WO2011111801A1 - Frame for large pellicle and large pellicle - Google Patents

Abstract

Disclosed is a frame for a large pellicle wherein handleability is satisfactory and occurrence of an air path is suppressed when used. In the frame for a large pellicle stretching and supporting a large pellicle film so as to cover the opening section, a frame section forming the rim of the opening section comprises junctions of at least three places along the axial direction of the frame section.

Description

Large pellicle frame and large pellicle

The present invention is used when manufacturing semiconductor devices such as IC (Integrated Circuit), LSI (Large Scale Integration), TFT LCD (Thin Film Transistor, Liquid Crystal Display), etc. The present invention relates to a frame for a large pellicle used for preventing foreign matter from adhering to a photomax or a reticle used in the lithography process.

Conventionally, in the manufacture of semiconductor circuit patterns and the like, dust-proof means called pellicles are disposed on both sides of a photomask or reticle to prevent foreign matter from adhering to the photomask or reticle.

As a general structure of a pellicle, a transparent thin film such as a polymer or glass is pasted on one side of a metal, ceramic, or polymer frame, and an adhesive layer for pasting on a mask on the opposite side. What provided (adhesive material) is mentioned. For example, a pellicle is formed from a transparent polymer film such as nitrocellulose or a cellulose derivative having a thickness of 10 μm or less on one edge surface of a frame having a thickness of several millimeters having a shape that matches the shape of a photomask or a reticle. A pellicle film is spread and bonded, and is attached to the other edge surface of the pellicle frame body on the surface of a photomask or reticle via an adhesive material.

When foreign matter adheres to the surface of a photomask or reticle, the foreign matter forms an image on the photoresist formed on the semiconductor wafer and causes a circuit pattern defect. However, the pellicle must be formed on at least the pattern surface of the photomask or reticle. When the is placed, the foreign substance adhering to the surface of the pellicle is out of focus, so that it does not form an image on the photoresist formed on the semiconductor wafer and the circuit pattern will not be defective.

In recent years, with the widespread use of various multimedia, there is a demand for a large pellicle applicable to a large photomask used in the photolithography process of a large color TFT LCD capable of high image quality and high definition display.

For example, Patent Document 1 proposes a large pellicle applicable to a large photomask.

Also, Patent Document 2 proposes a frame body using a reinforcing material having a larger elastic coefficient than that of the frame body and the frame body in order to cope with bending and distortion of the large pellicle frame body.

Patent Document 3 discloses a pellicle frame that is used for ultraviolet light exposure of 200 nm or less used in exposure that requires high resolution, and that does not affect the accuracy of mask flatness. It is also proposed to use a frame obtained by joining two or more types of materials having different elastic moduli in the thickness direction of the frame.

In addition, as a joint frame body in another field, Patent Document 4 discloses a frame for shielding a liquid crystal display.

JP 2001-109135 A JP 2006-284927 A JP 2009-063740 A JP 2005-141170 A

By the way, the pellicle frame is manufactured by punching a single sheet-like base material, and is often an integral type without a joint. This is based on the viewpoint of ensuring the flatness of the pellicle. However, depending on the flatness of the base material, there is a base material that cannot be used for manufacturing the pellicle frame. Further, although there is a base material having flatness, it is not easy to obtain the accuracy of the flatness of the pellicle frame as the size of the pellicle frame increases. For this reason, since the manufacturing process is time-consuming, the productivity is lowered and the cost of the pellicle frame is increased.

Also, as the size of the pellicle frame increases, the pellicle frame may be bent or distorted due to various factors such as the weight of the pellicle frame itself, the tension of the pellicle film, and the stress caused by the temperature change. For this reason, generally, a pellicle frame produced by punching out a single sheet-like base material having high rigidity is used.

Such bending or distortion of the pellicle frame is not preferable from the viewpoint of the handling property of the pellicle frame or pellicle. Further, when the pellicle frame is bent or distorted, an air path may be generated between the pellicle frame and the photomask or the like. In addition, such bending and distortion of the pellicle frame are caused by the tension of the pellicle film going inward after the pellicle film is attached to the pellicle frame. It is necessary to make it as small as possible because of the demand to secure it. On the other hand, there is a method of increasing the rigidity of the pellicle frame by increasing the cross-sectional area of the pellicle frame, but this method is not preferable in view of the effective exposure area.

In view of the above reasons, it is advantageous in terms of cost to use a divided frame (hereinafter referred to as “divided frame”) as a large pellicle frame. The present situation is that it has not been put into practical use as a product because it may bend or distort, and does not have sufficient rigidity characteristics to withstand practical use.

In this regard, in Patent Document 2 described above, in order to ensure rigidity, a member having higher rigidity than the pellicle frame body is joined to the joint portion of the divided frame body by a special method such as adhesive or friction stir welding. is doing. However, it is not easy to firmly bond members of different materials, and special processing is required for the joint portion such as the adhesive reservoir, and outgassing from the adhesive during the exposure occurs. There is concern and special welding techniques such as friction stir welding are required.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a large pellicle frame and a large pellicle that have good handling properties and can suppress the generation of an air path during use.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a frame for a large pellicle having a specific structure can solve the above problems, and have completed the present invention.

That is, the large pellicle frame according to the present invention is a large pellicle frame having a rectangular opening in plan view, and the frame forming the periphery of the opening is in the axial direction of the frame. A frame for a large pellicle having three or more joints along the frame.

Since the pellicle frame has three or more joint portions, each of the divided frame portions serves as a reinforcing material, and the flexure of the frame can be reduced synergistically. In other words, the overall rigidity of the pellicle frame will be increased, and bending can be suppressed. For example, when a large pellicle is fixed to a handling jig and inspection is performed, the pellicle can be handled in various directions. Hard to fall off the jig. Furthermore, since the rigidity is further increased, the accuracy of application is good when the image is applied to a photomask or the like, and the accuracy is maintained, so that an air path hardly occurs.

Furthermore, by forming the frame body with a plurality of members, it becomes possible to cut out a portion with good flatness of the base material, and the flatness of the frame body after joining is also improved. It is also possible to produce a large frame from a small base material, which has the advantage of cost reduction.

Conventionally, the pellicle frame has often been cut out from a single sheet-like base material based on the viewpoint of ensuring the flatness of the pellicle. The present invention has been made against such technical common sense and has the excellent effects as described above.

It is preferable that the joint portion is provided at a corner portion of the large pellicle frame.

The frame portion is made of at least one metal member selected from the group consisting of aluminum and an aluminum alloy. In the XRD measurement result of the axial cross section of the frame for a large pellicle, the peak intensity of the (111) plane / (200) The ratio of the peak intensity of the surface is preferably 1.0 or less.

Also, in the XRD measurement result of the axial section of the large pellicle frame, the ratio of the peak intensity of the (111) plane / the peak intensity of the (200) plane is preferably 0.8 or less.

Moreover, at least one convex part which protrudes toward the other member joined is provided in the edge part of one member joined in a junction part, and a convex part is fitted in the edge part of the other member. It is preferable that the recessed part to be made is provided, and the edge part of one member is joined to the edge part of the other member by fitting a convex part to a recessed part. In the present invention, “fitting” means that the convex portion is formed slightly larger than the concave portion, the concave portion is formed slightly smaller than the convex portion, or the convex portion and the concave portion are formed in the same size. When the convex portion is inserted into the concave portion and joined, the convex portion is compressed and deformed inward by the inner peripheral surface of the concave portion, or even if there is no compression deformation, the convex portion bites into the concave portion without a gap. It means a state that can be matched.

By adopting such a configuration, it becomes possible to bring the bending rigidity and shear rigidity to a level having no practical problem without using a reinforcing material, an adhesive, a special welding technique, or the like having rigidity higher than that of the frame. In addition, the stress concentration at the joint is alleviated due to inward bending due to the film tension after the film is attached to such a frame, so that gaps and backlash are less likely to occur at the joint. This is preferable because the shape is stable and the generation of dust due to looseness is small. For this reason, even when the inspection is performed with the large pellicle fixed to the handling jig, the pellicle hardly falls from the handling jig even when the position is changed in various directions.

Furthermore, it is preferable that the area of the opening is 1000 cm ² or more 35,000 ² or less.

And it is preferable that the joint strength in a joint part is 10 kgf or more. In this large pellicle frame, since the joint strength at the joint is 10 kgf or more, even if it is a divided frame, it is possible to suppress bending and distortion and to ensure rigidity.

Furthermore, it is preferable that the joining portion is formed by joining the end portions of the members to be joined with a chemical reaction type adhesive. In this way, by bonding the joint portion with a chemical reaction type adhesive, it is possible to improve the rigidity and dimensional stability of the frame for a large pellicle. By using a chemically reactive adhesive, the target dimensions such as the bonding angle and clearance can be adjusted, and the reaction can be started by an external stimulus, making it easy to maintain and fix the original position. Can be improved.

In this case, it is preferable that the chemically reactive adhesive includes at least one adhesive selected from the group consisting of an acrylic adhesive and an epoxy adhesive.

A large pellicle according to the present invention includes any of the large pellicle frames described above and a large pellicle film that is stretched and supported by the large pellicle frame so as to cover the opening.

According to the present invention, it is possible to provide a large pellicle frame, a pellicle, and a method for manufacturing a large pellicle frame that have good handling properties and can suppress the generation of an air path during use.

1 is a perspective view showing a large pellicle according to an embodiment. 1 is a plan view of a frame for a large pellicle according to an embodiment of the present invention. FIG. 3 is an enlarged perspective view showing the vicinity of a corner of the large pellicle frame shown in FIG. 2. It is a top view of the frame for large pellicles concerning other embodiments of the present invention. FIG. 5 is a partially enlarged perspective view showing an example of the vicinity of a corner of the large pellicle frame shown in FIG. 4. It is a top view of the frame for large pellicles concerning other embodiments of the present invention. FIG. 6 is an explanatory diagram for explaining a configuration of a joint portion of the large pellicle frame body shown in FIGS. 4 and 5. (A) is an enlarged view of the junction part of the frame for large pellicles shown in FIG. 6, (b) is an enlarged view which shows the modification. (A), (b), (c) is an enlarged view of a modification of the joint part of the pellicle frame according to each embodiment of the present invention. It is a schematic perspective view which shows the shape of the junction part in Example 2. FIG. It is an enlarged view of the junction part in a comparative example. It is an enlarged view of the junction part in a reference example. It is an enlarged view of the junction part in a reference example. It is an enlarged view of the junction part in an Example. It is an enlarged view of the junction part in a reference example. It is an expansion perspective view of the junction part (simple shape) of the frame for large pellicles concerning the embodiment of the present invention. It is an enlarged plan view of the joint (complex shape) of the frame for a large pellicle according to the embodiment of the present invention. It is an enlarged plan view of the joint (complex shape) of the frame for a large pellicle according to the embodiment of the present invention. It is an expanded side view of the junction part (complex shape) of the frame for large pellicles concerning the embodiment of the present invention. It is an expanded side view of the junction part (complex shape) of the frame for large pellicles concerning the embodiment of the present invention. It is an enlarged plan view of the joint (complex shape) of the frame for a large pellicle according to the embodiment of the present invention. (A), (b), (c) is an enlarged plan view of the joint (complex shape) of the frame for a large pellicle according to the embodiment of the present invention. It is an expansion perspective view of the junction part (complex shape) of the frame for large pellicles concerning the embodiment of the present invention. It is a figure which shows the chart of XRD which concerns on embodiment of this invention. It is a figure which shows the chart of XRD which concerns on the comparison form of this invention.

Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be described in detail. In addition, this invention is not limited to this following Embodiment, It can implement by changing variously within the range of the summary.

First, a pellicle according to an embodiment of the present invention will be described. FIG. 1 is a perspective view showing a large pellicle according to an embodiment of the present invention. The large pellicle 1 includes a large pellicle frame 2 and a large pellicle film 3 bonded and supported by the upper edge surface 2e of the large pellicle frame 2. Although not shown, the large pellicle 1 includes an adhesive layer applied to the lower edge surface of the large pellicle frame 2, and a protective film that adheres to the adhesive layer and protects the adhesive layer. Is further provided.

The large pellicle frame 2 is made of, for example, aluminum, aluminum alloys (5000 series, 6000 series, 7000 series, etc.), iron and iron alloys, ceramics (SiC, AlN, Al2O3, etc.), a composite material of ceramics and metal (Al -SiC, Al-AlN, Al-Al ₂ O ₃ etc.), carbon steel, tool steel, stainless steel series, magnesium alloy, polycarbonate resin, acrylic resin, etc. Yes. Since the large pellicle 1 is attached to the mask via the adhesive layer, a material having high rigidity and relatively small weight is preferable, and materials such as aluminum, aluminum alloy, magnesium alloy, and resin are preferable. The large pellicle frame 2 is configured by joining a plurality of members as described later, but at least the pair of members to be joined is preferably formed of a material having the same elastic modulus.

As the surface treatment of the large pellicle frame 2, anodizing, painting, paint coating, plating, low melting point glass frit, CVD, sputtering, etc. can be employed.

The large pellicle frame 2 is composed of a pair of opposed long sides 2a and 2b and a pair of opposed short sides 2c and 2d shorter than the long sides 2a and 2b, and has a rectangular opening. 4. In the large pellicle frame 2, the long side 2a and the long side 2b are formed to have the same length, and the short side 2c and the short side 2d are formed to have the same length. Area of the opening 4 is preferably 1000 cm ² or more, more preferably 3000 cm ² or more, more preferably 5000 cm ² or more, more preferably 10000 cm ² or more, particularly preferably 18000Cm ² or more, and most preferably be 23000Cm ² or more The upper limit is preferably 35000 cm ² or less.

A certain large pellicle frame 2 has a pair of long sides 2a and 2b made of a column member having a width of 16.5 mm, for example, and the length thereof is, for example, 1750 mm. Further, the pair of short sides 2c, 2d is formed of a column member having a width of 18.5 mm, for example, and the length thereof is, for example, 1550 mm. That is, the width of the short sides 2c and 2d is wider than the width of the long sides 2a and 2b in plan view (top view). The curvature of the corner (also referred to as the top) 5 of the large pellicle frame 2 is R = 20 mm. In addition, the vertex when it is assumed that there is no curvature in the corner 5 is hereinafter simply referred to as “vertex”. Grooves 7 are provided along the longitudinal direction (side direction) on the side surface 6 of the large pellicle frame 2.

The other large pellicle frame 2 has a pair of long sides 2a and 2b made of columnar members having a width of, for example, 9.0 mm, and the length thereof is, for example, 800 mm. Further, the pair of short sides 2c, 2d is formed of a columnar member having a width of 7.0 mm, for example, and the length thereof is, for example, 480 mm. That is, the width of the short sides 2c and 2d is narrower than the width of the long sides 2a and 2b in plan view (viewed from the top). The curvature of the corner 5 of the large pellicle frame 2 is, for example, R = 2 mm. Further, a groove portion 7 is provided along the longitudinal direction (side direction) on the side surfaces 6 of the short sides 2c and 2d of the large pellicle frame 2.

The large pellicle film 3 is made of a transparent polymer film such as nitrocellulose, a cellulose derivative, a fluorine polymer, or a cycloolefin polymer, and the thickness thereof is preferably, for example, 0.1 μm or more and 10 μm or less.

The large pellicle film 3 is stretched on the upper edge surface 2e so as to cover the opening 4 of the large pellicle frame 2, and is attached to and supported by the large pellicle frame 2.

Examples of the adhesive that bonds the large pellicle film 3 to the upper edge surface 2e of the large pellicle frame 2 include fluorine such as an acrylic resin adhesive, an epoxy resin adhesive, a silicone resin adhesive, or a fluorine-containing silicone adhesive. System polymers can be used.

In addition, as an adhesive material to support adhesion, styrene ethylene butylene styrene, styrene ethylene propylene styrene, or olefin-based hot-melt adhesive material, silicone adhesive material, acrylic adhesive material, or foam-based adhesive material Tape can be used. The thickness of the adhesive material layer is preferably set so that the total thickness of the large pellicle frame 2 and the adhesive material thickness does not exceed the prescribed distance between the large pellicle film 3 and the photomask. .01 mm or more and 10 mm or less is preferable.

Further, if a space exists inside the adhesive layer when the large pellicle film 3 is attached to the photomask, foreign matter may stay in the space. Therefore, when applying an adhesive to the lower edge surface of the large pellicle frame 2, considering that the pressure-sensitive adhesive layer is crushed and spread by the pressure applied when the large pellicle 1 is attached to the photomask, It is preferable to apply to the inside of the opening 4 of the large pellicle frame 2 so that the adhesive does not protrude into the opening 4 during pressurization. Specifically, it is preferable to apply so that the space inside the adhesive layer is within 0.35 times the application width of the adhesive layer. The application width of the pressure-sensitive adhesive layer is preferably 0.3 to 0.6 times the width of each side 2a to 2d of the large pellicle frame 2, and it extends along each side 2a to 2d of the large pellicle frame 2. It is preferable to apply.

As the protective film for protecting the adhesive material, a film made of polyethylene terephthalate resin or polyethylene resin can be used. Further, a release agent such as a silicone release agent or a fluorine release agent may be applied to the surface of the protective film according to the adhesive strength of the adhesive material. The thickness of the protective film is preferably, for example, 1 mm or less and 0.01 mm or more.

Next, the large pellicle frame 2 will be described with reference to FIG. FIG. 2 (eight divided structure) is a view (plan view) of the large pellicle frame 2 used in the large pellicle 1 shown in FIG. In FIG. 1, the description of the joint portion is omitted.

In the large pellicle frame 2, the frame portion constituting the peripheral portion of the opening 4 includes divided frame bodies 21 a and 21 b constituting the pair of long sides 2 a and 2 b, and both axial ends of the divided frame bodies 21 a and 21 b. Divided frame bodies 21e, 21h, 21f, 21g, which are provided in a continuous manner through the joints, and respectively form the four corners 5 of the large pellicle frame body 2, and the divided frame bodies 21e, 21h, 21f, The open ends of 21g are formed from divided frame bodies 21c and 21d that cross-link through a joint portion. That is, the large pellicle frame body 2 has eight joint portions along the axial direction of the frame portion constituting the peripheral edge portion of the opening 4. Thus, when providing a junction part near a corner | angular part, you may provide a junction part in the orthogonal | vertical direction or diagonal direction with respect to an axial direction.

In FIG. 2, the large pellicle frame 2 has a divided frame 21a, a divided frame 21d, and a divided frame 21f in the clockwise direction with the divided frame 21a as a base point and the opening axis of the opening 4 as a reference. The divided frame body 21b, the divided frame body 21g, the divided frame body 21c, the divided frame body 21h, and the divided frame body 21a are connected in this order. Here, in FIG. 2, the large pellicle frame body 2 having eight joints is shown, but the number of joints may be three or more, preferably 3 to 30, more preferably, 3 to 25 locations, more preferably 3 to 20 locations.

As described above, in the large pellicle frame 2, the long side 2a and the long side 2b have the same length, and the short side 2c and the short side 2d have the same length.

Moreover, the shape of the division | segmentation frame 21a and the division | segmentation frame 21b is substantially the same, the shape of the division | segmentation frame 21c and the division | segmentation frame 21d is substantially the same, and also the division | segmentation which forms the corner | angular part 5 respectively. The shapes of the frames 21e, 21h, 21f, and 21g are also substantially the same. Specifically, in FIG. 2, the length of the divided frame bodies 21a and 21b is, for example, 700 mm, and the length of the divided frame bodies 21c and 21d is, for example, 380 mm.

The distance between at least one of the joints and the corner closest to the joint is preferably 45% or less, more preferably 35% of the length of the side where the joint is provided. Hereinafter, it is more preferably 25% or less, and the lower limit is preferably 0% or more, more preferably 5% or more. Here, it is more preferable that two of the joint portions are provided via a common corner portion, and that the distance between the corner portion and the joint portion is within the above range.

The long side length Le is defined as the maximum distance in the long side axis direction at the opposing short side, and the short side length Ls is defined as the maximum distance in the short side axis direction at the opposing long side. Is done.

Further, the distance Lp between the joint and the corner closest to the joint is the distance between the point farthest from the center of the opening 4 and the vertex on the end face of the divided frame forming the corner. Is defined as

Specifically, in FIG. 2, the length of the divided frame bodies 21a and 21b is 875 mm, for example, and the length of the divided frame bodies 21c and 21d is 775 mm, for example. Therefore, Lp is, for example, 25% of the length of Le, and Lp is, for example, 25% of the length of Ls.

The length of the divided frame is defined as the maximum length along the circumferential direction of the frame (frame portion axis direction) between both end faces of the divided frame.

FIG. 3 is an enlarged perspective view showing the vicinity of the corner of the large pellicle frame 2 shown in FIG. The corner 5 in the large pellicle frame 2 includes, for example, a divided frame 21b that constitutes a part of the long side 2b, a divided frame 21d that constitutes a part of the short side 2d, and a substantially right angle therebetween. It is formed from divided frame bodies 21f provided continuously in the direction.

Here, convex portions are respectively formed on the end surface of the divided frame body 21b and the end surface of the divided frame body 21d, and concave portions corresponding to the convex shape are respectively formed on both end surfaces of the divided frame body 21f. Each of the members is connected with the convex portion in close contact with the concave portion. In addition, these division | segmentation frame bodies can be joined by apply | coating an adhesive agent etc. to a contact surface suitably.

The width of each side 2a to 2d of the frame 2 for the large pellicle 2 is preferably as thin as possible from the viewpoint of securing the exposure area. However, if the width is too small, the width of the large pellicle film 3 is increased due to the tension of the large pellicle film 3. There is a risk that the pellicle frame 2 is bent. Therefore, the width of each side 2a to 2d can be set to about 3 mm to 25 mm so that the width of each side takes into account the rigidity.

Further, as the thickness of the large pellicle frame 2 is reduced, the thinner the pellicle 1 is, the lighter and easier to handle. There is a possibility that a problem that 2 is bent occurs. Therefore, the thickness of the large pellicle frame body 2 can be preferably about 3.5 mm to 12 mm from the balance between the two sides according to the lengths of the sides 2a to 2d.

The present invention is not limited to the embodiment described above. For example, in the above embodiment, the shapes of the divided frame bodies are aligned to some extent, but the shapes of the divided frame bodies may be different from each other. In the above-described embodiment, eight joint portions are provided, but four joint portions may be provided. In this case, for example, the divided frame bodies 21c, 21h, and 21g can be formed as one divided frame body, and the divided frame bodies 21e, 21d, and 21f can be formed as one divided frame body.

Also, the joining method at the joint is not particularly limited, and an adhesive may be used in addition to an adhesive, or a screw may be used.

