the composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 61 to obtain a film for a DFR base material. As shown in Table 8, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 62 and 63 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

Example 64:

Mix polyester (A) and (B) at a mass ratio of 80% and 20% respectively. The resulting mixed raw material is used as the raw material for the outermost layer (surface layer), and polyester (A) is used as the raw material for the middle layer. Supplied to two extruders, each is melted at 285°C, and then co-extruded to a temperature of 40°C in the form of two layers of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge volume). Cooling and solidification are performed on a cooling roll to obtain an unstretched sheet. Then, after utilizing the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 65 shown in Table 7 below was applied to one side of the longitudinally stretched film and introduced. In the tenter, the film was stretched 4.0 times in the transverse direction at 95°C, and after heat treatment at 230°C, it was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 2 nm. The maximum surface height (Rt) of the surface is 70 nm. The characteristics of this film are shown in Table 9 below. As shown in Table 9, the film haze and dynamic friction coefficient of the DFR substrate film of Example 64 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface resistance, The air leakage index is also good.

Embodiments 65~68:

Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 64 to obtain a film for a DFR base material. As shown in Table 9, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 65 to 68 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

Comparative example 61:

Except that the coating layer was not provided, the film was produced in the same manner as in Example 61 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 8, it was a film with poor dynamic friction coefficient and damage resistance.

Comparative Examples 62 and 63:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 61 to obtain a film. Evaluate the obtained film The results are shown in Table 8. Since the coating liquid 74 does not contain a cross-linking agent, the film of Comparative Example 62 has a good coating appearance. However, even if it is a film with a coating layer, it has poor damage resistance. membrane. In addition, the film of Comparative Example 63 contains inorganic salts in the coating liquid 75. Therefore, the salt precipitated on the film surface during the film manufacturing process, resulting in a film with poor coating appearance, film haze, and poor damage resistance.

Comparative example 64:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 61 to obtain a film. The obtained film was evaluated, and the results are shown in Table 8. Although the coating liquid 79 contains a cross-linking agent, it contains particles with a particle diameter exceeding 1 μm, so grinding may occur. Due to the area of the particles AL The ratio exceeds 15%, so the film has poor damage resistance.

Comparative Examples 65 and 66:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 61 to obtain a film. The obtained film was evaluated, and the results are shown in Table 8. Although the coating liquid 64 of the film system of Comparative Example 65 contained a cross-linking agent, the area ratio of the particles AL was 0%, so the coating appearance and protection were poor. It is also a membrane with poor damage properties. The film system of Comparative Example 66 contains a cross-linking agent in the coating liquid 66, but since the area of the particles AS is 0.3% and the area of the particles AL is 98.3%, the coating appearance and damage resistance are also poor.

Comparative example 67:

Except that the coating layer was not provided, the film was produced in the same manner as in Example 64 to obtain a film. The obtained film was evaluated and the results were as shown in Table 9 since it did not have a coating layer. shows that it is a film with poor dynamic friction coefficient and damage resistance.

Comparative Examples 68 and 69:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 64 to obtain a film. The obtained film was evaluated, and the results are shown in Table 9. The film of Comparative Example 68 does not contain a cross-linking agent in the coating liquid 74. Therefore, although the film system of Comparative Example 68 has a good coating appearance, it does not contain a cross-linking agent. It is a membrane with poor protection against damage due to the combined agent. Since the coating liquid 75 of Comparative Example 69 contains inorganic salts, the salt precipitates on the film surface during the film manufacturing process, resulting in a film with poor coating appearance, film haze, and poor damage resistance.

Comparative example 70:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 64 to obtain a film. The obtained film was evaluated. As shown in Table 9, the results showed that although the coating liquid 78 contained a cross-linking agent, the area ratio of the particles AL exceeded 15%, so the film had poor damage prevention properties.

Comparative examples 71~76:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 64 to obtain a film. The obtained films were evaluated, and the results are shown in Table 9. Although the coating liquids 61 to 64 of the film systems of Comparative Examples 71 to 75 contained a cross-linking agent, the area ratio of the particles AL was 0%, so the coating was The appearance and damage resistance of the film are also poor or the surface wrinkles with large horizontal width are produced. Although the coating liquid 66 of the film system of Comparative Example 76 contains a cross-linking agent, the area of particles AS is 0.3% and the area of particles AL is 98.3%, so the coating It is a film with poor cloth appearance and damage resistance.

