JP2016087854A - Biaxially oriented polyester film for dry film resist supporter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester film for dry film resist supporter achieving high resolution of a resist, having no defects and capable of coping with quality improvement and productivity improvement.SOLUTION: There is provided a biaxially oriented polyester film for dry film resist having a laminate structure with three or more layers, film haze of less than 1.0%, surface roughness SRa (A) of 7 nm or less and SRz (A) of less than 100 nm of one surface (A) and surface roughness SRa (B) of 3 nm or more and less than 10 nm and SRz (B) of 100 nm or more and less than 700 nm of another surface (B) and reflection ratio at 365 nm and 405 nm when a light is injected from the B surface of less than 14%.SELECTED DRAWING: None

Description

The present invention relates to a polyester film for a dry film resist support.

Dry film resist (hereinafter DFR) is a manufacturing method used for forming circuits such as printed wiring boards, semiconductor packages, and flexible boards.
The DFR has a structure in which a photosensitive layer (photoresist layer) is laminated on a polyester film as a support and then sandwiched between protective films (cover films) made of an LDPE (low density polyethylene) film or the like. To create a conductor circuit using this DFR, the following steps are generally performed.
1) Step of laminating the protective film from the DFR and laminating it with the substrate / conductive substrate layer so that the exposed surface of the resist layer and the surface of the conductive substrate layer such as copper foil on the substrate are in close contact with each other .
2) Next, a photomask on which the conductor circuit pattern is baked is placed on a support made of a polyester film, and from there on the resist layer mainly composed of a photosensitive resin, ultraviolet rays (for example, I-line having a peak at 365 nm, A step of irradiating with exposure to H-line having a peak at 405 nm.
3) Then, after peeling the photomask and the polyester film, a step of dissolving and removing unreacted components in the resist layer with a solvent.
4) Next, a step of etching with acid or the like to dissolve and remove the exposed portion in the conductive base material layer.
After the step 4), the photoreactive portion in the resist layer and the conductive substrate layer portion corresponding to the photoreactive portion remain as they are. Thereafter, a conductor circuit on the substrate is formed through a process of removing the remaining resist layer. For this reason, it is requested | required that the polyester film which is a support body can permeate | transmit an ultraviolet-ray efficiently. Thereby, the conductor circuit pattern is accurately reflected on the resist layer. Particularly in recent years, with the miniaturization and weight reduction of IT equipment and the like, there is a demand for a polyester film for a dry film resist support that has excellent transparency, low haze, and high resolution. However, since the polyester film contains particles as an easy-sliding material in order to impart runnability and winding characteristics, light scattering by the particles is caused by both transmission and reflection during ultraviolet irradiation during the exposure process. There has been a problem that the resolution of the resist is lowered.

  Therefore, a dry film characterized in that the surface of the film is highly smoothed and the haze value is lowered (for example, Patent Documents 1, 2, and 4), and the transmittance at a wavelength of 365 nm is within a certain range. A polyester film for a resist support has been proposed (Patent Document 3). In addition, by providing a polyester film for photoresist (Patent Document 5) that is free from cleavage failure due to cleavage and elongation at the time of peeling of the base film and excellent in rollability of the base film itself, and an easy-slip layer, transparency and There has been proposed a polyester film for photoresist that achieves easy slipping (Patent Document 6).

JP-A-1995-333853 JP 2002-341546 A JP 2005-059285 A JP 2008-239743 A JP 2000-35671 A JP 2004-361446 A

However, even with these proposals, it is difficult to satisfy the demand for higher resolution, and the defects such as distortion and omission in resist patterning after development and the state of the resist pattern wall surface cannot be solved sufficiently. Still, there is a demand for quality improvement for higher resolution. Furthermore, as a result of supporting high resolution, the amount of particles added to the base film as a lubricant or applied on the base film is reduced, resulting in a decrease in yield in the film manufacturing process and the above DFR manufacturing process, especially in winding. Since related problems are conspicuously occurring, there is a demand for improvement in productivity (film winding property). In view of this situation, it is an object of the present invention to provide a biaxially oriented polyester film for a dry film resist support that can achieve high resolution of resist, has few defects, and can cope with quality improvement and productivity improvement.

The present invention has the following features.
(1) It is a polyester film having a laminated structure of three or more layers, the film haze is less than 1.0%, and the surface roughness SRa (A) of one surface (the surface is referred to as the surface (A)) 7 nm or less, SRz (A) is less than 100 nm, and the other surface (this surface is referred to as surface (B)) has a surface roughness SRa (B) of 3 nm or more and less than 10 nm and SRz (B) of 100 nm or more. A biaxially oriented polyester film for a dry film resist support, which is less than 700 nm and has a reflectance of less than 14% at 365 nm and 405 nm when light is incident from the surface (B) side.
(2) Polyester having a surface (A) having a surface (A) (the layer is referred to as layer A), particles having a maximum particle diameter DA of DA <0.4 μm, and a surface (B) When particles are contained in a layer (this layer is referred to as B layer), the maximum particle diameter DB of the particles is 0.4 μm ≦ DB <1.0 μm, and the film thickness T (μm), The biaxially oriented polyester film for dry film resist support according to (1), wherein DB / T ≦ 0.05.
(3) The biaxially oriented polyester film for dry film resist support according to (1) or (2), wherein a resist layer is laminated on the surface (A).
(4) The biaxially oriented polyester film for dry film resist support according to any one of (1) to (3), which is a polyester film melt-formed by coextrusion.