The large pellicle frame body is a large pellicle frame body having a rectangular opening in a plan view, and has a member that forms a peripheral edge of the opening by joining the ends together. The end of one member is provided with at least one protrusion that protrudes toward the other member to be joined, and the end of the other member is provided with a recess for fitting the protrusion. It is preferable that the end of one member is joined to the end of the other member by fitting the convex portion into the concave portion.

In this embodiment, “fitting” means that the convex portion is formed slightly larger than the concave portion, the concave portion is formed slightly smaller than the convex portion, or the convex portion and the concave portion have the same size. When the convex portion is formed and inserted into the concave portion and joined, the convex portion is compressed inward by the inner peripheral surface of the concave portion, or even if there is no compressive deformation, the convex portion has no gap in the concave portion. It means a state that can be engaged.

By adopting such a configuration, it is possible to reduce the bending rigidity and shear rigidity to practically no problem levels without using stiffeners, adhesives, special welding techniques, etc., which are more rigid than large pellicle frames. Become. In addition, stress concentration at the joint is reduced due to inward bending due to film tension after the large pellicle film is attached to the frame for such a large pellicle, resulting in gaps and backlash at the joint. It is preferable because the size and shape are stable, and the generation of dust due to looseness is small. Therefore, even when the position is changed in various directions when inspection is performed with the large pellicle fixed to the handling jig, the large pellicle is not easily dropped from the handling jig.

Also, by using a member (frame body having a joint) rather than cutting out from a single piece of base material, the number of cutting processes is reduced, and the residual stress applied to the frame body during processing is reduced. In addition, considering the anisotropy of the material, the divided frame body can use members having the same directionality, so that the anisotropy of the entire frame body is reduced. Since residual stress and anisotropy are thus reduced, the release due to stress distortion during the heating process in the large pellicle manufacturing process is reduced, and the size (thermal dimension) of the large pellicle is stable, which is preferable. For this reason, it is not necessary to perform heat treatment or the like in advance in order to release the residual stress, and there is a manufacturing merit that the number of processes is reduced. Further, since the stress strain tends to open in the course of time, the divided frame body having a small residual stress is preferable because the dimensions are stable even when stored for a long period of time.

In particular, when the frame is made of a metal member, the ratio of the peak intensity of the (111) plane / the peak intensity of the (200) plane is 1.0 or less in the XRD measurement result of the axial cross section of the pellicle frame. It is preferable. The fact that the peak intensity of the (200) plane is dominant means that the crystals of the metal member are arranged more evenly in the plane direction perpendicular to the axial direction of the pellicle frame (isotropic property). Increases and decreases anisotropy). Accordingly, since the internal stress at the time of molding becomes smaller, it becomes easier to form a frame body having excellent dimensional stability. In addition, when the frame is heated, the internal stress is small and the crystals are aligned in the plane direction perpendicular to the axial direction, so the stress is easily released and distortion is not easily generated. .

The ratio of the peak intensity of the (111) plane / the peak intensity of the (200) plane is more preferably 0.8 or less, and further preferably 0.4 or less.

Here, the peak of the (111) plane is a diffraction peak having a diffraction angle (2θ) in the range of 37.0 to 39.5 degrees in the X-ray diffraction measurement using Cu—Kα ray, (200) The surface peak is a diffraction peak in the range of 43.0 to 45.5 degrees in the X-ray diffraction measurement using Cu—Kα ray.

Furthermore, by forming the frame body with a plurality of members, it becomes possible to cut out portions with good flatness of the base material, and the flatness of the frame body after joining is also improved. It is also possible to produce a large frame from a small base material, which has the advantage of cost reduction.

In the large pellicle frame, it is preferable from the viewpoint of dimensional stability that the maximum lateral dimension (t) on the base side of the convex portion is shorter than the maximum lateral dimension (v) on the tip side. Further, the maximum lateral dimension (t) on the base side of the convex part is set to a length of 5% to 80% with respect to the width of the member on which the convex part is provided, and the maximum lateral dimension (v ) Is preferably set to a length of 10% to 90% with respect to the width of the member provided with the convex portion. Here, although the numerical value may be changed depending on the positioning of the member in the width direction, the measurement position in the width direction is not particularly limited, and it is sufficient that the above condition is satisfied by any measurement position in the width direction. It should be noted that the width dimension may be within the above numerical range in either one of the width on the large pellicle film surface side and the width on the mask adhesive side.

In the large pellicle frame, the maximum lateral dimension (t) on the base side of the convex portion is set to a length of 5% to 80% with respect to the thickness of the member on which the convex portion is provided. It is preferable to set the maximum lateral dimension (v) on the tip side to a length of 10% to 90% with respect to the thickness of the member provided with the convex portion. Here, it is assumed that the numerical value may change depending on the positioning of the member in the thickness direction, but there is no particular limitation on the measurement position in the thickness direction, and the above condition may be satisfied by any measurement position in the thickness direction. That's fine.

The maximum lateral dimension (t) on the base side of the convex part is the maximum dimension of the base part where the convex part is connected to the joining end surface of the member (for example, two points as shown in FIG. 7A in plan view). The maximum lateral dimension (v) on the tip side of the convex part means the tip side part of the convex part in the direction substantially perpendicular to the longitudinal direction of the member (the part excluding the root part) ) Means the maximum dimension.

Also, it is preferable to have three or more joints because it is easy to adjust the flatness. By using three or more places in this way, it becomes possible to increase the accuracy of flatness more easily than a single base material by increasing the processing accuracy of each part constituting the frame for a large pellicle. The dimensional accuracy will increase.

Further, in the frame for a large pellicle, the convex part has an excessive outer peripheral part that is compressed and deformed inward by the inner peripheral surface of the concave part when fitted with the concave part, or the concave part is fitted with the convex part. A surplus outer peripheral portion that is compressed and deformed inward by the outer peripheral surface of the convex portion at the time of joining. By adopting such a configuration, by fitting the end portions of the members from above and below, the excess outer peripheral portion is crushed and bulged outward, so that each joining portion is tightly and firmly joined without a gap. Therefore, bending rigidity, shear rigidity, and the like are increased without using a reinforcing material having higher rigidity than the frame. Further, since there is an extra outer peripheral portion, no adhesive is required, and there is no worry of outgassing during exposure. It is preferable that the dimension of the excess outer peripheral part is at least 0.001 mm or more (for example, 0.005 mm or more and 0.1 mm or less). In addition, an adhesive etc. can also be used when a surplus outer peripheral part is about 0 mm.

FIG. 4 shows an example (another embodiment) of a large-sized pellicle frame configured using a different divided frame from that in FIG. FIG. 4 shows an example of a four-divided frame body. In the large pellicle frame body 2, the frame portion constituting the peripheral portion of the opening 4 is a divided frame that is a member constituting each of the pair of long sides 4a and 4b. The body 41a and 41b and the division | segmentation frame bodies 41c and 41d which are the members which respectively comprise a pair of short sides 4c and 4d are formed. That is, the large pellicle frame body 2 has four joint portions along the axial direction of the frame portion constituting the peripheral edge portion of the opening 4. In the large pellicle frame 2, the long sides 4 a and the long sides 4 b are formed to have the same length, and the short sides 4 c and the short sides 4 d are formed to have the same length.

FIG. 5 is an enlarged perspective view showing an example of the vicinity of the corner of the large pellicle frame shown in FIG. By using a joint as shown in FIG. 5, it maintains rigidity and dimensional stability that have no practical problems as a frame for a large pellicle without using a member or adhesive that has higher rigidity than the frame, Yield can be improved.

FIG. 6 also shows an example (another embodiment) of a large-sized pellicle frame configured using a different divided frame from that in FIG. The large pellicle frame body 2 shown in FIG. 6 has an eight-divided structure and is configured by joining eight divided frame bodies. In the large pellicle frame 2, the frame portion constituting the peripheral portion of the opening 4 includes divided frame bodies 51 a, 51 a ′, 51 b, 51 b ′ which are members constituting the pair of long sides 5 a, 5 b, respectively. It is formed from divided frame bodies 51c, 51c ′, 51d, 51d ′ which are members constituting the pair of short sides 5c, 5d, respectively. That is, the large pellicle frame body 2 has eight joint portions along the axial direction of the frame portion constituting the peripheral portion of the opening 4. In the large pellicle frame 2, the long sides 5a and the long sides 5b are formed to have the same length, and the short sides 5c and the short sides 5d are formed to have the same length.

In the large pellicle frame body according to the embodiment shown in FIGS. 2 to 5, the shape in which the joint portion is provided in the vicinity of the corner portion is illustrated as an example. However, as shown in FIG. It may be provided. Although it is preferable to provide at each necessary portion on each side because thermal expansion due to heating or the like in the large pellicle manufacturing process can be mitigated at the joint, it is more preferable to provide the joint near the corner.

In the frame for a large pellicle according to the embodiment shown in FIG. 2, two long-side members constituting a pair of opposed long sides and two short-side members constituting a pair of opposed short sides And the corner member constituting the four corners, the ends of the long side member and the short side member are respectively joined to the corner member, and the long side is interposed via the corner member. It is good also as a frame body of the planar view rectangle shape by connecting the member for short and the member for short sides.

Also, in the large pellicle frame according to the embodiment shown in FIG. 4 or FIG. 5, two long side members constituting a pair of opposed long sides and two constituting a pair of opposed short sides. And the ends of the long side member and the short side member may be joined to each other to form a rectangular frame body in plan view. Thus, by having a joint part in each corner | angular part, a joint part can be arrange | positioned in the corner | angular part vicinity of planar view rectangular shape. And, when the joint is provided near the corner, since one side is cut out, the productivity becomes high, and it is equivalent to a cut from one base material by joining the vicinity of the corner with high rigidity. Further, it is preferable because the corner portion has a right-angled corner, so that the effective exposure area during exposure can be maintained (the dimension is stabilized).

FIG. 7 is an enlarged view of the joint portion of the large pellicle frame according to the embodiment shown in FIGS. 4 and 5. Moreover, Fig.8 (a) is an enlarged view of the junction part of the frame for large pellicles which concerns on embodiment shown in FIG. 6, FIG.8 (b) is the modification. FIG. 9 is an enlarged view of a modified example of the joint portion of the large pellicle frame according to each embodiment. In FIG. 9, any of (a), (b), and (c) can be taken. Further, these are merely examples, and do not limit the shape of the joint.

As shown to Fig.7 (a), in the frame for large pellicles which concerns on each embodiment of this invention, the other member (division | segmentation) joined to the edge part of one member (division | segmentation frame body) joined. At least one convex portion P protruding toward the frame body is provided, and a concave portion C into which the convex portion P is fitted is provided at the end of the other member (divided frame body). Then, by fitting the convex portion P into the concave portion C, the end portion of one member (divided frame body) is joined to the end portion of the other member (divided frame body).

By forming the joint portion into a fitting portion in this way, the bending rigidity and shear rigidity of the joint portion are at a level where there is no practical problem, and the frame body bends inward when a large pellicle film is attached. However, in this case as well, stress concentration is alleviated, so that gaps and backlash at the joints are less likely to occur, and the dimensions are stable even when a divided frame is used.

In the frame for a large pellicle according to the present embodiment, as shown in FIG. 7, the maximum lateral dimension t of the root side portion of the convex portion P provided on the end portion (joint end surface s) of one member is It is preferable to set it so as to be shorter than the maximum lateral dimension v of the tip side portion of this convex portion P (the portion that fits into the concave portion C formed in the joint portion u of the other member). Such a structure may be in the width direction of the member (divided frame) or in the thickness direction. If it is in the width direction, it is more preferable to prevent the frame from being bent to the inner side after the film is stretched. If it is in the thickness direction, even if the inner wall or the outer wall is raised, the mask adhesion The width direction in which the material or the film adhesive is applied is preferable because it becomes flat.

