Clip for pellicle storage container, pellicle storage body, and pellicle

Abstract

Provided are a clip for a pellicle storage container, a pellicle storage body, and a pellicle, wherein the amount of outgassing of an organic gas having a carbon number of 20 or less, which is evaluated under the following condition 1, is 150 μg or less per 1 g of the clip. - Condition 1 - A cut piece 1 g of a clip is arranged in a container as a sample, and 200 ml of hexane is used as an extraction solvent, and an extraction liquid is obtained by a 6-hour Soxhlet extraction method using a water bath at 80°C.　The obtained extraction liquid is analyzed by gas chromatography. In gas chromatography, a flame ionization detector is used for a detector, an amount of a component having a carbon number of 20 or less is detected, and a detected total amount of components having a carbon number of 20 or less is used as the amount of outgassing.

Description

Clip for pellicle storage container, pellicle container, and pellicle

[0001] The present disclosure relates to a clip for a pellicle storage container, a pellicle container, and a pellicle.

[0002] Photolithography, a technology for forming patterns by coating the surface of an object, such as an electronic component, printed circuit board, or display panel, with a photosensitive material and exposing it to light in a patterned pattern, uses a transparent substrate called a mask, with a pattern formed on one side. In these manufacturing processes, patterning is achieved by irradiating a photosensitive layer or other surface with light through the mask (also known as an exposure master or reticle). If foreign matter adheres to the mask, the light is absorbed by the foreign matter or reflected and bent by the surface of the foreign matter. This can result in deformation of the formed pattern or rough edges, compromising the dimensions, quality, and appearance of the patterned product. To address these issues, a method has been adopted in which a pellicle with a light-transmitting pellicle film is attached to the surface of the mask to prevent foreign matter from adhering to the mask.

[0003] In recent years, with the advancement of electronic components in performance and the miniaturization of circuit widths, pellicles have become more susceptible than ever to the effects of minute amounts of outgassing and fine particles. To prevent foreign matter from adhering to pellicles during transportation, pellicles are sometimes packaged in the following order: a polycarbonate case with a clip-fastened opening, an inner bag, a zippered bag, and an outer bag. One example of a pellicle storage container has been proposed, which uses urethane elastomer clips to secure the tray and cover of a pellicle for reducing the generation of wear particles generated by friction when the pellicle is placed inside the storage container for transportation (Japanese Patent Application Laid-Open No. 2007-128030).

[0004] As a result of extensive research, the inventors have newly discovered that outgassing of volatile organic components generated from clips used in packaging for packaging pellicles adheres to the packaged pellicle, and that in addition to outgassing of volatile components derived from the material itself that constitutes the pellicle, outgassing originating from the clips is one of the causes of pellicle contamination.

[0005] An object of one embodiment of the present disclosure is to provide a clip for a pellicle storage container that reduces outgassing of volatile organic components.An object of another embodiment of the present disclosure is to provide a pellicle storage container that uses a clip for a pellicle storage container and that reduces outgassing of volatile organic components, and a pellicle that reduces the amount of outgassing caused by adhesion of outgassed volatile organic components.

[0006] Specific means for solving the above problems include the following aspects. <1> A clip for a pellicle storage container, in which the outgassing amount of organic gases having 20 or fewer carbon atoms, as evaluated under the following condition 1, is 150 μg or less per 1 g of clip. -Condition 1- 1 g of a cut piece of the clip is placed in a container as a test sample, and an extract is obtained by Soxhlet extraction for 6 hours in a water bath at 80°C using 200 ml of hexane as an extraction solvent. The obtained extract is analyzed using gas chromatography. In the gas chromatography, a flame ionization detector is used as the detector to detect the amount of components having 20 or fewer carbon atoms, and the total amount of the detected components having 20 or fewer carbon atoms is taken as the outgassing amount.