  ADVANTAGE OF THE INVENTION According to this invention, even if it achieves the high resolution of a resist, there are few faults and the polyester film for dry film resist supports which can respond to quality improvement and productivity improvement can be provided.

  The polyester film for a photoresist support according to the present invention has a laminated structure of three or more layers containing a polyester resin as a main component. And the surface roughness SRa (A) of one surface (the surface is referred to as the surface (A)) is 7 nm or less and the SRz (A) is less than 100 nm, and the other surface (the surface is the surface (B)) The surface roughness SRa (B) must be 3 nm or more and less than 10 nm, and SRz (B) must be 100 nm or more and less than 700 nm. The polyester film of the present invention is preferably used by laminating a resist layer on the A side when used for a photoresist support.

  In order to impart high transparency to the polyester film, the layer (intermediate layer) existing between the A layer and the B layer is controlled while individually controlling the reflectance of the layer having the A surface and the layer having the B surface. For example, it is preferable to have a configuration that does not substantially contain particles.

  Moreover, the polyester film of the present invention needs to be biaxially oriented. In the present invention, the biaxial orientation refers to a state in which an unstretched (unoriented) film is stretched in a two-dimensional direction by a conventional method (showing a biaxially oriented pattern by wide-angle X-ray diffraction). Stretching can take sequential biaxial stretching and simultaneous biaxial stretching. In sequential biaxial stretching, the process of stretching in the longitudinal direction (longitudinal) and the width direction (transverse) can be performed once in the length-width direction, or twice in the length-width-length-width direction. You can also

  In the present invention, a polyester resin as a main component means that at least 70 mol% or more is obtained by polymerization from a monomer or a low polymer mainly composed of a dicarboxylic acid, a diol, and an ester-forming derivative thereof. Polyester. In the present invention, it is preferable to use an aromatic dicarboxylic acid as the dicarboxylic acid.

  Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and terephthalic acid is particularly preferable. These acid components may be used alone or in combination of two or more, and may be partially copolymerized with other aromatic dicarboxylic acids such as isophthalic acid or fatty acids.

  Examples of the diol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, and the like. Of these, ethylene glycol is preferably used. These diol components may be used alone or in combination of two or more.

  The polyester used in the biaxially oriented polyester film for dry film resist support of the present invention is preferably polyethylene terephthalate, polyethylene naphthalate, and a copolymer thereof, polybutylene terephthalate and a copolymer thereof, polybutylene naphthalate, and Examples of the copolymer include polyhexamethylene terephthalate and a copolymer thereof, polyhexamethylene naphthalate and a copolymer thereof, and polyethylene terephthalate is particularly preferable.

  The polyester used in the present invention can be produced by a conventionally known method. For example, a method in which an acid component is directly esterified with a diol component, and then the product of this reaction is heated under reduced pressure to perform polycondensation while removing excess diol component, or a dialkyl as an acid component A method of producing an ester by transesterifying it with a diol component and then performing polycondensation in the same manner as described above can be employed. At this time, conventionally known alkali metals, alkaline earth metals, manganese, cobalt, zinc, antimony, germanium, titanium compounds, and the like can be used as a reaction catalyst, if necessary.

  The intrinsic viscosity of the polyester is preferably a lower limit of 0.5 dl / g and an upper limit of 0.8 dl / g. More preferably, the lower limit is 0.55 dl / g and the upper limit is 0.70 dl / g.

  In the biaxially oriented polyester film for dry film resist support of the present invention, the surface roughness SRa (A) of one surface (A surface) is 7 nm or less and SRz (A) is less than 100 nm, and the other surface ( The (B surface) needs to have a surface roughness SRa (B) of 3 nm or more and less than 10 nm and SRz (B) of 100 nm or more and less than 700 nm. The biaxially oriented polyester film for dry film resist support of the present invention preferably has a resist layer laminated on the A side. By achieving a surface roughness in this range, it is possible to obtain appropriate smoothness that suppresses the influence of reflection on the film surface during exposure, and to form a highly fine resist pattern at the same time as processing. Handleability can be obtained. When the surface roughness SRa (A) of the A surface exceeds 7 nm or SRz (A) exceeds 100 nm, the incident angle of light in the exposure process due to the unevenness and the unevenness transferred from the film to the resist surface becomes nonuniform. In addition, the resist pattern may be lost due to the influence of reflection or scattering of light, which is unsuitable. The surface roughness SRa (A) of the A plane is more preferably 3 nm or more and 6 nm or less, and SRz (A) is more preferably 50 nm or more and 100 nm or less. On the other hand, the center line roughness SRa (B) of the B surface needs to be 3 nm or more and 10 nm or less, and SRz (B) needs to be 100 nm or more and less than 700 nm. When the resist layer is laminated on the A surface side of the polyester film of the present invention, the B surface is a surface in contact with the resist layer, and when the cover film is bonded and wound, it becomes a surface in contact with the cover film. When the center line roughness SRa (B) of the B surface is less than 3 nm or SRz (B) is less than 100 nm, the handling property deteriorates in the resist coating process, the coating becomes unstable, and coating spots occur. When winding after application, it is unsuitable because it may cause winding misalignment due to difficulty in removing the air that has been caught. Further, when the center line roughness SRa (B) of the B surface exceeds 10 nm or SRz (B) exceeds 700 nm, the incident angle of light in the exposure process becomes uneven due to the unevenness formed on the surface. This is not suitable because it causes noise when forming a resist pattern due to the influence of light reflection and scattering. The surface roughness SRa (B) of the B surface is more preferably 6 nm or more and 10 nm or less, and SRz (B) is more preferably 100 nm or more and 500 nm or less. In order to make the surface roughness of the A layer and the B layer within the above-mentioned range, specific organic particles described later are added to the polyester resin constituting the layer having the A surface (A layer) and the layer having the B surface (B layer). Alternatively, it can be achieved by containing a specific amount of inorganic particles.