The maximum lateral dimension t on the base side of the convex portion P is preferably set to a length of 5% to 80% with respect to the width of the member on which the convex portion P is provided. Further, it is preferable that the maximum lateral dimension v on the tip side of the convex portion P is set to a length of 10% to 90% with respect to the width of the member on which the convex portion P is provided. Further, the maximum lateral dimension t on the base side of the convex portion P is more preferably set to a length of 7% to 60% with respect to the width of the member, and is set to a length of 10% to 40%. Is more preferable. The maximum lateral dimension v on the tip side of the convex portion P is more preferably set to a length of 15% to 75% with respect to the width of the member, and is set to a length of 20% to 50%. Is more preferable. In addition, each said maximum horizontal dimension has shown the sum total of each maximum joining distance, when there exist with respect to the width | variety of a junction part.

When the maximum lateral dimension t on the base side of the convex portion P is smaller than 5% with respect to the width of the member, the catch at the joint portion (fitting portion) is weak, and the right and left tensile strength may be lowered, When the large pellicle film is attached, bending stress toward the inside of the frame body is not preferable because concentrated stress is applied to the joining end surface joining portion, and gaps and backlash may occur at the joining end surface portion. Further, when the maximum lateral dimension t on the base side of the convex portion P is larger than 80% with respect to the width of the member, the convex portion P is crushed and bulged outward when fitted from above and below. The inner and outer surfaces of the body may rise, which is not preferable. Furthermore, when the maximum lateral dimension v on the tip side of the convex portion P is smaller than 10% with respect to the width of the member, the catch at the joint (fitting portion) is weak and the right and left tensile strength may be reduced. Or when bending a large pellicle film to the inside of the frame, concentrated stress is applied to the joint end face joint, which may cause gaps and backlash at the joint end face. . Further, when the maximum lateral dimension v on the front end side of the convex portion P is larger than 90% with respect to the width of the member, the convex portion P is crushed and bulged outward when fitted from above and below. The inner and outer surfaces of the body may rise, which is not preferable.

Further, it is preferable that the maximum lateral dimension t on the base side of the convex portion P is set to a length of 5% to 80% with respect to the thickness of the member (divided frame body) on which the convex portion P is provided. Further, it is preferable that the maximum lateral dimension v on the tip side of the convex portion P is set to a length of 10% to 90% with respect to the thickness of the member (divided frame body) on which the convex portion P is provided. Further, the maximum lateral dimension t on the base side of the convex portion P is more preferably set to a length of 7% to 60% with respect to the thickness of the member, and is set to a length of 10% to 40%. Is more preferable. The maximum lateral dimension v on the tip side of the convex portion P is more preferably set to a length of 15% to 75% with respect to the thickness of the member, and is set to a length of 20% to 50%. Is more preferable. In addition, each said maximum horizontal dimension has shown the sum total of each maximum joining distance, when there exist two or more with respect to the thickness of a junction part.

When the maximum lateral dimension t on the base side of the convex portion P is smaller than 5% with respect to the thickness of the member, there is a possibility that the joint portion is easily loosened when the large pellicle membrane is bent inward due to the film tension. This is not preferable. Further, when the maximum lateral dimension t on the base side of the convex portion P is larger than 80% with respect to the thickness of the member, the convex portion P is crushed and bulged outward when fitted from the left and right. The upper and lower side surfaces of the frame body may rise, which is not preferable. Furthermore, when the maximum lateral dimension v on the tip side of the convex portion P is smaller than 10% with respect to the thickness of the member, the joint portion may be easily loosened when bent inward due to the film tension of the large pellicle film. It is not preferable because of its properties. Further, when the maximum lateral dimension v on the tip side of the convex portion P is larger than 90% with respect to the thickness of the member, the convex portion P is crushed and bulges outward when fitting from the left and right. The upper and lower side surfaces of the frame body may rise, which is not preferable. When the upper and lower side surfaces rise, it is not preferable because the flatness of the frame body is deteriorated and the attaching accuracy may be deteriorated.

As the shape of the convex portion P, a round pierced shape, a wedge shape, a square shape, a triangular shape, and other various shapes (such as shapes used in a jigsaw puzzle) can be adopted. The number of the convex parts P may exist from one to a plurality with respect to the width and thickness of the member (divided frame body). In the case of one piece, stress is concentrated on the starting end portion from the joint end face with respect to the inward bending of the frame body, so there is a possibility that a gap or a gap is left on the joint end face. For this reason, the end surface of the joint portion may be joined by another joining method in an auxiliary manner with caulking, an adhesive, or the like. Since the frame for a large pellicle is not so large in width and thickness, it is preferably 1 to 4, more preferably 1 to 2.

In addition, when the convex part P of a special shape as shown in FIG. 9C is adopted, the maximum lateral dimension t of the root side part of the convex part P is the maximum lateral dimension of the tip side part of the convex part P. It can also be set to the same length as v.

Further, in the large pellicle frame according to the present embodiment, the protrusion P provided at the end of one member to be joined is the end of the other member to be joined as shown in FIG. And an excessive outer peripheral portion (hereinafter referred to as “joining gap”) G that is compressed and deformed inward by the inner peripheral surface of the concave portion C when fitted with the concave portion C provided in the inner portion. The dimension of the bonding gap G is preferably 0.1 mm or less. When joining, fitting is performed from the top and bottom or from the left and right. Since this joining gap G is crushed and swelled outward when fitting, close joining is possible. If the size of the bonding gap G is larger than 0.1 mm, the portion to be crushed becomes large, and the frame body rises in the vertical and horizontal directions, which is not preferable. By having this bonding gap G, an adhesive or the like is not required, and it is possible to bond firmly only by fitting. The dimension of the bonding gap G is preferably 0.005 mm to 0.06 mm, and more preferably 0.01 mm to 0.04 mm.

In addition, even when a large pellicle frame is used as a split frame, it is possible to maintain rigidity and dimensional stability without using a highly rigid member or the like at the joint, and to improve the yield, It is preferable that the bonding strength at the portion is 10 kgf or more. By setting it as 10 kgf or more, even if it is a division | segmentation frame, while being able to suppress a bending and a distortion, rigidity can be ensured. Moreover, by comprising with the divided | segmented frame member, a dimension can be adjusted easily, while being able to ensure a dimensional accuracy, a manufacturing process can be simplified. Therefore, it is possible to easily obtain the same dimensional accuracy as that of the frame body having no joint portion. Therefore, even if it is a case where it is set as a division | segmentation frame, while being able to maintain rigidity and dimensional stability, without using a highly rigid member etc. for a junction part, a yield can be improved.

In addition, by using the divided frame body, the number of man-hours for cutting is reduced as compared with cutting out from a single sheet-like base material, and the residual stress applied to the frame member during processing is reduced. Further, considering the anisotropy of the material, since the frame member having the same direction can be used, the anisotropy of the entire large pellicle frame is reduced. Since the residual stress and anisotropy are thus reduced, the release due to stress strain or the like during the heating process in the large pellicle manufacturing process is reduced, and the dimensions of the large pellicle are stabilized. For this reason, it is not necessary to perform a heat treatment or the like in advance in order to release the residual stress, and there is a manufacturing advantage that the number of processes is reduced. In addition, since the stress strain tends to open in the course of time, the divided frame body having a smaller residual stress can ensure dimensional stability even when stored for a long period of time.

Furthermore, by forming a large pellicle frame with a plurality of frame members, it becomes possible to cut out portions with good flatness of the base material, and the flatness of the large pellicle frame after joining is also improved. . Moreover, it is possible to produce a large frame for a large pellicle from a small base material, which has an advantage of cost reduction.

It is preferable that the joining portion is composed of a convex portion formed at one end portion of the frame member and a concave portion joined to the convex portion formed at one end portion of the frame member. By setting it as such a structure, the joint strength of a junction part can be favorably 10 kgf or more.

The joined portion is preferably joined by any one of fitting, adhesive, and caulking. By using these bonding methods, the bonding strength of the bonding portion can be sufficiently ensured.

The frame member is configured such that a pair of opposed long sides and a pair of opposed short sides form a corner portion, and at least one of the joint portions and a corner portion closest to the joint portion. The distance between them is preferably 45% or less of the length of the side where the joint is provided. According to such a configuration, since the frame body is rectangular and the vicinity of the corner portion has high rigidity, the rigidity can be maintained by arranging the joint portion in the vicinity of the corner portion, and the large pellicle frame body is bent. Etc. can be suppressed. In addition, by providing a joint in the vicinity of the corner, the right angle is improved and the rectangular shape is maintained, so that the amount of deflection of the large pellicle frame is within the tolerance range (0% to 3%). be able to.

Also, the large pellicle film is attached to the large pellicle frame by applying a load to the large pellicle frame, but this load differs from 10 kgf to 70 kgf depending on the apparatus. Therefore, it is necessary to take measures to prevent the joint from being deformed by different loads depending on the apparatus. Further, when the shape of the frame for the large pellicle is deviated from a predetermined dimension, the joint is locally subjected to a load because the dimensions are corrected, and the joint may be deformed. In order to solve these problems, the joint strength of the joint is preferably 10 kgf or more, more preferably 15 kgf or more, and further preferably 25 kgf or more.

As a joining method that achieves the joining strength of the joining part as described above and can be used from the exterior as a large pellicle, it is preferable to fit a divided frame or use an adhesive. When making it fit, the shape which provided the convex part in the edge part of joining, and the recessed part made to fit in the other edge part is preferable. Furthermore, a shape in which the root dimension (proximal end side dimension) of the convex portion is smaller than the maximum lateral dimension on the distal end side is more preferable because it is resistant to tension in the length direction.

As described above, in the large pellicle frame body of the large pellicle, the joint strength at the joint portion of the divided frame body is set to 10 kgf or more. Therefore, even in the divided frame body, bending and distortion can be suppressed and rigidity can be suppressed. Can be secured. In addition, by configuring the large pellicle frame body with the divided frame body, the dimensions can be easily adjusted, the dimensional accuracy can be ensured, and the manufacturing process can be simplified. Therefore, the same dimensional accuracy as that of the frame body having no joint portion can be easily obtained. Therefore, when the divided frame is used, rigidity and dimensional stability can be maintained and yield can be improved without using a highly rigid member or the like for the joint portions 22a to 22h. In particular, when the large pellicle 1 is large, the configuration of the present embodiment is more effective.

The frame part of the frame for a large pellicle according to the present invention may have the ends of the frame part joined together with a chemical reaction type adhesive. As the adhesive, for example, a fluorine-based polymer such as an acrylic resin adhesive, an epoxy resin adhesive, a silicone resin adhesive, or a fluorine-containing silicone adhesive can be used. In addition, as an adhesive material to support adhesion, styrene ethylene butylene styrene, styrene ethylene propylene styrene, or olefin-based hot melt adhesive material, silicone adhesive material, acrylic adhesive material, or foam-based adhesive material A tape, a foamed hot melt, or the like can be used.

The thickness of the adhesive material layer is preferably set so that the total thickness of the large pellicle frame 2 and the adhesive material thickness does not exceed the prescribed distance between the large pellicle film 3 and the photomask. , 0.01 mm or more and 10 mm or less is preferable.