[0007] <2> Clips for pellicle storage containers, evaluated under the following condition 2, with the amount of outgassing generated from one clip being 2.000 μg or less. -Condition 2- The clips are placed in a container as a test specimen and heated at 50°C for 4 hours, and the generated outgassing is adsorbed onto 150 mg of adsorbent. 150 mg of adsorbent is then placed in a gas chromatograph mass spectrometer, and the total amount of outgassing of volatile organic components generated from the clips is measured under heating conditions of 280°C for 10 minutes. Here, the total amount of outgassing is calculated in n-decane terms, and the resulting total amount is divided by the number of clips used as the test specimen to determine the amount of outgassing per clip.

[0008] <3> The clip for a pellicle storage container according to <1> or <2>, which contains at least one resin selected from the group consisting of urethane resin, polyethylene resin, polyethylene terephthalate resin, polyvinyl chloride resin, polyamide resin, polycarbonate resin, acrylic resin, methacrylic resin, and phenolic resin.

[0009] <4> A pellicle container comprising a pellicle, a pellicle container for housing the pellicle, a pellicle container clip according to any one of <1> to <3> that secures the pellicle container from the outside, and a pellicle packaging that packages the pellicle container. <5> A pellicle container according to <4>, in which the total amount of outgassing of organic gases having 20 or less carbon atoms measured under the following condition 3 of the pellicle container clip that secures the pellicle container from the outside is 1500 μg or less. -Condition 3- A clip used in the pellicle container is placed in a container as a test sample, and an extract is obtained by Soxhlet extraction in a water bath at 80°C for 6 hours using 200 ml of hexane as an extraction solvent. The obtained extract is analyzed by gas chromatography. In the gas chromatography, a flame ionization detector is used as a detector to detect the amount of components having 20 or less carbon atoms, and the total amount of the detected components having 20 or less carbon atoms is taken as the outgassing amount. In the above condition 3, when a cut piece of a clip is evaluated as a specimen, the total amount of outgassing may be calculated using the following formula I: [(amount of outgassing from specimen) × (mass of clip)] / (mass of specimen) = total amount of outgassing Formula I

[0010] <6> A pellicle having a pellicle film, a master adhesive, and a pellicle frame, and having an outgassing amount of 2.9 μg or less when measured under the following condition 4. -Condition 4- The pellicle is heated at 50°C for 4 hours, and the outgassing generated is adsorbed onto 150 mg of adsorbent. 150 mg of the adsorbent is then placed in a gas chromatograph mass spectrometer, and the total amount of outgassing of volatile organic components generated from the pellicle is measured under heating conditions of 280°C for 10 minutes. Here, the total amount of outgassing is determined in n-decane equivalent. <7> A pellicle housing including a pellicle storage container for housing a pellicle, a pellicle storage container clip according to any one of <1> to <3> that secures the pellicle storage container from the outside, and a pellicle packaging that packages the pellicle storage container, wherein the pellicle placed in the pellicle storage container has a pellicle film, a master adhesive, and a pellicle frame, and has an outgassing amount of 2.9 μg or less when measured under the following condition 4. -Condition 4- The pellicle is heated at 50°C for 4 hours, and the outgassing generated is adsorbed onto 150 mg of adsorbent. 150 mg of the adsorbent is then placed in a gas chromatograph mass spectrometer, and the total amount of outgassing of volatile organic components generated from the pellicle is measured under heating conditions of 280°C for 10 minutes. Here, the total amount of outgassing is determined in n-decane equivalent. <8> The pellicle according to <6> or <7>, wherein the master adhesive is a styrene-butadiene adhesive.

[0011] According to one embodiment of the present disclosure, it is possible to provide a clip for a pellicle storage container in which outgassing of volatile organic components is reduced. According to another embodiment of the present disclosure, it is possible to provide a pellicle storage container in which the generation of outgassing of volatile organic components is reduced, and a pellicle in which the amount of outgassing due to adhesion of outgassing of volatile organic components is reduced, using the clip for a pellicle storage container.