  The biaxially oriented polyester film for a dry film resist support of the present invention preferably has a total film thickness of 10 to 50 μm. Particularly preferably, the thickness is 12 μm to 38 μm. If the total thickness is less than 10 μm, the strength may be insufficient and handling in the processing step may be difficult, and if it exceeds 50 μm, it may be difficult to make the light transmittance and haze value within the range of the present invention.

  In the polyester film in the present invention, it is preferable that the dimensional change rate is in the following range, because generation of distortion and wrinkles due to thermal shrinkage in the DFR processing step can be suppressed. The dimensional change rate can be achieved by appropriately adjusting the conditions such as relaxation and heat treatment in the film forming conditions by a known method. The dimensional change rate at 150 ° C. is preferably 2% or less in the longitudinal direction and 2.5% or less in the width direction, 0.5% or more and 1.7% or less in the longitudinal direction, and 1% or more and 2% or less in the width direction. preferable. The dimensional change rate at 100 ° C. is preferably 1% or less in both the longitudinal direction and the width direction, and more preferably in the range of 0.2% to 0.8%. If the dimensional change rate is below the lower limit of the above range, flatness defects due to tarmi occur when applying the resist layer, and if it exceeds the upper limit, shrinkage spots are generated in a tin shape due to shrinkage when applying the resist layer. However, the flatness becomes poor, and in any case, the coating thickness of the resist layer may be uneven.

  Moreover, it is preferable that the intensity | strength (henceforth this value is called F-5 value) when a film of a longitudinal direction expands 5% is 70-150 MPa. If the F-5 value in the longitudinal direction is less than 70 MPa, the processing characteristics may be deteriorated due to scratches due to insufficient strength. On the other hand, if the F-5 value in the longitudinal direction exceeds 160 MPa, it may be difficult to achieve both the F-5 value in the width direction. The F-5 value in the longitudinal direction is preferably 70 to 140 MPa, more preferably 80 to 130 MPa.

Furthermore, the F-5 value in the width direction is preferably 80 to 160 MPa. If the F-5 value in the width direction is less than 80 MPa, processing characteristics due to the occurrence of scratches due to insufficient strength may deteriorate, and if it exceeds 160 MPa, it may be difficult to achieve both the F-5 value in the longitudinal direction. It is preferably 80 to 150 MPa, more preferably 90 to 140 MPa. The sum of the longitudinal F-5 value and the longitudinal F-5 value is preferably 200 to 270 MPa, and particularly preferably 220 to 250 MPa. preferable. The F-5 value in the width direction is preferably equal to or greater than the F-5 value in the longitudinal direction, and the difference is more preferably 10 to 20 MPa.

  The breaking strength in the longitudinal direction is preferably 200 to 360 MPa, and more preferably 220 to 304 MPa. The breaking strength in the width direction is preferably 260 to 420 MPa, particularly preferably 280 to 400 MPa.

  The F-5 value and the breaking strength can be achieved by appropriately adjusting the stretching temperature and the stretching ratio in the longitudinal direction and the transverse direction.

  Furthermore, in the polyester film of the present invention, the film haze needs to be 1.0% or less. If it exceeds 1.0%, after the resist layer is laminated on the polyester film, ultraviolet ray scattering by the polyester film, which is the support of the resist layer, is increased when exposed to ultraviolet rays. The patterning is distorted, missing, and the state of the resist pattern wall surface deteriorates. Moreover, the transmittance | permeability of a polyester film is inhibited.

  The polyester film of the present invention is required to have a reflectance of less than 14% at wavelengths of 365 nm and 405 nm when light is incident from the B surface. In addition, the reflectance as used in the field of this invention represents the relative reflectance when the reflectance of a barium sulfate white standard board is 100% calculated | required by the measuring method mentioned later. The ultraviolet rays used in the step of exposing the resist layer mainly use I-line having a peak at 365 nm and H-line having a peak at 405 nm. Therefore, by reducing the reflectivity at wavelengths of 365 nm and 405 nm, it is possible to suppress the resist patterning after development from being distorted, missing, and the state of the resist pattern wall surface from being deteriorated.

  In order to achieve film haze and reflectivity at 365 nm and 405 nm when light is incident from the B side within the specified range, inhibition of light transmission by particles contained in the polyester resin constituting the film is suppressed. Furthermore, it is necessary to suppress scattering due to unevenness on the film surface. For this purpose, it is effective to reduce the particle size of the particles contained in the film and reduce the content, but in this case, the film surface becomes too smooth, and the slipperiness and running properties are poor. Thus, the processing characteristics are inferior. It is necessary to satisfy both contradictory functions of maintaining processing characteristics without deteriorating film haze and reflectance.