Further, if a space exists inside the adhesive layer when the large pellicle film 3 is attached to the photomask, foreign matter may stay in the space. Therefore, when applying an adhesive to the lower edge surface of the large pellicle frame 2, considering that the pressure-sensitive adhesive layer is crushed and spread by the pressure applied when the large pellicle 1 is attached to the photomask, It is preferable to apply to the inside of the opening 4 of the large pellicle frame 2 so that the adhesive does not protrude into the opening 4 during pressurization. Specifically, it is preferable to apply so that the width of the space inside the adhesive layer is within 0.35 times the application width of the adhesive layer. The application width of the pressure-sensitive adhesive layer is preferably 0.3 to 0.6 times the width of each side 2a to 2d of the large pellicle frame 2, and is applied to each side 2a to 2d of the large pellicle frame 2. It is preferable to apply along. As a protective film for protecting the adhesive material, a film made of polyethylene terephthalate resin or polyethylene resin can be used. Moreover, according to the adhesive force of an adhesive material, you may apply | coat a mold release agent, for example, a silicone type release agent, or a fluorine type release agent to the surface of a protective film. As for the thickness of a protective film, 0.01 mm or more and 1 mm or less are preferable, for example.

Since the frame having three or more joints can divide at least the members constituting the frame into two or more, the processing accuracy and dimensional accuracy of each part constituting the large pellicle frame in the manufacturing process As a result, it is possible to improve the dimensional accuracy of the frame body as compared with the case where there is a single joint. Therefore, by making it easy to control the dimensional accuracy of the frame itself, it becomes easy to control the amount of flexure of the frame body when the large pellicle film is attached to the frame body. It becomes possible to improve the dimensional stability. Here, each member is preferably as small as possible, that is, as the frame body is made of a large number of members, it is preferable from the viewpoint of processing variations.

Also, it is possible to improve the rigidity and dimensional stability of the frame by bonding the joint with a chemically reactive adhesive. By using a chemically reactive adhesive, the target dimensions such as the bonding angle and clearance can be adjusted, and the reaction can be started by an external stimulus, making it easy to maintain and fix the original position. Can be improved.

Among these, the adhesive is preferably in a liquid state, and when a liquid adhesive is used, the adhesive penetrates into the joint portion, and the liquid spreads throughout the joint portion, which is preferable from the viewpoint of manufacturing and rigidity. Further, among the liquids, an acrylic or epoxy adhesive is preferable. Acrylic adhesive is an adhesive whose chemical monomer before reaction has the following chemical formula (1). Among them, UV curable adhesives that cure by ultraviolet rays, thermosetting adhesives that cure by heat, block air An anaerobic curable adhesive that cures by heating, a cyanoacrylate (R = CN) type instantaneous adhesive that initiates reaction with a minute amount of moisture as an initiator is more preferred (R is H or C).

In addition, as an epoxy-based adhesive, there are a one-component type and a two-component type, which can be used, but a one-component type epoxy-based thermosetting type adhesive is more suitable than a two-component type epoxy-based thermosetting adhesive. An adhesive is preferable because it is effective in the pellicle manufacturing process. The total amount of the adhesive actually used is very small, and the one-pack type adhesive is preferable to the two-pack type adhesive because it is not necessary to use it while being aware of measurement / mixing and pot life. When using the two-component type, use more adhesive than necessary to increase the measurement accuracy, which may place a burden on the environment. Tends to decrease, and if the time from the measurement to the start of the reaction is not constant, the reactivity will vary. For this reason, a difference occurs in the degree of curing, and a difference in physical properties may occur. The difference in the degree of cure may cause the adhesive thickness to be non-uniform depending on the joint location, cause distortion, or cause dimensional variation. If you need caution. However, as an effective adhesive even in the two-pack type, a modified acrylic adhesive can be used for acrylic and a thermosetting adhesive can be used for epoxy. Although the modified acrylic adhesive is a two-component type, it does not need to be mixed, and can be cured by applying one solution to each of the surfaces to be joined and press-bonding them.

Furthermore, from the viewpoint of light resistance, an acrylic adhesive is preferable. Specifically, Three Bond 2247, 2242, 2249G (all manufactured by ThreeBond), Three Bond 2083, 2081D, 2082C, 2087L (both manufactured by ThreeBond) Manufactured), Three Bond 3923, 3928, 3920, 3925B, 3922, 3926, 3055, 3097 (all manufactured by ThreeBond), Aron Alpha series (manufactured by Tokyo Gosei Co., Ltd.), Three Bond 1735, 1721, 1797, 17X-050, 1796 1735 (all manufactured by Three Bond), Loctite® 638, “Loctite® 601” (both manufactured by Henkel Japan), Three® Bond1401 series (manufactured by Three Bond), and the like are preferable.

Among the acrylic pressure-sensitive adhesives, an anaerobic curable adhesive whose reaction is accelerated by blocking air is more preferable. Specific anaerobic curable adhesives include Loctite®638 and Loctite®601 (both manufactured by Henkel Japan). An anaerobic curable adhesive is preferable because the reaction is unlikely to occur at the portion protruding from the joint, and it can be easily wiped off, so that outgas and dust generation can be minimized and the joint is also strong. In particular, the use of an anaerobic curable adhesive makes it extremely difficult for reactions to occur, and it is noteworthy that outgassing and dust generation can be minimized. This is because there is no field that has been required to suppress outgassing as an adhesive, and the present inventors have found an anaerobic curable adhesive having an effect of preventing haze caused by outgassing.

As a joining method other than the adhesive used in the present invention, caulking may be used to reinforce the adhesive. Use of an adhesive is preferable because various bonding shapes are possible and the bonding strength can maintain a practically usable level of rigidity. On the other hand, when joining by laser welding without using an adhesive, the joining strength is high, but unevenness is produced in the joined portion, so that only the joined portion is extremely poor in flatness and the appearance is not preferable. In addition, when joining by shrinkage without using an adhesive, the appearance is good because extra pressure such as pressing is not required when mating, but in the case of an aluminum alloy with high thermal conductivity, shrinkage shrinkage is required. This is not preferable because the effect of the above cannot be expected and the bonding strength may be lowered. Cooled swallows are preferable because they have the same effect as fried swallows.

The shape of the joining portion may be any shape as long as the thickness of the adhesive to be joined is 1.0 mm or less. The planar shape of the bonded portion (the shape when the bonded portion is viewed from above or from the side) is preferably a complex shape rather than a simple shape. Here, the simple shape means that the planar shape of the joint J is a straight line extending in a direction substantially perpendicular to the length direction of the member, as shown in FIG. Further, the complex shape means a shape having a relatively large adhesion area as compared with a simple shape (for example, a shape formed by combining a plurality of straight lines or curves). As the complicated shape, for example, a shape as shown in FIG. 17 can be adopted, and as shown in FIG. 18, a shape that suppresses as much as possible that the adhesive using portion is exposed on the side surface of the joint surface of the large pellicle frame. Further preferred. Further, as shown in FIG. 19, when viewed from the thickness direction of the frame, a stepped shape, an oblique shape as shown in FIG. 20, and an end of one member constituting the joint J as shown in FIG. 21 are convex. Various shapes can be employed, such as a constricted shape as shown in FIG. 22 and a shape in which the center of the end of the frame has a quadrangular prism shape as shown in FIG. In the case of a constricted shape, a round pierced shape, a wedge shape, a square shape, a triangular shape, and other various shapes (for example, shapes used in a jigsaw puzzle) can be adopted.

Also, depending on the amount of adhesive applied, an adhesive pool is designed inside the joint to reduce the amount of adhesive protruding to the surface of the frame when joining, and there is excess adhesive in the joint. You may produce the shape which can absorb.

Within the large pellicle manufacturing process, the frame has a process of cutting an unnecessary film after the large pellicle film is stretched, but the frame tends to bend inward due to the tension of the film. For this reason, a complex shape having a larger bonding area than a simple shape is preferable because it can relieve stress when bending inward and does not have looseness or gaps at the joint.

Next, a method for manufacturing the large pellicle frame 2 shown in FIG. 2 will be described.

First, the divided frames 21a to 21h are formed by extruding at least one metal member selected from the group consisting of aluminum and aluminum alloys. Each of the divided frame bodies 21a to 21h to be formed is provided with at least one convex portion projecting toward the other member joined to the one end portion at one end portion joined at the joint portion, And the recessed part fitted by a convex part is provided in the other edge part. The divided frames 21a to 21d are linear members joined at the four corners 5 of the large pellicle frame 2, and the divided frames 21e to 21h are the four members of the large pellicle frame 2. It is a member constituting the corner 5.

Then, by fitting the convex portions of the formed divided frame bodies 21a to 21h into the concave portions, the end portion of one divided frame body is joined to the end portion of the other divided frame body. Thus, the large pellicle frame body 2 shown in FIG. 2 is manufactured.

Next, a method for manufacturing the large pellicle frame 2 shown in FIG. 4 will be described.

First, the divided frame bodies 41a to 41d are formed by extruding at least one metal member selected from the group consisting of aluminum and aluminum alloys. The divided frame bodies 41a to 41d to be formed are provided with at least one convex portion projecting toward the other member joined to the one end portion at one end portion joined at the joint portion, And the recessed part fitted by a convex part is provided in the other edge part. The divided frame bodies 41a to 41d are linear members joined at the four corners 5 of the large pellicle frame body 2.

Then, by fitting the convex portions of the formed divided frame bodies 41a to 41d into the concave portions, the end portion of one divided frame body is joined to the end portion of the other divided frame body. Thus, the large pellicle frame body 2 shown in FIG. 4 is manufactured.

The present invention is not limited to the embodiment described above. For example, in the above embodiment, the shapes of the divided frame bodies are aligned to some extent, but the shapes of the divided frame bodies may be different from each other.

Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples as long as the gist thereof is not exceeded.

[Example 1]
The material of the large pellicle frame (the material of all the divided frames) was an aluminum alloy, the thickness was 6.5 mm, and the long side was 16.5 mm wide and 1750 mm long. The short side had a width of 18.5 mm and a length of 1550 mm, and was provided with a groove over the entire length of the short side. The depth of the groove was 5 mm and the height of the groove was 2 mm. Moreover, the curvature of the corner was 20 mm. Other than that, a large pellicle frame was formed as shown in FIG. The length of the divided frames 21a and 21b was 875 mm, and the length of the divided frames 21c and 21d was 775 mm. Therefore, Lp was 25% of the length of Le, and Lp was 25% of the length of Ls. Loctite 638 (manufactured by Henkel) was used as the adhesive at the joint.

This large pellicle frame was set up vertically with the short side in the vertical direction and the long side in the horizontal direction with respect to the ground, and then a handling jig was mounted in the vertical direction. The handling jig is composed of a handle portion that is gripped by an operator and a holding portion that is connected to the handle portion and holds a large pellicle, and the holding portion has a U-shape. The holding part is composed of a pair of engaging parts that are inserted into and engaged with a groove formed on the short side of the large pellicle frame, and a support part that connects the handle part and supports the long side. ing. The engaging portion is a long member having a thickness equivalent to the width of the groove portion formed on the short side. The length of the member engaging portion is 700 mm, and the width of the engaging portion is 33 mm. The distance between the pair of engaging portions is 1742 mm. The support portion is a long member having a thickness equivalent to the long side of the large pellicle frame, and the length of the support portion is 1752 mm.