[0012] Fig. 1 is a plan view showing an example of a pellicle storage container clip. Fig. 2A is a side view of the pellicle storage container clip as seen from one opening side. Fig. 2B is a side view of the pellicle storage container clip as seen from the other opening side. Fig. 3 is a perspective view showing an example of a pellicle storage container whose four corners are sealed by the pellicle storage container clips shown in Fig. 1. Fig. 4 is a schematic cross-sectional view showing an example of a pellicle.

[0013] In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the present disclosure, when multiple substances corresponding to each component are present, the amount of each component means the total amount of multiple substances unless otherwise specified. In this specification, the term "process" does not only refer to an independent process, but also includes processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0014] <Pellicle Storage Container Clip 1> A first aspect of the pellicle storage container clip of the present disclosure is a pellicle storage container clip in which the outgassing amount of organic gases having 20 or less carbon atoms is 150 μg or less per 1 g of the clip, as evaluated under the following condition 1. In this disclosure, unless otherwise specified, the term "clip" refers to a "pellicle storage container clip."

[0015] - Condition 1 - 1 g of a cut piece of paperclip is placed in a container as a test sample, and an extract is obtained by Soxhlet extraction for 6 hours in a water bath at 80°C using 200 ml of hexane as the extraction solvent. The obtained extract is analyzed using gas chromatography. In gas chromatography, a flame ionization detector is used as the detector to detect the amount of components with a carbon number of 20 or less, and the total amount of the detected components with a carbon number of 20 or less is taken as the outgassing amount of organic gas with a carbon number of 20 or less. In condition 1, the components of organic gas with a carbon number of 20 or less (hereinafter also referred to as specific organic gas) are determined by using an n-paraffin mixed standard solution to identify the peak position of the corresponding carbon number in gas chromatography, and then analyzing the components with a known concentration of n-C ２０ H ４２ The value is derived from a calibration curve obtained by gas chromatography GC-FID when a standard solution of

[0016] In Condition 1, in consideration of variations in the amount of outgassing between clips from which the specimen is collected, the specimen may be collected from a plurality of different clips and the average value of the measured values ​​may be taken. When specimens are collected from a plurality of different clips and the average value of the measured values ​​is taken, from the viewpoint of accuracy of the amount of outgassing, it is preferable to collect cut pieces as specimens from at least four clips and use the average value, and it is more preferable to use the average value of eight clips.

[0017] In a first aspect of the clip of the present disclosure, the outgassing amount of specific organic gases is 150 μg or less per gram of clip. From the viewpoint of suppressing outgassing of the pellicle itself, it is preferably 100 μg or less per gram of clip, more preferably 50 μg or less per gram of clip, even more preferably 40 μg or less per gram of clip, particularly preferably 30 μg or less per gram of clip, and most preferably below the detection limit or 0 μg. Examples of specific organic gases include hydrocarbon compounds having 20 or less carbon atoms selected from aliphatic hydrocarbon compounds and aromatic hydrocarbon compounds. Outgassing refers to gases generated from materials constituting the clip, including resins, etc.

[0018] Furthermore, considering the outgassing amount throughout the entire pellicle container, the outgassing amount of the specific organic gas is preferably 405 μg or less per clip, more preferably 162 μg or less, even more preferably 135 μg or less, and particularly preferably 60 μg or less. This is because the mass of a resin clip typically used to seal a pellicle container is preferably in the range of 2 g to 5 g per clip. A general-purpose clip has a mass of approximately 2.7 g. There are no particular limitations on the shape of the clip, and any clip with a known sealing mechanism can be appropriately selected and applied as long as it can seal the pellicle container. Examples of clips include fasteners shaped as shown in FIG. 1.