  As particles contained in the polyester layer constituting the surface, organic and inorganic particles can be used, for example, silicon oxide, calcium carbonate, aggregated alumina, aluminum silicate, mica, clay, talc, barium sulfate, etc. Examples of the organic type include polyimide resins, olefins or modified olefin resins, cross-linked polystyrene resins, and silicone resins. In adopting these particles, in order to suppress the increase in light transmittance and haze value, the surface of the particle is modified with a surfactant or the like, and the method of improving the affinity with the polyester is a method around the added particle. It can preferably be employed in terms of suppressing the generation of voids. Further, the particle shape is almost spherical and the difference in refractive index from the polyester is preferably smaller because it can suppress scattered light when ultraviolet rays pass through the film layer, and colloidal silica and organic particles are particularly preferable. Furthermore, silicone particles and crosslinked polystyrene particles are suitable.

  Among these, crosslinked polystyrene particles made of a styrene-divinylbenzene copolymer prepared by emulsion polymerization are preferable because the particle shape is close to a true sphere, the particle size distribution is uniform, and uniform protrusions can be formed.

  More specifically, the maximum particle diameter DA of the particles contained in the polyester layer (A layer) having one surface (A surface) is DA <0.4 μm, and the other surface (B surface) has polyester. The maximum particle size DB contained in the layer (B layer) is preferably 0.4 μm ≦ DB <1.0 μm. The maximum particle diameter as used in the field of this invention represents the equivalent circle diameter of the particle | grains calculated | required by the method mentioned later. When a resist layer is laminated on the A surface, the formation of the resist layer is affected when the particles contained in the A layer are affected by the reflection or scattering of light irradiated in the exposure process. When the maximum particle diameter DA contained in the A layer is 0.4 μm or more, the influence of the particles becomes noise when forming the resist pattern, and the resist pattern may be chipped. Further, the B surface constitutes the opposite surface of the resist layer. However, if it is affected by the reflection or scattering of light irradiated in the exposure process by the particles contained in the B layer, the formation of the resist layer is affected. When the maximum particle size DB included in the layer B is 1.0 μm or more, the influence of the particles becomes noise when forming the resist pattern, and the resist pattern may be chipped. Also, if the average particle diameter DB is less than 0.4 μm, the handling property is deteriorated in the resist coating process, the maximum becomes unstable, the coating spots are generated, and air taken in at the time of winding after coating is generated. Winding misalignment may occur due to difficulty in removal.

  Moreover, when it is set as the whole film thickness T, it is preferable that it is DB / T <= 0.05. When DB / T is larger than 0.05, the influence of particles becomes noise when forming a resist pattern, and the resist pattern may be chipped.

  The polyester film of the present invention needs to be a polyester film having a laminated structure of three or more layers. Examples of the film having a three-layer laminated structure include those composed of A layer / C (intermediate layer) / B layer. Examples of the film having a laminated structure of four or more layers include those in which the intermediate layer has a laminated structure. The particle type, average particle diameter, and content contained in the A layer and B layer as the surface layer portion may be different. Particles may be added to the polyester layer constituting the surface layer in the coating step, but from the viewpoint of dispersibility of the particles, a polyester resin composition containing the particles is used to perform melt film formation by a coextrusion method. It is preferable to obtain.

  In the above configuration, the layer thickness (A layer, B layer) constituting the surface of the film is preferably 0.1 to 2 μm, more preferably 0.2 to 1.0 μm, still more preferably 0.4 to 0.8 μm. When the particle size is less than 0.1 μm, dropout of the particles added to the polyester layer increases, and when the particle size exceeds 2 μm, the average diameter and the amount of particles added may be further reduced in order to achieve the above-described haze. It becomes necessary, and it may be difficult to achieve compatibility with processing characteristics.

  The A layer and the B layer may further contain agglomerated alumina together with the aforementioned particles. Here, the agglomerated alumina represents an aggregate of several to several hundred particles having an average primary particle diameter of 5 to 30 nm. The average primary particle diameter of the aggregated alumina is more preferably an average primary particle diameter of 8 to 15 nm. As the agglomerated alumina, those produced by the flame hydrolysis method using anhydrous aluminum chloride as a raw material or the hydrolysis of alkoxide alumina can be employed. Agglomerated alumina is known in crystal form such as δ type, θ type, and γ type, and in particular, δ type alumina can be preferably used. These agglomerated alumina can be used by adding at the time of polyester polymerization.For example, as a slurry of ethylene glycol, which is part of the raw material at the time of polyester polymerization, pulverization and dispersion of a sand grinder, etc. By carrying out, agglomerated alumina having an average secondary particle diameter of 0.01 to 0.2 μm can be obtained. When the agglomerated alumina thus obtained is added to the film, it is arranged in the plane direction by biaxial stretching, so it does not form substantial protrusions, has little effect on the surface roughness, and is transparent. Since the property is good, deterioration of light transmittance and haze value can be suppressed. By including the aggregated alumina, the effect of reinforcing the background of the film surface is greatly obtained, the wear resistance is improved, and the effect of suppressing the dent defect generated when contacting the roll during stretching is obtained. Aggregated alumina is preferably contained in the polyester resin composition constituting the surface layer (A layer, B layer), and the content thereof is preferably 0.1 to 1% by weight with respect to the entire polyester resin composition.