Next, with the handling jig attached, the position of the large pellicle frame was changed to be horizontal, and the position was returned to the vertical direction. Such an operation was performed 10 times. As a result, the result was that the large pellicle frame of the present embodiment did not come off the handling jig.

Next, a styrene ethylene butylene styrene-based hot melt adhesive is used as an adhesive for the large pellicle frame, and the large pellicle frame has a thickness of 1.8 mm, a coating width of 6 mm, and a distance of 2 mm from the opening. It was applied along each side of the pellicle frame.

And in a clean room, it was pasted on blue plate glass instead of a photomask. The large pellicle frame was affixed by the width of the large pellicle frame along a straight line connecting the corners of each side using a bonding device. As a result, the entire surface of the adhesive layer could be pressed, and the adhesive layer could be pressed uniformly. Further, a large pellicle frame was attached as it was and left in a vertical state for one month, but no air pass or the like was generated.

[Example 2]
A plane in which the width of the long side is 9 mm, the length of the long side is 780 mm, the width of the short side is 7 mm, the length of the short side is 470 mm, and the shape of the joint is from the inner peripheral vertex to the outer peripheral vertex of the frame A frame for a large pellicle was formed in the same manner as in Example 1 except that the shape was changed. FIG. 10 is a schematic perspective view showing the shape of the joint portion in the second embodiment. In this case, Lp is 0% of the length of Le, and Lp is 0% of the length of Ls. When the presence or absence of the occurrence of an air path was evaluated in the same manner as in Example 1, no air path or the like was generated.

[Comparative Example 1]
A frame for a large pellicle was formed in the same manner as in Example 1 except that no joint was provided.

When the handling property of this large pellicle frame was confirmed in the same manner as in Example 1, a result that it was detached from the handling jig twice was obtained.

Further, when the presence or absence of an air path was confirmed in the same manner as in Example 1, it was visually confirmed that an air path was generated at several locations in the central part of the long side.

[Comparative Example 2]
A frame for a large pellicle was formed in the same manner as in Comparative Example 1 except that a joint was provided at the center position in the side direction of the pair of long sides (that is, two joints were provided).

When the presence or absence of an air path was confirmed in the same manner as in Example 1 for this large pellicle frame, it was visually confirmed that several air paths occurred in the central part of the long side.

[Example 3]
The material of the large pellicle frame (the material of all the divided frames) was an aluminum alloy, the thickness was 4.0 mm, and the long sides were 6.0 mm wide and 430 mm long. The short side had a width of 6.0 mm and a length of 300 mm, and was provided with a groove over the entire length of the short side. The groove depth was 2 mm and the groove height was 1.5 mm. . Further, the curvature of the corner portion was R = 2 mm. Otherwise, a large pellicle frame was formed as shown in FIG. The length of the divided frames 21a and 21b was 370 mm, and the length of the divided frames 21c and 21d was 240 mm. The joining part was made into the shape by which one round convex part was provided in the edge part of one member like FIG. The maximum horizontal dimension on the root side of the convex part is set to a length of 1.6 mm, the maximum horizontal dimension on the tip side of the convex part is set to 3.0 mm, the dimension of the joint gap is set to 0.03 mm, The adhesive was fitted from above and below without using an adhesive. As a result of visual inspection, there was no problem in appearance.

(Dimensional stability measurement)
After measuring the external dimensions of the above frame body and performing a heat treatment at 140 ° C. for 10 minutes on a hot plate, the external dimensions of the central part of the long side were measured to determine the amount of deformation. External dimensions were measured with Mitutoyo FAL-1600 series. The results are shown in Table 1.

(Joint strength test)
Next, a bonding strength test was performed. A sample of a 100 mm rod-shaped member including the same joint shape portion as described above was produced. The joining portion was at a position of 50 mm, which is half of a 100 mm rod-shaped member. Chucking 10mm from the joint with the width direction facing the upper surface (chucking is in the range of 10mm to 30mm from the joint), and apply the force on the opposite side of chucking to the place 10mm from the joint It was measured. The measuring device was an Imada digital force gauge. The results are shown in Table 1.

Next, a styrene ethylene butylene styrene-based hot melt pressure-sensitive adhesive having a thickness of 1.4 mm was applied to the large pellicle frame along each side of the large pellicle frame.

Separately, a large pellicle film of cellulose ester was formed on a substrate by spin coating, and the film was adhered to a temporary frame, and then peeled off from the substrate. This temporary frame was made of aluminum. Then, an acrylic film adhesive is applied to the opposite side of the hot pellicle frame coated with the hot melt pressure sensitive adhesive to the opposite side where the hot melt pressure sensitive adhesive is not applied, and the large pellicle film of the temporary frame is bonded. Then, the excess film was cut to produce a large pellicle, and the appearance was visually inspected to confirm that there was no problem. Since the frame body was bent inward after cutting, the joint surface of the joint portion was visually confirmed after the shape was stabilized. The results are shown in Table 1.

[Example 4]
The width of the long side was set to 9.0 mm, the length was set to 800 mm, the width of the short side was set to 7.0 mm, the length was set to 480 mm, and the curvature of the corner portion was set to R = 0 mm. The length of the other grooves and the thickness of the frame were the same as in Example 1. In this example, the divided frames as shown in FIG. 4 were used, 41c and 41d were 480 mm, and 41a and 41b were 790 mm. As shown in FIG. 8A, the joint portion has a shape in which two round convex portions are provided at the end of one member. The maximum horizontal dimension on the base side of the convex part is set to a length of 1.5 mm, the maximum horizontal dimension on the tip side of the convex part is set to 2.0 mm, and the dimension of the joint gap is set to 0.02 mm, The adhesive was fitted from above and below without using an adhesive. As a result of visual inspection, there was no problem in appearance. Thereafter, a large pellicle was prepared in the same manner as in Example 3 except that the thickness of the hot-melt adhesive material was changed to 2.0 mm, and evaluation was performed in the same manner. The results are listed in Table 1.

[Example 5]
The long side width is 21.0 mm, the length is 2000 mm, the short side width is 19.5 mm, the length is 1800 mm, and the corner curvature is R = 0 mm. 0.0 mm. The length and depth of the other grooves were the same as in Example 1. In this example, the divided frames as shown in FIG. 6 were used, 51c, 51c ′, 51d, and 51d ′ were each 900 mm, and 51a, 51a ′, 51b, and 51b ′ were 982 mm each. The joining part was made into the shape by which three trapezoid-shaped convex parts were provided like Fig.9 (a). The maximum lateral dimension on the root side of the convex part is set to a length of 2.1 mm, the maximum lateral dimension on the tip side of the convex part is set to 4.2 mm, the dimension of the joint gap is set to 0.015 mm, The adhesive was fitted from above and below without using an adhesive. As a result of visual inspection, there was no problem in appearance. Thereafter, a large pellicle was prepared in the same manner as in Example 3 except that the thickness of the hot-melt adhesive material was changed to 2.0 mm, and evaluation was performed in the same manner. The results are listed in Table 1.

[Comparative Example 3]
A cut frame from a single base material without a joint was prepared. The long side width was 9.0 mm, the length was 800 mm, the short side width was 7.0 mm, and the length was 480 mm. The material was an aluminum alloy, and a large pellicle frame having a thickness of 4.0 mm was used. Grooves were provided over the entire length of the short side, the groove depth was 2 mm, and the groove height was 1.5 mm. Further, the curvature of the corner portion was R = 2 mm. Other than that, a large pellicle was prepared in the same manner as in Example 3 and evaluated in the same manner. The results are listed in Table 1. However, since there are no joints, no joint strength test was performed.

[Comparative Example 4]
After forming the frame for a large pellicle in the same manner as in Example 3 except that the shape of the bonded part is as shown in FIG. 11 and bonded using a two-component room temperature curing urethane adhesive, the Example A large pellicle was prepared in the same manner as in No. 3 and evaluated in the same manner. The results are listed in Table 1. When a large pellicle frame was produced and then visually inspected, adhesive sagging occurred, and an appearance of the adhesive due to sagging adhesive was observed.

[Reference Example 1]
The joining part was made into the shape by which two regular triangular convex parts were provided in the edge part of one member like FIG. The maximum lateral dimension on the root side of the convex part is set to a length of 2.0 mm, the dimension of the joint gap is set to 0 mm, and a large pellicle frame is manufactured by joining by laser welding. Similarly, a large pellicle was prepared and evaluated in the same manner. The results are listed in Table 1. When a visual inspection was carried out after the production of the large pellicle frame, unevenness after welding occurred at the joint, and the appearance was not good. In addition, the appearance after manufacturing the large pellicle also showed that the concavo-convex part was shining and looked like a foreign object, and the inspection performance was not good.

[Reference Example 2]
The joining part was made into the shape by which three trapezoid-shaped convex parts were provided in the edge part of one member like FIG. The maximum horizontal dimension on the base side of the convex part is set to a length of 4.2 mm, the maximum horizontal dimension on the tip side of the convex part is set to a length of 2.1 mm, and the dimension of the joint gap is set to 0 mm, A frame for a large pellicle was produced by bonding using a shrinking swivel. Thereafter, a large pellicle was produced in the same manner as in Example 5 and evaluated in the same manner. The results are listed in Table 1. A visual inspection was conducted after the production of the large pellicle frame, but the appearance was good, but because the bonding strength was weak, gaps and backlash were found in the visual inspection after the production of the large pellicle, and there were foreign objects there. Was caught. Moreover, the shape was not rectangular.

[Example 6]
The material of the large pellicle frame (the material of all the divided frames) was an aluminum alloy, and had a thickness of 4.0 mm, a long side width of 6.0 mm, and a length of 430 mm. In addition, the short side had a width of 6.0 mm, a length of 300 mm, a groove was provided over the entire length of the side surface of the short side, the groove depth was 2 mm, and the groove height was 1.5 mm. The curvature of the corner was R = 2 mm. In other configurations, a frame for a large pellicle was produced with the configuration shown in FIG. The length of the divided frame constituting the long side was 370 mm, and the length of the divided frame constituting the short side was 240 mm. As shown in FIG. 14, the joining portion has a stepped shape in which an end surface 81a having a step of the divided frame body 80a and an end surface 81b having a step of the divided frame body 80b are brought into contact with each other. The specific dimensions in FIG. 14 were 1.3 mm vertically from the lower surface, 10 mm in the longitudinal direction, 1.3 mm vertically, 10 mm in the longitudinal direction, and further 1.4 mm vertically, and an adhesive was used. Loctite 638 (manufactured by Henkel) was used as the adhesive. As a result of visual inspection, there was no problem in appearance.

(Measurement method for dimensional stability measurement)
The measuring apparatus was a laser displacement meter (Keyence LJ-G030). One regular square standard sample was prepared according to the outer dimensions of the frame. Separately, 5 samples were prepared for each example under the conditions of Examples and Comparative Examples, and compared with a regular square standard sample. The portion with the greatest difference was x if it was 1.0 mm or more even in one sample out of 5 samples, Δ if it was 0.5 mm or more and less than 1.0 mm, and ○ if it was less than 0.5 mm.

(Joint strength test)
Next, a bonding strength test was performed. A sample of a 100 mm rod-shaped frame including a joint portion having the same shape as described above was produced. The joint part was a 50 mm position, which is a half of a 100 mm rod shape. Chucking 10mm from the joint with the width direction facing the upper surface (chucking is in the range of 10mm to 30mm from the joint), and apply the force on the opposite side of chucking to the place 10mm from the joint It was measured. The measuring device was an Imada digital force gauge. The results are shown in Tables 2 and 3.