[0019] FIG. 1 is a plan view showing an example of a clip. The clip 20 shown in FIG. 1 is made of resin and has a trapezoidal shape in a plan view, with an opening 22A on one side being wider than an opening 22B on the other side. FIG. 2A is a side view of the clip 20 as seen from one opening side, and FIG. 2B is a side view of the clip 20 as seen from the other opening side. As shown in the side views of FIGS. 2A and 2B, the clip 20 may have a shape having a protrusion 26 that fits into a recess (not shown) provided in the bottom of a pellicle storage container 24. FIG. 3 is a perspective view showing an example of the clip 20 shown in FIG. 1 attached to four corners from the outside of the pellicle storage container 24. FIG. 3 shows an example using a pellicle storage container 24 that is rectangular in a plan view. The pellicle storage container 24 illustrated in FIG. 3 includes a main body and a lid. 1 can be inserted into the four corners of the pellicle storage container 24 from the wider opening 22B (the other opening) side of the clip 20 to fasten the body and lid of the pellicle storage container 24. As shown in Fig. 3, by fastening the four corners of the pellicle storage container 24, which is rectangular in plan view, with the clips 20 from the outside of the pellicle storage container 24, the convex portions 26 of the clips 20 fit into the concave portions provided in the bottom of the pellicle storage container 24, and by fastening the body and lid of the pellicle storage container 24 at the four corners, the pellicle storage container 24 can be sealed from the outside by the four clips 20, i.e., fixed.

[0020] <Clip 2 for pellicle storage container> A second aspect of the clip for pellicle storage container of the present disclosure is a clip for pellicle storage container in which the amount of outgassing generated from one clip is 2.000 μg or less, as evaluated under the following condition 2.

[0021] Condition 2: A clip is placed in a container as a test sample and heated at 50°C for 4 hours, and the generated outgas is adsorbed onto 150 mg of adsorbent. 150 mg of adsorbent is then placed in a gas chromatograph mass spectrometer (hereinafter sometimes abbreviated as GCMS), and the total amount of outgassing of volatile organic components generated from the clip is measured under heating conditions of 280°C for 10 minutes. Here, the total amount of outgassing is calculated in n-decane terms, and the resulting total amount is divided by the number of test clips to determine the amount of outgassing per clip.

[0022] The GCMS measurement conditions applied in this disclosure are as follows: Measurement device name: GCMS-QP2010plus (Shimadzu Corporation) Column: DB-1 (inner diameter: 0.32 mm, length: 60 m, thickness: 1.00 μm) Scan range: 35 m / Z to 450 m / Z Ionization: 0.78 kV Measurement method: The amount of gas generated at 280°C for 5 minutes was calculated in n-decane equivalent.

[0023] In condition 2, taking into consideration variations in the amount of outgassing between clips from which the specimen is collected, it is preferable to collect specimens from multiple different clips and take the average of these measured values. In condition 2, from the viewpoint of accuracy of the amount of outgassing, it is preferable to collect specimens from at least four clips and use the average value, and it is more preferable to use the average value of eight clips. In the present disclosure, unless otherwise specified, the average value of eight clips is used as the total amount of specific organic gas.

[0024] In a second aspect of the clip of the present disclosure, the amount of outgassing of volatile organic components emitted from the clip is 2,000 μg or less per clip, and from the viewpoint of suppressing outgassing from the pellicle itself, it is preferably 0.5 μg or less per clip, more preferably 0.05 μg or less per clip, even more preferably 0.04 μg or less per clip, particularly preferably 0.03 μg or less per clip, and most preferably below the detection limit or 0 μg.

[0025] Here, the volatile organic component refers to an organic component that volatilizes under conditions of 25° C. and 1 atm. Examples of the volatile organic component include hydrocarbon compounds such as aromatic hydrocarbon compounds and aliphatic hydrocarbon compounds.

[0026] From the viewpoint of the effect of suppressing outgassing of the pellicle, it is preferable that the clip of the present disclosure has an outgassing amount of specific organic gases measured under the above-mentioned condition 1 specified in the first aspect of the present disclosure of 150 μg or less per gram of clip, and an outgassing amount of volatile organic components measured under the above-mentioned condition 2 specified in the second aspect of the present disclosure of 2,000 μg or less per clip.