  Next, the manufacturing method of the biaxially-oriented polyester film for dry film resist supports of this invention is demonstrated. As a method of adding inert particles to polyester in melt film formation by co-extrusion method, for example, inert glycol is dispersed in a predetermined ratio in ethylene glycol, which is a diol component, for example, coarse particles of 3 μm or more. After high-precision filtration capable of collecting 95% or more, this ethylene glycol slurry is added at an arbitrary stage before completion of polyester polymerization. Here, when adding the particles, for example, it is preferable to add the water sol or alcohol sol obtained at the time of synthesis without drying once because the dispersibility of the particles is good and the generation of coarse protrusions can be suppressed. Also effective for the effect of the present invention is a method in which a water slurry of particles is directly mixed with predetermined polyester pellets, supplied to a vent type twin-screw kneading extruder and kneaded into polyester.

  In this way, the particle-containing master pellets prepared for each layer and the pellets substantially free of particles and the like are mixed at a predetermined ratio, dried, and then supplied to a known melt laminating extruder. As the extruder for producing the biaxially oriented polyester film for a dry film resist support of the present invention, a uniaxial or biaxial extruder can be used. Moreover, in order to omit the drying process of a pellet, the vent type extruder which provided the vacuum drawing line in the extruder can also be used. In addition, when providing an intermediate layer, since the amount of extrusion is the largest, use a so-called tandem extruder that shares the function of melting the pellets and the function of maintaining the molten pellets at a constant temperature. Can do. In order to extrude the layer constituting the surface of the biaxially oriented polyester film for dry film resist support of the present invention, it is preferable to use a biaxial vent type extruder because the dispersibility of the particles can be kept good.

  The polymer melted and extruded by the extruder is filtered through a filter. Since even a very small foreign substance enters a film and becomes a coarse protrusion defect, it is effective to use a high-accuracy filter that collects 95% or more of a foreign substance of 5 μm or more, for example. Subsequently, the sheet is extruded from a slit-shaped slit die and cooled and solidified on a casting roll to form an unstretched film. That is, it laminates using a plurality of extruders, a plurality of layers of manifolds or a merge block (for example, a merge block having a rectangular merge portion), extrudes a sheet from a die, and cools with a casting roll to produce an unstretched film. In this case, a method of installing a static mixer and a gear pump in the polymer flow channel is effective from the viewpoint of stabilizing the back pressure and suppressing thickness fluctuation.

  The stretching method may be simultaneous biaxial stretching or sequential biaxial stretching.

  In the case of sequential stretching, the first longitudinal stretching is important, and the stretching temperature is preferably 90 to 130 ° C, more preferably 105 to 120 ° C. When the stretching temperature is lower than 90 ° C., the film is easily broken, and when the stretching temperature is higher than 130 ° C., the film surface is easily damaged by heat, which is not preferable. Further, from the viewpoint of preventing stretching unevenness and scratches, stretching is preferably performed in two or more stages, and the total magnification is preferably 3 to 4.5 times, more preferably 3.2 to 4 in the length direction. .2 times, preferably 3.2 to 5 times, more preferably 3.9 to 4.5 times in the width direction. In order to achieve the target breaking strength of the film, a timely magnification can be selected, but in order to increase the breaking strength in the width direction, it is more preferable to set the stretching ratio in the width direction higher than in the longitudinal direction. If the temperature and magnification range are out of this range, problems such as uneven stretching or film breakage are caused, and it is difficult to obtain a film characterized by the present invention. After re-longitudinal or transverse stretching, heat setting is preferably performed at 200 to 230 ° C., more preferably 210 to 230 ° C., preferably 0.5 to 20 seconds, more preferably 1 to 15 seconds. In particular, when the heat setting temperature is lower than 200 ° C., the crystallization of the film does not proceed, the structure is not stable, and the target characteristics such as heat shrinkage cannot be obtained. Thereafter, it is preferable to apply a relaxation treatment of 0.1 to 7.0% in the longitudinal and / or width direction.

  In the stretching process, contact between the film and the roll is unavoidable, and the difference between the peripheral speed of the roll and the speed of the film is suppressed as much as possible, and as the stretching roll, non-adhesive silicone that is easy to control the surface roughness and the like A roll is preferred. Although it is possible to use ceramic, “Teflon” (registered trademark) or metal rolls as in the prior art, only the film surface is locally heated, causing adhesion and scratching the film surface. In some cases, it is not preferable.

  Furthermore, the surface roughness Ra of the stretching roll is preferably 0.005 to 1.0 μm, more preferably 0.1 to 0.6 μm. When Ra is larger than 1.0 μm, unevenness on the roll surface during stretching is transferred to the film surface. On the other hand, when it is smaller than 0.005 μm, the roll and the film background adhere to each other, and the film is easily damaged by heat. It is not preferable. In order to control the surface roughness of the drawing roll, it is effective to appropriately adjust the particle size of the abrasive for polishing the drawing roll, the number of times of polishing the drawing roll, and the like. In particular, with respect to the stretching roll, it is preferable to increase the number of polishing of the stretching roll in order to avoid adhesion and accumulation of polyester degradation products and oligomers, which are considered to be the cause of the dimple defects on the film surface.

  Further, the total contact time between the roll and the film in the stretched portion is preferably 0.1 seconds or less, more preferably 0.08 seconds or less, which is particularly effective in producing the film. When the contact time between the stretching roll and the film is longer than 0.1 seconds, only the film surface is locally heated by the heat of the stretching roll, which may cause a deterioration in micro-planarity during heat load, or The film may be scratched. As a method for shortening the contact time, for example, a method in which a film is stretched in parallel between nip rolls without being wound around a stretch roll is effective.