Next, a styrene ethylene butylene styrene-based hot-melt pressure-sensitive adhesive having a thickness of 1.4 mm was applied to the large pellicle frame along each side of the large pellicle frame.

Separately, a large pellicle film of cellulose ester was formed on the substrate by spin coating, the large pellicle film was adhered to a temporary frame, and then peeled off from the substrate. This temporary frame was made of aluminum. After that, in the frame for large pellicles coated with the hot melt adhesive material, an acrylic film adhesive is applied to the opposite surface where the hot melt adhesive is not applied, and the large pellicles film of the temporary frame is bonded. And cured. Then, the excess film was cut to produce a large pellicle, and the appearance was visually inspected to confirm that there was no problem. Since the large pellicle frame was bent inward after cutting, the joint surface of the joint portion was visually confirmed after the shape was stabilized. The results are shown in Tables 2 and 3.

[Example 7]
The large pellicle frame had a long side width of 9.0 mm, a length of 800 mm, a short side width of 7.0 mm, a length of 480 mm, and a corner portion with a curvature of R = 0 mm. The length and depth of the other grooves and the thickness of the large pellicle frame were the same as in Example 6. The large pellicle frame was divided into four parts as shown in FIG. 4, the length of the divided frame material constituting the long side was 790 mm, and the length of the divided frame material constituting the short side was 480 mm. The joining portion has a shape shown in FIG. The maximum joint distance of each joint end face is 1.5 mm with respect to the above width, the maximum joint distance of each joint part inner surface is 2.0 mm, and the joint part inner face is crushed when fitted to 0.02 mm with respect to the size of the joint part inner surface. A part (surplus part) was provided. And it fitted from the up-down direction, without using an adhesive agent. As a result of visual inspection, there was no problem in appearance. Thereafter, a large pellicle was prepared in the same manner as in Example 6 except that the thickness of the hot-melt adhesive material was changed to 2.0 mm, and evaluation was performed in the same manner. The results are shown in Tables 2 and 3.

[Example 8]
The frame for the large pellicle has a long side width of 21.0 mm, a length of 2000 mm, a short side width of 19.5 mm, a length of 1800 mm, a corner with a curvature of R = 0 mm, and a thickness of the frame. The thickness was 6.0 mm. The length and depth of the other grooves were the same as in Example 6. The large pellicle frame was divided into eight parts as shown in FIG. 6, the length of the divided frame constituting the long side was set to 900 mm, and the length of the divided frame constituting the short side was set to 982 mm. The joining portion has a shape shown in FIG. The maximum joint distance of each joint end surface is 2.1 mm with respect to the above width, the maximum joint distance of each joint part inner surface is 4.2 mm, and the clearance is 0.015 mm. The mating was done. As a result of visual inspection, there was no problem in appearance. Thereafter, a large pellicle was prepared in the same manner as in Example 6 except that the thickness of the hot-melt adhesive material was changed to 2.0 mm, and evaluation was performed in the same manner. The results are shown in Tables 2 and 3.

[Comparative Example 5]
The large pellicle frame was prepared by cutting out a single sheet-like base material having no joint. The width of the long side was 9.0 mm, the length was 800 mm, the width of the short side was 7.0 mm, and the length was 480 mm. The material was an aluminum alloy, and the thickness was 4.0 mm. On the side surface of the short side, a groove was provided over the entire length, the depth of the groove was 2 mm, and the height of the groove was 1.5 mm. The curvature of the corner was R = 2 mm. Other than that, a large pellicle was produced in the same manner as in Example 6 and evaluated in the same manner. The results are shown in Tables 2 and 3. However, since there are no joints, no joint strength test was performed.

[Comparative Example 6]
The configuration of the joining portion was the same as that of Example 6 except that laser welding was performed with a simple shape (shape obtained by vertically cutting the frame) as shown in FIG. The results are shown in Tables 2 and 3. After spreading the large pellicle film, there was a backlash in the appearance and foreign matter was generated.

[Comparative Example 7]
After forming a large pellicle frame in the same manner as in Example 6 except that the shape of the joint is a simple bond as shown in FIG. 11 and joined using a two-component room-temperature-curing urethane adhesive. A pellicle was prepared in the same manner as in Example 6 and evaluated in the same manner. The results are shown in Tables 2 and 3. When a large pellicle frame was produced and then visually inspected, adhesive sagging occurred, and an appearance of the adhesive due to sagging adhesive was observed.

[Reference Example 3]
As shown in FIG. 12, in the large pellicle frame, the shape of the junction is an equilateral triangle, and two junctions are formed. Each side was set to 2.0 mm, and joining was performed by the method of fraying. Other than that, the same large pellicle frame as in Example 7 was fabricated and then evaluated in the same manner as in Example 6. The results are shown in Tables 2 and 3. When a visual inspection was performed after producing a frame for a large pellicle, unevenness after welding occurred at the joint, which was not good in appearance. In addition, the appearance after manufacturing the large pellicle also showed that the concavo-convex part was shining and looked like a foreign object, and the inspection performance was not good.

[Reference Example 4]
As shown in FIG. 15, the large pellicle frame has three joint portions in which the shape of the joint portion is such that the end surfaces 71a and 71b of the split frame bodies 70a and 70b are formed with trapezoidal tenons and grooves. The formed shape was used. A maximum pellicle frame was manufactured by setting the maximum bonding distance of each bonding end face to 4.2 mm with respect to the above width and 2.1 mm to the maximum bonding distance of the inner surface of each bonding portion, using shrink shrinks. Thereafter, a large pellicle was prepared in the same manner as in Example 6 and evaluated in the same manner. The results are shown in Tables 2 and 3. Visual inspection after manufacturing the frame for the large pellicle showed good appearance, but because the bonding strength was weak, gaps and backlash were observed in the visual inspection after the large pellicle was manufactured. Was caught. Moreover, the shape was not rectangular.

Next, the present embodiment will be described more specifically with reference to Examples 9 to 11 and Comparative Example 8. However, the present embodiment is not limited to the following examples as long as the gist thereof is not exceeded.

(Measurement method of dimensional stability)
The measurement device was a laser displacement meter (Keyence LJ-G030). One regular square standard sample was prepared according to the outer dimensions of the frame. Separately, 5 samples were prepared for each example under the conditions of the following Examples and Comparative Examples, and the difference in size between the regular square standard sample and the outer dimensions was compared. The location where the difference between the outer dimensions is the largest is x if at least 1.0 mm of 5 samples, Δ if it is 0.5 mm or more and less than 1.0 mm, and ○ if it is less than 0.5 mm.

(Measuring method of bond strength test)
The measuring device was an Imada digital force gauge. A part of a 100 mm rod-shaped frame including the joint portion was produced, and the joint portion was set at a position 50 mm from the end. Place 10mm in the length direction of the frame body from the joint part with the width direction of a part of the frame body facing the upper surface, and chuck (fix) from the width direction, and place 10mm from the chucking part to the opposite direction of the joint part Then, pressure was applied by a measuring device from the plane direction and the side direction.

[Example 9]
The material of the large pellicle frame (the material of all the divided frames) was an aluminum alloy, the thickness was 4.0 mm, and the long sides were 6.0 mm wide and 430 mm long. The short side had a width of 6.0 mm and a length of 300 mm, and was provided with a groove over the entire length of the short side. The groove depth was 2 mm and the groove height was 1.5 mm. . Further, the curvature of the corner portion was R = 2 mm. Otherwise, a large pellicle frame was formed as shown in FIG. The length of the divided frames 21a and 21b was 370 mm, and the length of the divided frames 21c and 21d was 240 mm. All the joints J have a simple shape as shown in FIG. As the adhesive, an anaerobic curable acrylic adhesive (trade name: Henkel Loctite 638 (manufactured by Henkel)) was used to produce a bonded frame. As a result of visual inspection, there was no problem in appearance.

Separately, two 100 mm rod-shaped samples with joints formed for the joint strength test were prepared. The results of the bond strength test are shown in Table 4.

Next, a styrene ethylene butylene styrene-based hot-melt pressure-sensitive adhesive having a thickness of 1.4 mm was applied to the large pellicle frame along each side of the large pellicle frame. Separately, a large pellicle film of cellulose ester was formed on a substrate by spin coating, and the film was adhered to a temporary frame, and then peeled off from the substrate. This temporary frame was made of aluminum. Then, an acrylic film adhesive is applied to the opposite side of the hot pellicle frame coated with the hot melt pressure sensitive adhesive to the opposite side where the hot melt pressure sensitive adhesive is not applied, and the large pellicle film of the temporary frame is bonded. And cured, and the excess film was cut. The dimensional stability results are listed in Table 4.

[Example 10]
The long side width was 9.0 mm, the length was 800 mm, the short side width was 7.0 mm, the length was 480 mm, and the corner curvature was R = 0 mm. Two other groove lengths and frame thicknesses were produced in the same manner as in Example 9. In Example 10, the divided frame body shown in FIG. 4 was used, 81c and 81d were 480 mm, and 81a and 81b were 790 mm. The planar shape of the joint portion J is a regular triangle shape with a side of 4 mm as shown in FIG. 17, except that one regular triangle convex portion (concave portion) is provided on the joint end surface. It was produced in the same manner as in Example 9. As a result of visual inspection, there was no problem in appearance. A joint strength test was performed in the same manner as in Example 9. The results are shown in Table 4. Thereafter, a large pellicle was prepared in the same manner as in Example 9 except that the thickness of the hot melt adhesive material was set to 2.0 mm, and the frame was evaluated in the same manner. The results are listed in Table 4.

[Example 11]
The width of the long side is 21.0 mm, the length is 2000 mm, the width of the short side is 19.5 mm, the length is 1800 mm, the curvature of the corner is R = 0 mm, and the thickness of the frame is 6.0 mm. did. The length and depth of the other grooves were the same as in Example 9. In Example 11, the divided frame body as shown in FIG. 6 was used, the lengths of 51c, 51c ′, 51d, and 51d ′ were each 900 mm, and the lengths of 51a, 51a ′, 51b, and 51b ′ were each 982 mm. The shape of the joint portion J is a constricted shape as shown in FIG. 22, and three constricted convex portions are provided on the joint end surface. It was produced in the same manner as in Example 9 except that the maximum lateral dimension on the root side of the convex part was set to 2.1 mm and the maximum lateral dimension on the tip side of the convex part was set to 4.5 mm. As a result of visual inspection, there was no problem in appearance. A joint strength test was performed in the same manner as in Example 9. The results are shown in Table 4. Thereafter, a large pellicle was prepared in the same manner as in Example 9 except that the thickness of the hot melt adhesive material was set to 2.0 mm, and the frame was evaluated in the same manner. The results are listed in Table 4.

[Reference Example 5]
A large pellicle frame is manufactured in the same manner as in Example 9 except that the shape of the joint J is a simple shape as shown in FIG. did. The evaluation method was the same as in Example 9. The results are listed in Table 4. The appearance was an unacceptable level as a large pellicle because irregularities occurred in the joint J and foreign matter was caught.

[Reference Example 6]
A large pellicle was produced in the same manner as in Example 10 except that the shape of the joint J was the same as in Example 10 except that laser welding was used instead of the adhesive to join the joints. The evaluation method was performed in the same manner as in Example 9, and the results are shown in Table 4. Appearance was not acceptable as a large pellicle because irregularities occurred in the joint J and foreign matter was caught.

