JP2013182205A - Coating material and pellicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material and a pellicle which can suppress damage at the time of handling to prevent dust and have resistance to abrasion, in order to improve inspectability.SOLUTION: A coating material is used to coat a pellicle frame 2 that stretches and supports a pellicle film 3 covering an opening 5, and includes synthetic resin and an inorganic powder agent.

Description

  The present invention relates to lithography for manufacturing a semiconductor device such as an IC (Integrated Circuit), an LSI (Large Scale Integration), and a TFT LCD (Thin Film Transistor, Liquid Crystal Display). The present invention relates to a coating material applied to a pellicle frame body of a pellicle used for preventing foreign matter from adhering to a photomax or a reticle used in a process, and a pellicle.

  2. Description of the Related Art Conventionally, in manufacturing semiconductor circuit patterns and the like, dust prevention means called a pellicle is 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 attached to one side of a pellicle frame made of metal, ceramics, or polymer, and an adhesive for attaching to a mask on the opposite side. What provided the layer (adhesive material) is mentioned. For example, the pellicle is 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 pellicle frame having a shape matching the shape of a photomask or a reticle. A pellicle film made of 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, a 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 has been demanded.

  The above-described pellicle frame is usually processed to be black. For example, Patent Document 1 discloses that the pellicle frame body is alumite-treated and then sealed to perform blackening. Patent Document 2 discloses that the pellicle frame is blackened by electrodeposition coating. Patent Document 3 discloses a pellicle frame body having an appropriate film strength and high chemical resistance by electrodeposition coating of an epoxy resin.

Japanese Patent Laid-Open No. 06-250383 JP 2007-333910 A International Publication WO2011-007523

  By the way, the pellicle frame is manufactured by punching one 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. Depending on the flatness of the base material, there is a base material that cannot be used to manufacture the pellicle frame. As the size of the pellicle frame increases, it is not easy to obtain the accuracy of the flatness of the pellicle frame. For this reason, the manufacturing process is time-consuming, which causes a decrease in yield and an increase in the cost of manufacturing the pellicle frame. In addition, in order to blacken the pellicle frame body, a large-scale tank is required to subject the pellicle frame body to alumite treatment and electrodeposition coating treatment. I was invited. Furthermore, with a large pellicle frame, it is difficult to uniformly carry out an alumite treatment or an electrodeposition coating treatment, and it has been difficult to improve the accuracy of flatness.

  Therefore, it has been proposed to paint the pellicle frame. However, since the adhesion between the coating material and the frame member cannot be ensured, it is easy to peel off, and the paint is scraped when operating with a handling jig. And foreign matter were generated, and the reality was poor. Also, depending on the coating surface condition, uneven coating of the film adhesive or mask adhesive may occur.

  In addition, since the pellicle does not like the generation of dust, it is inspected several times before it is actually used in an exposure machine. For this reason, the color of the paint is preferably a dark color such as black, dark blue color, dark brown color, etc. in order to make the inspection efficiency and easily find foreign matter. In addition, if a coating material is applied to the pellicle frame body, it may be mistaken for a foreign substance, and the inspection may take a long time. Therefore, a uniform coating surface is required for the pellicle frame.

  Even when the adhesion between the pellicle frame and the coating material is good, if the surface is too hard, the pellicle frame does not follow the bending when it is bent during handling. As a result, the coating film may crack and generate dust. Therefore, the coating film formed of the coating material has good adhesion to the material (pellicle frame), and the surface needs to be soft enough to follow bending during handling. Furthermore, it is desirable that the surface of the coating film not be shaved by the razor in the process of cutting an excess portion of the pellicle film using, for example, a razor. The coating film satisfying such conditions was not realistic except for electrodeposition coating.

  The present invention has been made in order to solve the above-described problems, and can provide a coating material and a pellicle that can suppress breakage during handling and suppress dust generation, have resistance to scraping, and improve inspection. The purpose is to provide.

  As a result of intensive studies, the present inventors have found that coating damage can be suppressed and resistance can be provided by coating a specific coating material on the frame member. In particular, in the present invention, the coating material contains an inorganic powder that is usually used as a mixture for improving colorability and strength.