  After the biaxially stretched film is cooled in the conveying step, the edge is cut and wound to obtain an intermediate product. In this conveying step, the thickness of the film is measured, the data is fed back and used to adjust the film thickness by adjusting the die thickness and the like, and foreign matter detection is performed by a defect detector.

  In the biaxially oriented polyester film for dry film resist support of the present invention, it is preferable to suppress the generation of chips when cutting the edge. Edge cutting is performed using a round blade, a shear blade, and a straight blade, but when using a straight blade, it is preferable not to always make the location where the blade hits the film the same location, because it is possible to suppress wear of the blade. It is. For this reason, it is preferable to have a mechanism for oscillating the blade to the upper limit. Moreover, it is preferable to provide a suction device at a film cutting location to suck generated chips and scraped powder generated by cutting the film ends after cutting.

  The intermediate product is wound into a suitable width and length by a slitting process, and a roll of the biaxially oriented polyester film for mold release according to the present invention is obtained. When cutting the film in the slitting process, it can be selected from the same cutting method as the above-described edge cutting.

  The intermediate product is slit to a desired width to obtain the biaxially oriented polyester film for dry film resist of the present invention.

Hereinafter, the present invention will be described in detail with reference to examples.
The measurement method and evaluation method according to the present invention are as follows.

(1) Maximum particle diameter of particles The layer constituting the film surface is measured as follows. The polymer is removed from the film by plasma low temperature ashing to expose the particles. The processing conditions are selected such that the polymer is ashed but the particles are not damaged as much as possible. The treated sample was observed with a scanning electron microscope (SEM; model S-4000 manufactured by Hitachi, Ltd.), the particle image was taken into an image analyzer (LUZEX_AP manufactured by Nireco Corporation), and the equivalent circle equivalent diameter was measured. The volume average particle diameter of is determined. The magnification of SEM is appropriately selected from 5000 to 20000 times depending on the particle diameter. Measure the equivalent circle equivalent diameter of at least 5000 particles, arbitrarily changing the observation location, and determine the maximum particle diameter from the middle value of the equivalent circle equivalent diameter of the top 2% from the larger of the measured equivalent circle equivalent diameter data. Ask for.

  About the layer which does not comprise the film surface, a film cross section is observed by 3000 to 20000 times by a particle diameter using a transmission electron microscope (TEM; Hitachi, Ltd. H-600 type | mold). The TEM slice thickness is about 100 nm, the equivalent circle equivalent diameter of 1000 particles is measured at different locations, and the middle of the equivalent circle equivalent diameter of the top 2% of the particles from the larger equivalent circle equivalent diameter data measured. The maximum particle size is obtained from the value.

  In addition, when measuring the volume average particle diameter of the particles, when observed by SEM and TEM, even if 10 fields of view are confirmed at 5000 times, if no particles are found, the particles should be substantially not contained. to decide.

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

(3) Film Lamination Thickness Using a transmission electron microscope (TEM; H-600 type manufactured by Hitachi, Ltd.), the cross section of the film is observed with an ultrathin section (RuO ₄ staining) at an acceleration voltage of 100 kV. The total thickness is obtained from the entire cross section, and the laminated thickness is obtained from the deepest point of the particles observed at the interface, that is, the depth from the surface, that is, the laminated thickness. The magnification may be appropriately set depending on the total thickness and the layer thickness of the film to be measured. In general, 1000 times is appropriate for measuring the total thickness, and 10,000 to 100,000 times is appropriate for measuring the laminated thickness.
In order to presume at what magnification the particle image should be obtained in order to discriminate the laminated interface, such as when there are few particles, it is assumed from the distribution (mapping) of elements in the cross section by SEM-XMA of the cross section It is efficient to estimate the stack thickness and determine the set magnification in TEM.

(4) Elongation at break, strength at break, F-5 value Instron type tensile tester (Orientec Co., Ltd. film tensile strength automatic measuring device "Tensilon" universal testing machine RTC- in accordance with JIS C2151-1990) 1210). A sample film with a width of 10 mm is subjected to a tensile test under the conditions of 100 mm between test lengths and a pulling speed of 200 mm / min. The strength when the film stretches by 5% is set to F-5 value, and the stress when the film breaks is obtained. The breaking strength was obtained, and the strain (elongation rate) when the film broke was obtained to obtain the breaking elongation. The measurement is performed at 23 ° C. and a humidity of 65% RH.

(5) Dimensional change rate Two lines are drawn on the film surface so that the width is 10 mm and the measurement length is about 100 mm, and the distance between the two lines is accurately measured at 23 ° C., and this is defined as L0. This film sample was left in an oven at 100 ° C. or 150 ° C. for 30 minutes under a load of 1.5 g, and then the distance between the two lines was measured again at 23 ° C., and this was designated as L1. The rate of dimensional change at the temperature is obtained.
Dimensional change rate (%) = {(L0−L1) / L0] × 100.

(6) Film surface roughness (SRa, SRz value)
Measured using a three-dimensional fine surface shape measuring instrument (ET-350K manufactured by Kosaka Manufacturing Co., Ltd.) From the surface profile curve obtained, arithmetic average roughness SRa value, ten-point average surface roughness SRz according to JIS B0601 Find the value. The measurement conditions are as follows.
X direction measurement length: 0.5 mm, X direction feed rate: 0.1 mm / second.
Y direction feed pitch: 5 μm, number of Y direction lines: 40.
Cut-off: 0.25 mm.
Stylus pressure: 0.02 mN.
Height (Z direction) Magnification: 50,000 times.