Example 81:

Mix polyester (A), (B), and (C) at mass ratios of 75%, 20%, and 5% respectively. The resulting mixed raw materials are used as the raw materials for the outermost layer (surface layer). Polyester (A) As the raw material for the middle layer, it is supplied to two extruders respectively. After being melted at 285°C, it is co-extruded into two types of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge amount). The film was transferred to a cooling roller set at 35°C for cooling and solidification to obtain an unstretched sheet. Then, after utilizing the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 85 shown in Table 10 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 4 nm. The maximum surface height (Rt) of the surface is 100 nm. The characteristics of this film are shown in Table 11 below. As shown in Table 11, the film haze and dynamic friction coefficient of the DFR substrate film of Example 81 are low, the transparency of the coating layer is maintained, and the smoothness is good. Good coating appearance, damage resistance, surface resistance and air leakage index are also good.

Examples 82 and 83:

Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 81 to obtain a film for a DFR base material. As shown in Table 11, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 82 and 83 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

Example 84:

Mix polyester (A) and (B) at a mass ratio of 80% and 20% respectively. The resulting mixed raw material is used as the raw material for the outermost layer (surface layer), and polyester (A) is used as the raw material for the middle layer. Supplied to two extruders, each is melted at 285°C, and then co-extruded to a temperature of 40°C in the form of two layers of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge volume). Cooling and solidification are performed on a cooling roll to obtain an unstretched sheet. Then, after utilizing the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 85 shown in Table 10 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 2 nm. The maximum surface height (Rt) of the surface is 70 nm. The characteristics of this film are shown in Table 12 below. As shown in Table 12, the film haze and dynamic friction coefficient of the DFR substrate film of Example 84 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface resistance, The air leakage index is also good.

Examples 85 and 86:

Except that the composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 84 to obtain a film for a DFR base material. As shown in Table 12, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 85 and 86 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

Embodiment 87~88:

Except that the composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 84 to obtain a film for a DFR base material. As shown in Table 12, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 87 and 88 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

Comparative example 81:

Except that the coating layer was not provided, the film was produced in the same manner as in Example 81 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 11, it was a film with poor dynamic friction coefficient and damage prevention properties.

Comparative example 82:

Except that the coating agent composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 81 to obtain a film. Conduct the obtained membrane As a result of the evaluation, as shown in Table 11, the coating liquid 94 contains a polyether compound, so even a film having a coating layer has poor damage resistance.

Comparative example 83:

Except that the coating agent composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 81 to obtain a film. The obtained film was evaluated, and the results are shown in Table 11. Although the coating liquid 98 contains a cross-linking agent, it contains particles with a particle diameter exceeding 1 μm, so grinding may occur. Due to the area of the particles AL The ratio exceeds 15%, so the film has poor damage resistance.

Comparative Examples 84 and 85:

Except that the coating agent composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 81 to obtain a film. The obtained film was evaluated, and the results are shown in Table 11. Although the coating liquid 84 of the film system of Comparative Example 84 contained a cross-linking agent, the area ratio of the particles AL was 0%, so the coating appearance and protection were poor. It is also a membrane with poor damage properties. Although the coating liquid 86 of the film of Comparative Example 85 contains a cross-linking agent, the area of the particles AS is 0.3% and the area of the particles AL is 98.3%, so the coating appearance and damage resistance are also poor.

Comparative example 86:

Except that the coating layer was not provided, the film was produced in the same manner as in Example 84 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 12, it was a film with a poor dynamic friction coefficient or damage resistance, resulting in surface wrinkles with a large width.

Comparative example 87:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 84 to obtain a film. The obtained film was evaluated. The results are shown in Table 12. Since the coating liquid 94 contains a polyether compound, the film has poor damage resistance even if it has a coating layer.

Comparative example 88:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 84 to obtain a film. The obtained film was evaluated. As shown in Table 12, the results showed that although the coating liquid 97 contained a cross-linking agent, the area ratio of the particles AL exceeded 15%, so the film had poor damage resistance.

Comparative examples 89~94:

Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 84 to obtain a film. The obtained films were evaluated, and the results are shown in Table 12. Although the coating liquids 81 to 84 of the film systems of Comparative Examples 89 to 93 contained a cross-linking agent, since the area ratio of the particles AL was 0%, it also produced Films with large surface wrinkles or films with poor coating appearance and damage resistance. Although the coating liquid 86 of the film of Comparative Example 94 contains a cross-linking agent, the area of the particles AS is 0.3% and the area of the particles AL is 98.3%, so the coating appearance and damage resistance are also poor.

[Industrial availability]

The polyester film for a dry film resist base material of the present invention can be suitably used as a base film for a dry film resist used in the production of printed wiring boards, for example.