  Conventionally, an alumite treatment has been generally applied to a pellicle frame. Dye is used for this alumite treatment, but an inorganic powder agent is unnecessary. In addition, in the case of electrodeposition coating that is realistic other than alumite treatment, it is known to add a coloring pigment such as carbon black for coloring, but in the pellicle field, it is an inorganic that is dispersible from the viewpoint of dust generation. There is a tendency to avoid adding powder as much as possible. This is because it is easily assumed that the surface of the pellicle frame body is easily roughened due to the dispersibility of the inorganic powder, leading to dust generation or poor adhesion.

  The inventors of the present invention include an inorganic powder agent in the synthetic resin, thereby suppressing dust generation due to damage to the coating film formed from the coating material, and excellent in abrasion resistance of the coating film during handling. As a result, the present invention has been completed.

  That is, the coating material according to the present invention is a coating material applied to a pellicle frame body that stretches and supports a pellicle film covering the opening, and includes a synthetic resin and an inorganic powder agent.

  In one Embodiment, more than 0 mass parts and 60 mass parts or less are included with respect to 100 mass parts of synthetic resins.

  In one embodiment, the pencil hardness after coating and drying is B or more and 8H or less.

  In one embodiment, the contact angle with the pellicle frame is 65 ° or more and 98 ° or less.

  In one embodiment, the synthetic resin is at least one synthetic resin selected from the group consisting of epoxy-based, acrylic-based, and fluorine-based resins.

  A pellicle according to the present invention includes a pellicle frame covered with the above-described coating material, and a pellicle film on which a pellicle film is stretched and supported so as to cover an opening of the pellicle frame.

  ADVANTAGE OF THE INVENTION According to this invention, while being able to suppress damage at the time of handling and suppressing dust generation, it has the effect that it has the tolerance with respect to shaving, and can aim at the improvement of testability.

1 is a perspective view showing a pellicle according to an embodiment of the present invention. It is the figure which looked at the pellicle shown in FIG. 1 from the top. It is the III-III sectional view taken on the line in FIG. It is a table | surface which shows an evaluation result. It is a figure which shows the pellicle frame of an Example.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the description, the same reference numerals are used for the same elements or elements having the same function, and redundant description is omitted.

  FIG. 1 is a perspective view showing a pellicle according to an embodiment of the present invention, and FIG. 2 is a top view of the pellicle shown in FIG. As shown in each figure, the pellicle 1 includes a pellicle frame 2 and a pellicle film 3 that is stretched and supported on the upper edge surface 2e of the pellicle frame 2. Although not shown, the pellicle 1 further includes an adhesive layer applied to the lower edge surface of the pellicle frame 2 and a protective film that is adhered to the adhesive layer and protects the adhesive layer. ing. The pellicle 1 is a large pellicle, and the pellicle frame 2 is a large pellicle frame.

  The pellicle frame 2 includes, 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-Al2O3, etc.), carbon steel, tool steel, stainless steel series, polymer, etc., and has a substantially rectangular shape in plan view. Among these, aluminum and aluminum alloys are more preferable because they have adhesiveness, moisture resistance, and flexibility and hardness following the bending of the frame during handling in order to be used as a pellicle frame.

The 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. In the 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. The pellicle frame 2 has a rectangular opening 4, and the long sides 2 a and 2 b and the short sides 2 c and 2 d form the periphery of the opening 4. The opening area of the opening 4 is preferably 1000 cm ² or more, more preferably 2000 cm ² or more and 35,000 ² or less. Note that the pellicle frame 2 may or may not have a joint.

  The pair of long sides 2a and 2b is formed of a column member having a width of, for example, 9.0 mm, and the length thereof is, for example, 800 mm. The pair of short sides 2c and 2d is made of a column member having a width of, for example, 7.0 mm, and the length thereof is, for example, 480 mm. That is, the width of the short sides 2c and 2d in plan view (top view) is narrower than the width of the long sides 2a and 2b. The curvature of the corner 5 of the pellicle frame 2 is, for example, R = 2 mm. Grooves 7 are provided along the longitudinal direction (side direction) on the side surface 6 of the pellicle frame 2.

  The width of each side 2a to 2d of the pellicle frame 2 is preferably as thin as possible from the viewpoint of securing an exposure area. However, if the width is too small, the pellicle frame 2 is stretched by the tension of the pellicle film 3 when the pellicle film 3 is expanded. There is a risk that the problem of bending will occur. Since the width takes into account the rigidity with respect to the length of each side, each side 2a to 2d can be about 3 mm to 25 mm.