(7) Haze of film In accordance with JIS K7105-1981, a sample cut into a dimension of length 4.0 × width 3.5 cm from the center in the film width direction was used as a sample, and haze was measured using a haze meter (HGM-manufactured by Suga Test Instruments). 2DP (for C light source)).

(8) Reflectance Measured with a spectrophotometer (Shimadzu Corporation UV2450) attached with an integrating sphere attachment device (ISR2200, Shimadzu Corporation), with barium sulfate as a standard plate, and light incident from the B side. Then, the relative reflectance at wavelengths of 365 nm and 405 nm with the standard plate as 100% was measured.
<Standard plate creation method>
34 g of barium sulfate white standard reagent (EASTMAN White Reflectance Standard Cat No.6091) was put into a cylindrical recess having a diameter of 50.8 mm and a depth of 9.5 mm, and compressed using a glass plate, and the compression density was about 2 g / cm. ³ barium sulfate white standard plate was prepared.

(9) Visual inspection of resist resolution A visual evaluation method of resist resolution by a biaxially oriented polyester film for a dry film resist support was performed in the following procedure.
(I) A negative resist “PMER N-HC600” manufactured by Tokyo Ohka Co., Ltd. was applied on a 6-inch Si wafer that had been polished on one side, and a resist layer having a thickness of 7 μm was prepared by rotating with a large spinner. Next, a pre-heat treatment was performed for about 20 minutes under a temperature condition of 70 ° C. using a ventilation oven with nitrogen circulation.
(Ii) The polyester film is stacked so as to come into contact with the resist layer, the polyester film is laminated on the resist layer using a rubber roller, and a photomask patterned with chromium metal is disposed thereon, Exposure was performed using an I-line stepper on the photomask.
(Iii) After peeling the polyester film from the resist layer, the resist layer was placed in a container containing the developer N-A5 and developed for about 1 minute. Then, it removed from the developing solution and washed with water for about 1 minute.
(Iv) The state of L / S (μm) (Line and Space) of the resist pattern prepared after development was observed at 1000 magnifications using a scanning electron microscope SEM. The resolution of the resist was evaluated according to the following criteria.
○: L / S = 10/10 μm can be clearly confirmed.
Δ: L / S = 10/10 μm cannot be clearly confirmed, but L / S = 15/15 μm can be clearly confirmed.
X: L / S = 15/15 μm cannot be clearly confirmed.

(10) Winding performance A film is slit to a width of 1000 mm and a length of 5000 m, wound on an FWP core having a length of 1100 mm, an inner diameter of 6 inches and a wall thickness of 7 mm, and the winding state is observed, and there are no appearance defects such as wrinkles. Things were accepted. Each 10 slits were made, and the winding performance was judged according to the following criteria.
Pass rate 90% or more: ◎
Pass rate 80% or more and less than 90%: ○
Pass rate 60% or more and less than 80%: △
Pass rate 50% or more and less than 60%: ×
Pass rate less than 50%: XX.

[Example 1]
(1) Preparation of polyester pellets (Preparation of polyester A)
Esterification reaction is carried out while distilling water at 255 ° C. with 86.5 parts by weight of terephthalic acid and 37.1 parts by weight of ethylene glycol. After completion of the esterification reaction, 0.02 part by weight of trimethyl phosphoric acid, 0.06 part by weight of magnesium acetate, 0.01 part by weight of lithium acetate, and 0.0085 part by weight of antimony trioxide were added. The polycondensation reaction was carried out by heating up to 0 ° C. to obtain polyester pellets having an intrinsic viscosity of 0.63 dl / g.
(Creation of polyester B, C and polyester D)
In addition, a water slurry of divinylbenzene / styrene copolymer crosslinked particles having a volume average particle diameter of 0.3 μm and a volume shape factor f = 0.51 obtained by a method for adsorbing monomers is substantially free of the above particles. A homopolyester pellet is contained using a vent type twin-screw kneader to obtain a master pellet containing 1% by weight of divinylbenzene / styrene copolymer crosslinked particles having a volume average particle diameter of 0.3 μm with respect to the polyester (polyester B). .

Master pellets containing divinylbenzene / styrene copolymer crosslinked particles having a volume average particle size of 0.45 μm and 0.8 μm were obtained in the same manner as the master pellets containing 1% by weight with respect to the polyester (polyester C and polyester D, respectively).
(Creation of polyester E)
In the production of polyester in the same manner as described above, after transesterification, the volume average particle size 0.2 μm, the volume shape factor f = 0.51, the volume average particle size 0.06 μm, the volume shape factor f = 0.51, the Mohs hardness No. 7 spherical silica was added and a polycondensation reaction was performed to obtain silica-containing master pellets containing 1% by weight of the particles with respect to the polyester (Polyester E). The spherical silica to be used was obtained by adding a mixed solution consisting of ethanol, pure water, and ammonia water as a basic catalyst to this mixed solution while stirring the mixed solution of ethanol and ethyl silicate, and the resulting reaction solution The mixture was stirred to carry out a hydrolysis reaction of ethyl silicate and a polycondensation reaction of this hydrolysis product, followed by stirring after the reaction to obtain monodispersed silica particles.