[Reference Example 7]
A large pellicle was produced in the same manner as in Example 11 except that the shape of the joint J was the same as that in Example 11 and was joined by laser welding instead of an adhesive. The evaluation method was performed in the same manner as in Example 9, and the results are shown in Table 4.

[Reference Example 8]
A large pellicle was produced in the same manner as in Example 11 except that the shape of the joint J was the same as in Example 11 except that the adhesive was baked and welded. The evaluation method was performed in the same manner as in Example 9, and the results are shown in Table 4.

[Reference Example 9]
A large pellicle was prepared in the same manner as in Example 11 except that the shape of the joint J was the same as in Example 11, except that it was cooled instead of adhesive and was welded. The evaluation method was performed in the same manner as in Example 9, and the results are shown in Table 4.

[Comparative Example 8]
A single frame with no joints was made. The long side width was 9.0 mm, the length was 800 mm, the short side width was 7.0 mm, the length was 480 mm, and the corner curvature was R = 2.0 mm. Two other groove lengths and frame thicknesses were produced in the same manner as in Example 9. The evaluation method was performed in the same manner as in Example 9, and the results are shown in Table 4.

Next, the present embodiment will be described more specifically with reference to Examples 12 to 17 and Comparative Examples 10 to 11. However, the present embodiment is not limited to the following examples unless it exceeds the gist. Absent.

(Measurement method of XRD)
With respect to the axial direction of the frame for the pellicle, a cross section is cut out from the vertical surface with an accuracy of ± 1 degree, and as a mechanical polishing, mirror polishing is performed using an abrasive, and then a line diffraction measurement is performed under the following conditions: (111) The peak intensity ratio was calculated based on the detected intensity at the peak top of the diffraction surface and the (200) diffraction surface.

Measuring device: Rigaku Ultima-IV
X-ray source: Cu tube (40 kV, 10 mA),
Detector: D / tex Ultra (one-dimensional detector)
Optical system: Concentrated optical system (no spectral crystal, Ni-filt, no beam stopper)
Vertical restriction slit: 10mm
Optical slit (SS-DS-RS): 1 deg-open-open solar slit (incident side, outgoing side): solor V5, sol-5 deg
Measurement mode: 2θ / ω scan Scanning speed: 0.1 deg / min
Sample spin speed: 75 rpm
Scanning range: 2θ = 35 to 85 deg (0.02 deg / step)

(Measurement method for thermal dimensional stability measurement)
The measuring apparatus was a laser displacement meter (Keyence LJ-G030). The outer dimensions of the center of the long side and the center of the short side before heating were measured. Then, after heating in an oven set at 180 degrees for 30 minutes, natural cooling (room temperature for about 3 hours) was performed, and the outer dimensions of the center of the long side and the center of the short side were measured again to confirm the amount of displacement after heating. .

[Example 12]
The material for the large pellicle frame (the material of all the divided frames) is made of extruded aluminum alloy, has a thickness of 4.0 mm, a long side of 9.0 mm, a length of 800 mm, and a short side. The width was set to 7.0 mm, the length was 480 mm, and the curvature of the corners was R = 0 mm. Grooves were provided over the entire length of the short side, the groove depth was 2 mm, and the groove height was 1.5 mm. Other than that, the divided frame body as shown in FIG. 4 is used, 41c and 41d are 480 mm, and 41a and 41b are 790 mm. As shown in FIG. 8A, the joint portion has a shape in which two round convex portions are provided at the end of one member. The maximum horizontal dimension on the base side of the convex part is set to a length of 1.5 mm, the maximum horizontal dimension on the tip side of the convex part is set to 2.0 mm, and the dimension of the joint gap is set to 0.02 mm, The adhesive was fitted from above and below without using an adhesive.

Measure the thermal dimensional stability of the frame, and the results are listed in Table 5. Moreover, orientation was confirmed by XRD measurement of the same frame, and the result is shown in FIG.

[Example 13]
Example of the material of the large pellicle frame (all divided frame materials), except that the rolled frame made of aluminum alloy was used to cut the long and short divided frames parallel to the roll direction. A frame was prepared in the same manner as in No. 12, and evaluations other than XRD measurement were performed. The results are shown in Table 5.

[Example 14]
A frame was prepared in the same manner as in Example 12 except that the same material as in Example 13 was used, the long side was cut out parallel to the rolling direction of the rolling, and the short side was cut out perpendicular to the rolling direction of the rolling. Evaluations other than were made. The results are shown in Table 5.

[Comparative Example 10]
The same evaluation as in Example 12 was performed except that the material of the frame was rolled and the sheet was not provided with a joint. The results are shown in Table 5 and FIG.

[Example 15]
The material of the large pellicle frame (the material of all the divided frames) was an aluminum alloy, the thickness was 4.0 mm, and the long sides were 6.0 mm wide and 430 mm long. The short side had a width of 6.0 mm and a length of 300 mm, and was provided with a groove over the entire length of the short side. The groove depth was 2 mm and the groove height was 1.5 mm. . Further, the curvature of the corner portion was R = 2 mm. Otherwise, a large pellicle frame was formed as shown in FIG. The length of the divided frames 21a and 21b was 370 mm, and the length of the divided frames 21c and 21d was 240 mm. All the joints J have a simple shape as shown in FIG. As the adhesive, an anaerobic curable acrylic adhesive (trade name: Henkel Loctite 648 (manufactured by Henkel)) was used to produce a bonded frame. As a result of visual inspection, there was no problem in appearance.

Separately, two 100 mm rod-shaped samples with joints formed for the same joint strength test as in Example 9 were prepared. The results of the bond strength test are shown in Table 6.

Next, a styrene ethylene butylene styrene-based hot-melt pressure-sensitive adhesive having a thickness of 1.4 mm was applied to the large pellicle frame along each side of the large pellicle frame. Separately, a large pellicle film of cellulose ester was formed on a substrate by spin coating, and the film was adhered to a temporary frame, and then peeled off from the substrate. This temporary frame was made of aluminum. Then, an acrylic film adhesive is applied to the opposite side of the hot pellicle frame coated with the hot melt pressure sensitive adhesive to the opposite side where the hot melt pressure sensitive adhesive is not applied, and the large pellicle film of the temporary frame is bonded. And cured, and the excess film was cut. The results of dimensional stability similar to Example 9 are shown in Table 6.

[Example 16]
The long side width was 9.0 mm, the length was 800 mm, the short side width was 7.0 mm, the length was 480 mm, and the corner curvature was R = 0 mm. Two other groove lengths and frame thicknesses were produced in the same manner as in Example 15. In Example 16, the divided frame body as shown in FIG. 4 was used, 81c and 81d were 480 mm, and 81a and 81b were 790 mm. As the planar shape of the joint portion J, an equilateral triangle shape having a side of 4 mm as shown in FIG. 17 is adopted, and one such equilateral triangle convex portion (concave portion) is provided on the joint end surface. The adhesive was prepared in the same manner as in Example 15 except that a modified acrylic adhesive (trade name: Three Bond 3923/3928 (manufactured by Three Bond)) was used. As a result of visual inspection, there was no problem in appearance. A joint strength test was performed in the same manner as in Example 15. The results are shown in Table 6. Thereafter, a large pellicle was produced in the same manner as in Example 15 except that the thickness of the hot-melt adhesive material was 2.0 mm, and the frame body was evaluated in the same manner. The results are listed in Table 6.

[Example 17]
The width of the long side is 21.0 mm, the length is 2000 mm, the width of the short side is 19.5 mm, the length is 1800 mm, the curvature of the corner is R = 0 mm, and the thickness of the frame is 6.0 mm. did. The length and depth of the other grooves were the same as in Example 15. In Example 17, the divided frame body as shown in FIG. 6 was used, the lengths 51c, 51c ′, 51d, and 51d ′ were each 900 mm, and the lengths 51a, 51a ′, 51b, and 51b ′ were each 982 mm. The shape of the joint portion J is a constricted shape as shown in FIG. 22, and three constricted convex portions are provided on the joint end surface. The maximum horizontal dimension on the base side of the convex part is set to 2.1 mm, the maximum horizontal dimension on the tip side of the convex part is set to 4.5 mm, and an epoxy adhesive (trade name Loctite 0151 (Henkel) is used as the adhesive. ) Was used in the same manner as in Example 15 except that. As a result of visual inspection, there was no problem in appearance. A joint strength test was performed in the same manner as in Example 15. The results are shown in Table 6. Thereafter, a large pellicle was produced in the same manner as in Example 15 except that the thickness of the hot-melt adhesive material was 2.0 mm, and the frame body was evaluated in the same manner. The results are listed in Table 6.

[Comparative Example 11]
A large pellicle was prepared in the same manner as in Example 15 except that a chloroprene rubber adhesive (Konishi G17 (manufactured by Konishi)) was used as the adhesive, and evaluation was performed in the same manner. The results are listed in Table 6.

The present invention can be suitably used particularly in the field of large pellicles where handling is a problem.

DESCRIPTION OF SYMBOLS 1 ... Large pellicle, 2 ... Large pellicle frame body, 2a, 2b, 4a, 4b, 5a, 5b ... Long side, 2c, 2d, 4c, 4d, 5c, 5d ... Short side, 2e ... Upper edge surface, 21a , 21b, 41a, 41b ... division frame (long side member), 21c, 21d, 41c, 41d, ... division frame (short side member), 21e, 21f, 21g, 21h ... division frame (corner part) Members), 21b ', 21d' ... split frame, 3 ... large pellicle film, 4 ... opening, 5 ... corner, 6 ... side face, 7 ... groove, 70a, 70b ... split frame, 71a, 71b ... End face, 80a, 80b ... division frame, 81a, 81b ... end face, C ... concave part, G ... joining gap (excess outer peripheral part), P ... convex part.

Claims (10)

A frame for a large pellicle having a rectangular opening in plan view,
The frame for forming the periphery of the opening has a frame for a large pellicle having three or more joints along the axial direction of the frame. 2. The large pellicle frame according to claim 1, wherein the joint portion is provided at a corner of the large pellicle frame. The frame portion is made of at least one metal member selected from the group consisting of aluminum and an aluminum alloy. In the XRD measurement result of the axial section of the large pellicle frame body, the peak intensity of (111) plane / (200 3. The large pellicle frame according to claim 1, wherein the ratio of the peak intensity of the surface is 1.0 or less. The ratio of (111) plane peak intensity / (200) plane peak intensity is 0.8 or less in the XRD measurement result of the axial cross section of the large pellicle frame. A frame for a large pellicle according to any one of the above. At least one convex portion projecting toward the other member to be joined is provided at the end portion of one member joined at the joint portion, and the convex portion is fitted at the end portion of the other member. A recess to be joined,
The large pellicle according to any one of claims 1 to 4, wherein an end of the one member is joined to an end of the other member by fitting the convex portion into the concave portion. Frame body. Large pellicle frame according to any one of claims 1 to 5, wherein the area of the opening is 1000 cm ² or more 35,000 ² or less. The frame for a large pellicle according to any one of claims 1 to 6, wherein the joint strength at the joint is 10 kgf or more. The frame for a large pellicle according to any one of claims 1 to 7, wherein the joining portion is formed by joining ends of the members to be joined with a chemical reaction type adhesive. The frame for a large pellicle according to claim 8, wherein the chemically reactive adhesive includes at least one adhesive selected from the group consisting of an acrylic adhesive and an epoxy adhesive. A large pellicle comprising the large pellicle frame according to any one of claims 1 to 9 and a large pellicle film supported by the large pellicle frame so as to cover the opening.

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