  Further, regarding the thickness of the pellicle frame body 2, the thinner the pellicle 1, the lighter and easier to handle the pellicle 1. However, if the pellicle film 3 is too thin, the pellicle frame body 2 will be bent by the tension of the pellicle film 3. Problems may arise. The thickness of the pellicle frame body 2 is preferably about 3.5 mm to 12 mm from the balance between the two according to the length of each side 2a to 2d.

  As described above, the pellicle frame 2 is manufactured by punching one sheet-like base material, and is often an integral type that does not have a joint. In the configuration having a joint, since the alumite treatment is difficult at the joint and the joint can be clearly recognized, a gap is formed in the joint due to a strong acid or alkali alumite treatment, or dimensional deformation of the pellicle frame 2 occurs. Or the surface texture may change starting from the joint. Therefore, it is more preferable to use a coating material as the surface treatment method in the configuration in which the joint portion is provided in the pellicle frame 2.

  The 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 10 μm or less and 0.1 μm or more, for example. The pellicle film 3 is spread on the upper edge surface 2 e so as to cover the opening 4 of the pellicle frame 2, and is attached to and supported by the pellicle frame 2.

  As an adhesive for adhering the pellicle film 3 to the upper edge surface 2e of the pellicle frame 2, 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 is used. be able to.

  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 pressure-sensitive adhesive layer is set within a range not exceeding the distance between the pellicle film 3 and the photomask in which the total thickness of the pellicle frame 2 and the thickness of the pressure-sensitive adhesive is defined. 01 mm or more is preferable.

  In addition, when the pellicle film 3 is attached to the photomask, if there is a space inside the adhesive layer, foreign matter may stay in the space. Therefore, when applying the pressure-sensitive adhesive to the lower edge surface of the pellicle frame 2, the pressure-sensitive adhesive layer is crushed and spread by the pressure applied when the pellicle 1 is attached to the photomask. It is preferable to apply to the inside of the opening 4 of the pellicle frame 2 so that the adhesive does not protrude into the opening 4. 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 pellicle frame 2, and is applied along each side 2a to 2d of the pellicle frame 2. It is preferable.

  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 on the surface of a protective film. The thickness of the protective film is preferably, for example, 1 mm or less and 0.01 mm or more.

  As shown in FIG. 3, a coating film P is formed on the entire surface of the pellicle frame 2 having the above-described configuration. The coating film P that coats the surface of the pellicle frame 2 is formed of a coating material. 3 is a cross-sectional view taken along line III-III in FIG.

  Here, the coating material must be a material that can withstand the impact of the pellicle frame body 2 during the handling of the pellicle 1, the contact of the handling jig, and the transportation. In order to withstand contact and impact caused by the bending of the pellicle frame body 2, the coating material must be flexible. On the other hand, in order for the coating film P to be able to withstand handling jigs and impacts during transportation, it is also necessary to have both hardness and adhesion between the pellicle frame material. In other words, the physical properties of the coating material require properties that are contradictory to flexibility and hardness.

  In this embodiment, the coating material for forming the coating film contains a synthetic resin and an inorganic powder. The synthetic resin is not particularly limited, but is preferably at least one synthetic resin selected from the group consisting of epoxy-based, acrylic-based, and fluorine-based resins from the viewpoint of scraping during handling. When these resins and inorganic powders are combined, the wear resistance during handling is dramatically improved.

  As the inorganic powder agent, those that give the coating material functionality are good, and pigments are preferable. Among pigments, extender pigments are particularly preferred because they are preferably matte, scratch resistant and colorless. Inorganic powders are preferred because they also have matte and scratch resistant properties. Furthermore, as the inorganic powder agent, natural rocks having a refractive index of about 1.4 to 1.8, clays, or iron oxides are preferable. The above rocks and clays are, for example, kaolin, talc, silica, iron tetroxide, iron oxides, diatoms, calcium, magnesium, iron oxides, silicon oxide, silica sand, clays, anhydrous silicic acids. In particular, titanic acid or titanate, silicic acid or silicate, zirconate and the like are particularly preferable. In addition, the above inorganic powder is preferable because it is transparent or close to that in the paint and does not adversely affect the color. Moreover, as a particle size of an inorganic powder agent, it is 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.2-15 micrometers. If it is this range, since the gloss of a coating material can be suppressed and it does not affect a color, it is preferable.