(Creation of polyester F)
Furthermore, calcium carbonate having an average particle diameter of 1.0 μm was prepared to prepare a 10% ethylene glycol slurry. This slurry was subjected to a dispersion treatment with a jet agitator for one hour, and was subjected to high-precision filtration with a filter having a collection efficiency of 95% of 5 μm or more.
Dimethyl terephthalate is added with 1.9 moles of ethylene glycol and magnesium acetate tetrahydrate and 0.055% phosphoric acid to perform transesterification, and the slurry containing calcium carbonate is added after the transesterification. Subsequently, 0.025% of antimony trioxide was added, the temperature was raised and the polycondensation reaction was performed by evacuation, containing 1% of calcium carbonate with an average particle size of 1.0 μm, containing calcium carbonate with an intrinsic viscosity of 0.63 dl / g Master pellets were obtained. (Polyester F).

(Creation of polyester G)
Further, δ-alumina is made into 10% ethylene glycol slurry as agglomerated alumina, pulverized and dispersed using a sand grinder, and further filtered using a 3 μm filter with a collection efficiency of 95%. Was added to the transesterification product prepared in the above, followed by addition of antimony trioxide, and a polycondensation reaction was performed to obtain master pellets having an intrinsic viscosity of 0.62 dl / g containing 2% of aggregated alumina. (Polyester G)
(2) Preparation of polyester pellets The polyester pellets to be supplied to the extruders of each of the layers A, B and C are prepared in the following ratio (composition). In addition, the ratio described below is a weight ratio (unit: weight%) with respect to the polyester pellet which comprises each layer.

A layer polyester A: 41.4
Polyester E: 10.0
Polyester G: 48.6.

B layer polyester A: 94.6
Polyester B: 2.4
Polyester D: 3.0.

C layer polyester A: 100
(3) Manufacture of biaxially oriented polyester film After stirring the raw materials prepared for each layer described above in a blender, the raw materials for layer A and B are the raw materials after stirring, and the vents for layer A and layer B The raw material of the C layer was dried under reduced pressure at 160 ° C. for 8 hours, and then supplied to the single screw extruder for the B layer. 3 which consists of layer A, layer B, and layer C after melt extrusion at 275 ° C. and filtration with a high-accuracy filter that collects 95% or more of foreign matters of 5 μm or more in a rectangular three-layer confluence block. Layer lamination was used. Thereafter, the film is wound around a casting drum having a surface temperature of 23 ° C. on a cooling roll through a slit die maintained at 285 ° C. by using an electrostatic application casting method, and solidified by cooling to obtain an unstretched laminated film.

  This unstretched film was stretched 4.2 times in the longitudinal direction at 110 ° C. using a stretching roll having a surface roughness Ra of 0.2 μm. At this time, the total contact time between the roll and the film in the stretching portion was 0.03 seconds. Further, after stretching 4.5 times in the width direction with hot air at 115 ° C. with a stenter, heat treatment was performed at 215 ° C. for 4 seconds under constant length, and then 0.1% in the longitudinal direction and 3.2% in the width direction. % Relaxation treatment was performed to obtain an intermediate product of a biaxially stretched film having a thickness of 16 μm. The intermediate product is slit with a slitter to obtain a roll of biaxially stretched film having a thickness of 16 μm. As a result of measuring the lamination thickness of the biaxially stretched film, the layer A was 1.01 μm, the layer B was 14.36 μm, and the layer C was 0.63 μm. The evaluation results of the obtained film are shown in Table 2.

[Examples 2 to 4, Comparative Examples 1 to 4]
Biaxial in the same manner as in Example 1 except that the composition of layers A, B, and C, the stretching ratio in the longitudinal direction, and the contact time between the roll and the film during stretching in the longitudinal direction are changed as shown in Table 1. An oriented laminated polyester film was obtained. The results of the laminated thickness of the obtained film are shown in Table 1, and the evaluation results of the film are shown in Table 2.

Since the biaxially oriented polyester film of the present invention has good transmission / reflection characteristics and slipperiness, it can be suitably used for a dry film resist support. Moreover, it can use suitably also for uses, such as a film for window pasting, the base film for waterless flat plates, the film for support bodies of a liquid crystal aligning film, using the reflective characteristic of this invention.

Claims (4)

A polyester film having a laminated structure of three or more layers,
The film haze is less than 1.0%,
The surface roughness SRa (A) of one surface (this surface is referred to as surface (A)) is 7 nm or less and SRz (A) is less than 100 nm,
The other surface (the surface is referred to as the surface (B)) has a surface roughness SRa (B) of 3 nm or more and less than 10 nm and SRz (B) of 100 nm or more and less than 700 nm.
A biaxially oriented polyester film for a dry film resist support, wherein the reflectance at wavelengths of 365 nm and 405 nm when light is incident from the surface (B) side is less than 14%. Particles are contained in the polyester layer having the surface (A) (this layer is referred to as A layer), and the maximum particle diameter DA of the particles is DA <0.4 μm,
Particles are contained in the polyester layer having the surface (B) (this layer is referred to as B layer), and the maximum particle diameter DB of the particles is 0.4 μm ≦ DB <1.0 μm,
And when it is set as thickness TB (micrometer) of B layer, it is DB / T <= 0.05, The biaxially-oriented polyester film for dry film resist supports of Claim 1 characterized by the above-mentioned. The biaxially oriented polyester film for dry film resist support according to claim 1 or 2, wherein a resist layer is laminated on the surface (A). The method for producing a biaxially oriented polyester film for a dry film resist support according to any one of claims 1 to 3, wherein the film is obtained by melt film formation by a coextrusion method.