Claims (16)

A polyester film for a dry film resist base material, characterized in that: there is a coating layer on at least one side of the polyester film, and the content of the antistatic agent in the coating layer is 45% by mass or less, and the coating layer The layer contains particles, and the area ratio of particles AS with a particle diameter of 30 to 80 nm is 60 to 99.9% relative to the total area of particles occupying the surface of the coating layer when the surface of the coating layer is observed. Within the range, the area ratio of particles AL with a particle size of 100 to 400 nm is within the range of 0.1 to 15%, and does not substantially contain particles with a particle size exceeding 1 μm. A polyester film for a dry film resist base material, characterized in that: there is a coating layer on at least one side of the polyester film, the coating layer contains a surfactant, and the coating layer contains particles. When the surface of the coating layer is observed, the total area of the particles occupying the surface of the coating layer, the area ratio of particles AS with a particle diameter of 30 to 80 nm is in the range of 60 to 99.9%, and the particle diameter is 100 The area ratio of ~400nm particles AL is in the range of 0.1~15%, and does not substantially contain particles with a particle size exceeding 1 μm. A polyester film for a dry film resist base material, characterized in that: a coating layer is provided on at least one side of the polyester film, and the coating layer does not substantially contain inorganic salts, and the coating layer contains particles, When the surface of the coating layer is observed, the area ratio of particles AS having a particle diameter of 30 to 80 nm is in the range of 60 to 99.9%, and the particle diameter is The area ratio of particles AL between 100 and 400 nm is in the range of 0.1 to 15%, and does not substantially contain particles with a particle size exceeding 1 μm. A polyester film for a dry film resist base material, characterized in that: a coating layer is provided on at least one side of the polyester film, and the coating layer does not substantially contain a polyether compound, and the coating layer contains particles , relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed, the area ratio of particles AS with a particle diameter of 30 to 80 nm is in the range of 60 to 99.9%, and the particles The area ratio of particles AL with a diameter of 100 to 400 nm is in the range of 0.1 to 15%, and does not substantially contain particles with a diameter exceeding 1 μm. A polyester film for a dry film resist base material, characterized in that at least one side of the polyester film has a coating layer formed of a coating liquid containing a cross-linking agent, and an antistatic agent in the coating layer The content is less than 45% by mass. The coating layer contains particles A-1 and particles A-2. The average particle size of particle A-1 is 0.001~0.06 μm, and the average particle size of particle A-2 is 0.06. ~1.0μm. A polyester film for a dry film resist base material, characterized in that at least one side of the polyester film has a coating layer formed of a coating liquid containing a cross-linking agent, and the coating layer contains a surfactant , The coating layer contains particle A-1 and particle A-2. The average particle diameter of particle A-1 is 0.001~0.06 μm, and the average particle diameter of particle A-2 is 0.06~1.0 μm. A polyester film for a dry film resist base material, characterized in that at least one side of the polyester film has a coating layer formed of a coating liquid containing a cross-linking agent, and the coating layer does not substantially contain Inorganic salt, the coating layer contains particle A-1 and particle A-2, the average particle diameter of particle A-1 is 0.001~0.06 μm, and the average particle diameter of particle A-2 is 0.06~1.0 μm. A polyester film for a dry film resist base material, characterized in that at least one side of the polyester film has a coating layer formed of a coating liquid containing a cross-linking agent, and the coating layer does not substantially contain Polyether compound, the coating layer contains particles A-1 and particles A-2, the average particle diameter of the particle A-1 is 0.001~0.06 μm, and the average particle diameter of the particle A-2 is 0.06~1.0 μm. The polyester film for a dry film resist base material according to any one of claims 1 to 8, wherein the average surface roughness (Ra) of the surface with the above-mentioned coating layer is in the range of 1 to 10 nm. The polyester film for a dry film resist base material according to any one of claims 1 to 8, wherein the air leakage index of the surface with the above-mentioned coating layer measured according to JIS P8119 is 400000 seconds or less. The polyester film for a dry film resist substrate according to any one of claims 1 to 8, wherein the thickness of the coating layer is in the range of 0.001 to 1 μm. The polyester film for a dry film resist base material according to any one of claims 1 to 8, wherein the coating layer contains wax. The polyester film for a dry film resist base material according to any one of claims 1 to 8, wherein the polyester film contains particles B that can impart slipability. The polyester film for a dry film resist substrate according to any one of claims 1 to 8, wherein the coating layer is formed from a coating liquid, the coating liquid contains a cross-linking agent, and the cross-linking agent is melamine compound or

oxazoline compounds. As claimed in claim 14, the polyester film for a dry film resist base material, wherein the content of the cross-linking agent relative to all non-volatile components in the coating liquid is 5 to 85 mass %. A dry film resist having a photosensitive resin layer on the opposite side to the coating layer side of the polyester film for a dry film resist base material according to any one of claims 1 to 15.