  The shape of the inorganic powder may be any shape such as a flat shape, a spherical shape, and a three-dimensional shape, but more preferably a flat shape. When the inorganic powder is in a flat shape, it is arranged parallel to the coating surface and suppresses shrinkage in the coating surface direction, so that it works in a direction to reduce internal strain and works in a direction to relieve internal stress. Therefore, it is preferable. Also, the distance that the solvent detours through the coating film becomes longer and the evaporation of the solvent becomes slower, so the solvent in the coating film remains for a long time and works to reduce the internal stress of the coating film. preferable.

  Furthermore, the proportion of the inorganic powder in the synthetic resin is preferably more than 0 parts by mass and 60 parts by mass or less, more preferably 7-40 parts by mass, and most preferably 10-30 parts by mass with respect to 100 parts by mass of the synthetic resin. preferable.

  When the inorganic powder agent is included, since it does not have gloss, the light from the condenser lamp is scattered during the inspection of the pellicle frame body 2 to improve the foreign matter inspection, and further, both the adhesion and flexibility are improved. . Further, when the proportion of the inorganic powder is 40 parts by mass or less, the inorganic powder is appropriately dispersed in the coating material, so that the bonding force between the base material and the main component of the pellicle frame 2 is improved, and the adhesion Sexuality is improved. Moreover, since it can suppress that a viscosity becomes high and fluidity | liquidity is maintained, it is excellent in workability | operativity. Furthermore, since the increase in the elastic modulus of the coating film P can be suppressed, the occurrence of defects such as peeling, cracking and warping of the coating film P can be suppressed.

  The glass transition point of the coating material is preferably 50 ° C. or higher and 350 ° C. or lower, more preferably 50 ° C. or higher and 200 ° C. or lower, and more preferably 80 ° C. or higher and 150 ° C. or lower. Preferably there is.

  If the glass transition point is higher than 50 ° C., the coating surface can be prevented from becoming soft even when it becomes hot and humid during transportation, and the adhesion to the film adhesive or the adhesive layer is deteriorated. Can be prevented. If the glass transition point is lower than 350 ° C, the increase in internal stress can be suppressed, so the occurrence of voids and granular bulges is suppressed, and it is prevented from being mixed with foreign substances and taking a long time to be inspected. It is preferable because it can be prevented from becoming a foreign substance. In addition, if the difference between the coefficient of linear expansion and the frame member is large, the internal stress increases, and thus there is a risk that the coating film P will swell, peel off, crack, etc. Since the thermal expansion as the film P is suppressed, it is preferable to consider the difference in the linear expansion coefficient.

  Further, the pencil hardness of the coating film P formed by applying the coating material is preferably B or more and 8H or less, more preferably F or more and 6H or less, and further preferably F or more and 5H or less. preferable. When the pencil hardness is higher than B, it is possible to prevent the coating film P from becoming too soft, and thus it is difficult to rub against the handling jig and the generation of foreign matter can be suppressed. Further, when the pencil hardness is less than 8H, since it is not too hard, it can endure momentary expansion and contraction, can follow the bending during handling, and can suppress the occurrence of cracks and peeling.

  The coating material having such physical properties is preferably a coating type. The coating-type coating material referred to here is one in which coating is carried out in a liquid state, followed by heating, whereby polymerization proceeds and a coating film P is formed. As a method of coating the coating material in a liquid state, air spray, electrostatic coating, dip coating, and roll coating are desirable, and among these, an air spray method is preferable.

  The contact angle between the coating material and the pellicle frame 2 is preferably 65 ° to 98 °. The angle is preferably 70 ° to 97 °, and more preferably 75 ° to 95 °. In the process of applying the film adhesive to one end surface (upper edge surface 2e) of the pellicle frame 2 and spreading the pellicle film 3, the film adhesive needs to be uniformly and thinly applied to one end surface of the pellicle frame 2 There is. At this time, if the contact angle is within the above range, the film adhesive is moderately stretched, so that coating unevenness hardly occurs and the adhesion to the pellicle film 3 is improved.

  In the manufacturing process of the pellicle frame 2, a heat treatment is performed after applying the coating material. The heating temperature at this time is preferably 100 ° C. or higher. And an application | coating method and a heating temperature are adjusted so that it may be settled in the range of said glass transition point and pencil hardness at the temperature of 100 degreeC or more, and the optimal polymerization degree is selected. For the best coating, it is preferable to use an epoxy-based, acrylic-based or fluorine-based material as the coating material, and it is most preferable to use a fluorine-based or acrylic-based material. The coating film P may be a single layer, and if it is a multilayer coating, the adhesion with aluminum can be improved.

  Further, the inspection of the pellicle frame body 2 is preferably black, dark blue color, dark brown color or the like because it checks the presence or absence of foreign matter by light reflection. Therefore, carbon black etc. are contained as a black pigment.

  Generally used pellicle frame 2 is made of an aluminum alloy. From the viewpoint of the thermal expansion coefficient of the aluminum alloy, the coating material for forming the coating film P is preferably a resin having a large elongation, but it is also necessary to suppress the decrease in the hardness of the coating film P. The coating material which has is preferable. Further, since the aluminum alloy is considered to be covered with chemically and physically adsorbed water, the adsorbed water (surface OH group) and the compound showing a crosslinking reaction or hydrogen bond may be present at the end or side chain of the coating material. It is preferable that it exists in.

  For example, in the case of having an organic silicon compound or the like, the adhesion is improved by forming adsorbed water and a siloxane bond by hydrolysis or condensation reaction of the organic silicon compound. In addition, in the case of having a polar group such as a carboxyl group, it is considered that the adhesion is improved due to a strong interaction with adsorbed water, such as a hydrogen bond or an acid-base interaction. The polar group is most preferably a carboxyl group, and examples thereof include a hydroxyl group, a metal salt of a carboxylic acid (for example, sodium salt, magnesium salt, etc.), an alkyl ester, a phenol, an amino acid, an aliphatic amine and the like. These compounds are preferably equivalent to the number of OH groups on the surface. The equivalent here is a range of polar group: OH group = 1: 0.8 to 1.2. If the above compound is present in excess, moisture is adsorbed at the interface, which may cause swelling or peeling of the coating film. Specifically, Epona series (Origin Electric Co., Ltd.), Orijitsuku series (Origin Electric Co., Ltd.), FUSCOAT series (Million Paint Co., Ltd.), ARBt series (Kubo Takataka Paint Co., Ltd.), Super Rack Eco (manufactured by Nippon Paint) and the like can be mentioned.

  The pellicle frame 2 has a coating film P thickness of a predetermined portion (corner portion 5) of the long side 2a, 2b or short side 2c, 2d, and a thickness of about 20 times or less that of the other portion (center portion). It is preferable to do. Unreasonable force may be applied to the corners by attaching a handling jig or the like. Further, since the corner portion has high rigidity, it tends to be strongly attached to the mask. When the pellicle is peeled from the mask, a stronger force may be applied to the corner portion than near the center. At this time, if the coating film at the corners is 20 times or more thicker than the other parts, the adhesiveness is deteriorated, so that the coating film may be peeled off. Therefore, the thickness of the coating film P at the corner 5 is preferably 20 times or less that of the other part, more preferably 0.05 times to 20 times that of the other part. Further, the film thickness itself of the coating film P may be 5 μm to 100 μm. It is preferable that the portion to be subjected to this specific characteristic is the corner portion 5 of the pellicle frame body 2, and more preferably one corner portion 5 than the four corner portions 5, but the number is particularly limited. However, the effect becomes more conspicuous when the number is one or more.

  Then, the manufacturing method of the pellicle frame 2 is demonstrated. First, a frame member having long sides 2a and 2b and short sides 2c and 2d made of, for example, aluminum or an aluminum alloy is prepared. Next, the above-mentioned coating material is applied to the frame member by, for example, an air spray method. At this time, in the corner portion 5, the coating thickness is made thicker than other portions. Then, the frame member to which the coating material is applied is subjected to heat treatment, and the coating film P is formed on the surface of the frame member. Thus, the pellicle frame body 2 is formed. Thereafter, the pellicle film 3 is spread on the pellicle frame 2 to form the pellicle 1.

  As described above, the coating material for coating the pellicle frame body 2 of the pellicle 1 includes the synthetic resin and the inorganic powder. Accordingly, even when the pellicle frame 2 is bent, the adhesion between the pellicle frame 2 and the coating material can be secured, and thus the coating film P can be prevented from peeling off. Moreover, since it has predetermined intensity | strength, the abrasion of the coating film P by a handling jig etc. can also be prevented. Therefore, generation | occurrence | production of damage, such as a crack of the coating film P, can be suppressed. Moreover, by preventing the coating film P from being damaged, it is possible to prevent outgassing or foreign matter generation (dust generation) due to peeling of the coating film P or the like. As a result, haze can be suppressed. Moreover, since a large-scale apparatus is not required, cost can be reduced. In particular, when the pellicle 1 is large, the configuration of this embodiment is more effective.

  In addition, by using a coating material, unevenness in coating is reduced and flatness can be maintained. Furthermore, since the coating material is often polymerized by applying heat, the heat treatment of aluminum can be performed at the same time, and the deformation of the dimensions due to the application of heat during the use of the pellicle can be prevented.

  Moreover, the pencil hardness of the coating film P is B or more and 8H or less. By setting it as such pencil hardness, the intensity | strength which can endure the impact during handling jigs and transportation can be ensured. Further, since the pellicle film 3 is stretched and supported on the pellicle frame 2, a general razor can be used in the process of cutting an excess portion of the pellicle film 3 because it has a predetermined strength. Thereby, it is not necessary to use special equipment and instruments in the manufacturing process, and an increase in facilities can be prevented.

  The coating material used for forming the coating film P is a coating type. Thus, by using a coating type coating material, a coating method such as air spray, electrostatic coating, dip coating, roll coating or the like can be used. Thereby, the coating film P can be formed uniformly and the flatness of the pellicle frame 2 can be ensured.

  The pellicle frame 2 is composed of a pair of opposing long sides 2a and 2b and a pair of opposing short sides 2c and 2d. At least one formed by the long sides 2a and 2b and the short sides 2c and 2d. The thickness of the coating film P at one corner 5 is not more than 20 times the thickness of the central part of the long sides 2a, 2b or the short sides 2c, 2d. According to such a configuration, even when an excessive force is applied to the corner 5, the adhesion is good, so that peeling, cracking, and the like can be suppressed.

  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 unless it exceeds the gist.

[Example 1]
The pellicle frame was made of 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 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 pellicle frame was formed as shown in FIG. As the coating material, an epoxy resin coating (trade name “Epona Series” manufactured by Origin Electric Co., Ltd.) containing 17 parts by mass of (iron trioxide) as an inorganic powder agent with respect to 100 parts by mass of the synthetic resin, Spray coating was performed so as not to cause coating unevenness and material sagging, and heating was performed at 140 ° C. for 30 minutes to form a coating film having a glass transition point of 80 ° C. and a pencil hardness of H. The evaluation results are shown in FIG.

[Outgas evaluation]
A rod-like sample having a length of 10 cm was prepared and measured by GC-MS (manufactured by SUPELCO) by a heat desorption method. The conditions were a heating temperature of 50 ° C., a heating time of 60 minutes, an adsorbent Carbopack B + Carbosieve SIII, and a carrier gas (He).

[Handling]
The mounting operation was carried out five times with a handling jig, and shaving during mounting was visually inspected with a condenser lamp. “◯” indicates that the result is good for all five times, “Δ” indicates that the scratch was generated once but there was no problem as a pellicle, and “x” indicates that the pellicle had a defect and was defective more than once.

[Pencil hardness]
A rod-shaped sample having a length of 10 cm was prepared, and the pencil hardness was measured by a scratch hardness test (JIS K5600-5-4).

[Adhesion test]
A rod-shaped sample having a length of 10 cm was prepared, and an adhesion test was performed by an adhesion test (JIS K5600-5-6). The classifications 0 to 1 were “◯”, the classification 2 was “Δ”, and the classifications 3 to 5 were “x”.

[Contact angle measurement]
A rod-like sample having a length of 10 cm was prepared, and measurement was performed using FACE model CAS S-150 (manufactured by Kyowa Interface Science Co., Ltd.).

[Inspection]
In the dark room, the manufactured pellicle frame was irradiated with a condenser lamp to visually inspect the foreign matter. The visual inspection was confirmed by 10 workers to confirm the elucidation of foreign matter. “O” when 8 to 10 out of 10 judges that a foreign object is easy to find out, “△” when 5 to 7 out of 10 judges that a foreign object is easy to find out, and “×” otherwise. It was.

[Example 2]
The pellicle frame is made of an aluminum alloy, the long side width is 9.0 mm, the length is 800 mm, the short side width is 7.0 mm, the length is 480 mm, and the corner has a curvature of R = 0 mm. It was. Other groove lengths / depths and frame thicknesses were produced in the same manner as in Example 1. The coating material is a silicon acrylic resin paint (trade name “ORIJI TUKU Series” Origin Electric Co., Ltd.) containing 26 parts by mass of inorganic powder (hydrous magnesium silicate) and 5 parts by mass of carbon black for 100 parts by mass of synthetic resin Spray coating was performed so that coating unevenness and material sagging did not occur, and heating was performed at 140 ° C. for 30 minutes to form a coating film having a glass transition point of 100 ° C. and a pencil hardness of H. . The evaluation results are shown in FIG.

[Example 3]
The pellicle frame is made of an aluminum alloy, 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, and a corner curvature of R = 0 mm. Moreover, the thickness of the frame was 6.0 mm. The length and depth of the other grooves were the same as in Example 1. The coating material is a silicon acrylic resin paint (trade name “ORIJI TUKU Series” Origin Electric Co., Ltd.) containing 5 parts by mass of inorganic powder (hydrous magnesium silicate) and 5 parts by mass of carbon black for 100 parts by mass of synthetic resin. ), Spray coating was performed so that coating unevenness and sagging of materials did not occur, and heating at 140 ° C. for 30 minutes produced a coating film with a glass transition point of 100 ° C. and pencil hardness of H . The evaluation results are shown in FIG.

[Example 4]
The pellicle frame is made of an aluminum alloy, 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, and a corner curvature of R = 0 mm. Moreover, the thickness of the frame was 6.0 mm. The length and depth of the other grooves were the same as in Example 1. The coating material is a silicon acrylic resin paint (trade name “ORIJI TUKU Series” Origin Electric Co., Ltd.) containing 11 parts by mass of inorganic powder (hydrous magnesium silicate) and 3 parts by mass of carbon black for 100 parts by mass of synthetic resin. Spray coating was performed so that coating unevenness and material sagging did not occur, and heating at 100 ° C. was performed for 30 minutes to create a coating film with a glass transition point of 100 ° C. and a pencil hardness of H. . The evaluation results are shown in FIG.

[Example 5]
The pellicle frame is made of an aluminum alloy, 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, and a corner curvature of R = 0 mm. Moreover, the thickness of the frame was 6.0 mm. The length and depth of the other grooves were the same as in Example 1. As the coating material, an acrylic resin paint (trade name “Fuscoat Series” manufactured by Million Paint Co., Ltd.) containing 25 parts by mass of inorganic powder (talc) and 5 parts by mass of carbon black with respect to 100 parts by mass of the synthetic resin. Used, spray coating was performed so as not to cause coating unevenness and material sagging, and heating at 100 ° C. was performed for 30 minutes to prepare a coating film having a glass transition point of 100 ° C. and a pencil hardness of 2H. The evaluation results are shown in FIG.

[Example 6]
As the pellicle frame, as shown in FIG. The material of the pellicle frame including the joint (the material of all the divided frames) is an aluminum alloy, the thickness is 4.0 mm, the long side is 9.0 mm, the length is 790 mm, and the short side is wide. Was 7.0 mm, the length was 480 mm, and the curvature of the corner was R = 0 mm. Grooves were provided over the entire length of the short side surface, the groove depth was 2.0 mm, and the groove height was 1.5 mm. The joining portion has the shape shown in FIG. The maximum joint distance of each joint end face is 1.5 mm with respect to the above-mentioned width, the maximum joint distance of each joint part inner surface is 2.0 mm, and the size of each face of the joint part is 0.02 mm. A part (surplus part) was provided. Then, a pellicle frame was manufactured by fitting from above and below without using an adhesive.

  The coating material is an acrylic fluorine resin paint (trade name “Fuscoat Series” manufactured by Million Paint Co., Ltd.) containing 25 parts by mass of inorganic powder (talc) and 5 parts by mass of carbon black with respect to 100 parts by mass of synthetic resin. Was used, spray coating was performed so as not to cause coating unevenness and material sagging, and heating at 100 ° C. was performed for 30 minutes to prepare a coating film having a glass transition point of 120 ° C. and a pencil hardness of 5H. The evaluation results are shown in FIG.

[Example 7]
The pellicle frame is made of an aluminum alloy, 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, and a corner curvature of R = 0 mm. Moreover, the thickness of the frame was 6.0 mm. The length and depth of the other grooves were the same as in Example 1. As a coating material, urethane resin paint (trade name “Milliurethane Series”), which contains 20 parts by mass of inorganic powder (mixture of talc and silica powder) and 5 parts by mass of carbon black with respect to 100 parts by mass of synthetic resin. (Paint Co., Ltd.) is used, spray coating is performed so that coating unevenness and material sag do not occur, and a coating film with a glass transition point of 90 ° C. and pencil hardness of F by heating at 100 ° C. for 30 minutes. Created. The evaluation results are shown in FIG.

[Comparative Example 1]
The pellicle frame was made of 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 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 pellicle frame was formed as shown in FIG. As the coating material, 5 parts by mass of carbon black and 100 parts by mass of synthetic resin are used. Silicon acrylic resin paint (trade name “ORIJI TUKU series” manufactured by Origin Electric Co., Ltd.) without inorganic powder agent is used. Spray coating was performed so as not to cause sagging of the material, and heating at 140 ° C. was performed for 30 minutes to form a coating film having a glass transition point of 100 ° C. and a pencil hardness of 2H. The evaluation results are shown in FIG.

[Comparative Example 2]
The pellicle frame is made of an aluminum alloy, the width of the long side is 9.0 mm, the length is 800 mm, the width of the short side is 7.0 mm, the length is 480 mm, and the curvature of the corner is R = 0 mm. It was. The length and depth of the other grooves and the thickness of the frame were produced in the same manner as in Example 1. As the coating material, use an epoxy resin paint without an inorganic powder agent (trade name “ODEX” manufactured by Shinto Paint Co., Ltd.) and perform spray coating to prevent coating unevenness and material sagging. By performing heating for 20 minutes, a coating film having a glass transition point of 30 ° C. and a pencil hardness of 2B was formed. The evaluation results are shown in FIG.

[Comparative Example 3]
The pellicle frame is made of an aluminum alloy, the width of the long side is 9.0 mm, the length is 800 mm, the width of the short side is 7.0 mm, the length is 480 mm, and the curvature of the corner is R = 0 mm. It was. The length and depth of the other grooves and the thickness of the frame were produced in the same manner as in Example 1. As the coating material, 5 parts by mass of carbon black and 100% by mass of synthetic resin, urethane resin paint (trade name “BYKETO Sumitomo Bayer Urethane Co., Ltd.”) without inorganic powder agent are used. Spray coating was performed so as not to occur, and heating was performed at 120 ° C. for 20 minutes to form a coating film having a glass transition point of 40 ° C. and a pencil hardness of 3 B. The evaluation results are shown in FIG.

[Comparative Example 4]
The same thing as Example 2 was produced except having made 70 mass parts of inorganic powders with respect to 100 mass parts of synthetic resins. There was too much pigment and the dispersibility was bad and could not be applied.

  DESCRIPTION OF SYMBOLS 1 ... Pellicle, 2 ... Pellicle frame, 3 ... Pellicle film | membrane, 4 ... Opening part.

Claims (6)

A coating material applied to a pellicle frame that stretches and supports a pellicle film covering an opening,
A coating material comprising a synthetic resin and an inorganic powder.   The coating material of Claim 1 which contains more than 0 mass parts and 60 mass parts or less of the said inorganic powder agent with respect to 100 mass parts of said synthetic resins.   The coating material of Claim 1 or Claim 2 whose pencil hardness after apply | coating and drying is B or more and 8H or less.   The coating material as described in any one of Claims 1-3 whose contact angle with the said pellicle frame is 65 to 98 degree.   The coating material according to any one of claims 1 to 4, wherein the synthetic resin is at least one synthetic resin selected from the group consisting of epoxy-based, acrylic-based, and fluorine-based resins.   A pellicle frame body covered with the coating material according to any one of claims 1 to 5, and a pellicle film on which a pellicle film is stretched and supported so as to cover an opening of the pellicle frame body. Pellicle.

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