[0027] The clip of the present disclosure preferably contains a resin having a durometer hardness of D55 to D69. Durometer hardness can be measured using a Type D durometer indenter in accordance with JIS K7215-1986 "Durometer Hardness Test for Plastics" as defined in the Japanese Industrial Standards (JIS). When the resin contained in the clip has a durometer hardness of D55 or more, the generation of dust caused by friction of the clip surface at the contact point between the clip and the pellicle storage container is effectively suppressed. When the resin has a durometer hardness of D69 or less, the generation of dust caused by friction of the storage container surface at the contact point between the clip and the pellicle storage container is effectively suppressed. The durometer hardness of the resin contained in the clip is preferably in the range of D55 to D69, and more preferably in the range of D58 to D64.

[0028] The clip of the present disclosure preferably contains at least one resin selected from the group consisting of urethane resin, polyethylene resin, polyethylene terephthalate resin, polyvinyl chloride resin, polyamide resin, polycarbonate resin, acrylic resin, methacrylic resin, and phenolic resin. Examples of polyamide resins include PA6 and PA66. From the viewpoint of outgassing suppression, the clip preferably contains at least one resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyurethane resin. The clip may contain only one type of resin, or two or more types.

[0029] From the viewpoint of suppressing outgassing of the clip itself, a clip containing the above resin may be heat-treated at a temperature below the softening point of the resin after production. Heating the clip containing the resin at the softening point of the resin, for example, 50°C to 100°C, preferably 60°C to 90°C, for 10 to 30 hours, preferably 20 to 30 hours, is thought to reduce the volatile components inherent in the resin contained in the clip, more effectively suppress outgassing, and more easily achieve the conditions for the outgassing of specific organic gases measured under condition 1 above and the outgassing of volatile organic components measured under condition 2 above.

[0030] The pellicle container of the present disclosure includes a pellicle, a pellicle container that contains the pellicle, a clip for a pellicle container of the present disclosure that secures the pellicle container from the outside, and a pellicle packaging that packages the pellicle container. The pellicle packaging of the present disclosure reduces the amount of outgassing from the pellicle due to adhesion of volatile organic components outgassed from the clip used in the pellicle container.

[0031] The term "pellicle container" is used to mean a pellicle and each packaging member that packages the pellicle.

[0032] In the pellicle housing of the present disclosure, the pellicle is placed in a pellicle storage container made of resin such as polycarbonate, and the pellicle storage container is secured by clips at its four corners, making it less susceptible to influence from other packaging materials. Furthermore, the clips of the present disclosure suppress the generation of outgassing, such as specific organic gases and volatile organic components, that can cause pellicle contamination, to a low level, thereby further reducing the amount of outgassing from the pellicle due to adhesion of outgassing generated from the packaging material of the pellicle storage container. Furthermore, since a pressure difference between the inside and outside of the pellicle storage container can make it difficult to open, which can lead to problems when opening the pellicle storage container, it is preferable that the inside of the pellicle storage container is not sealed.

[0033] The clip used in the pellicle housing of the present disclosure preferably has a total outgassing amount of organic gases having 20 or less carbon atoms measured under the following condition 3: 648 μg or less. Condition 3: A cut piece of a clip used in the pellicle housing is placed in a container as a specimen, and an extract is obtained by Soxhlet extraction in a water bath at 80°C for 6 hours using 200 ml of hexane as an extraction solvent. The obtained extract is analyzed by gas chromatography. In the gas chromatography, a flame ionization detector is used as the detector to detect the amount of components having 20 or less carbon atoms, and the total amount of detected components having 20 or less carbon atoms is defined as the outgassing amount. The evaluation method under condition 3 is the same as the measurement method under condition 1, except that the specimen is changed from 1 g of a cut piece of a clip to the entire amount of clips used in the pellicle housing. Under condition 3, when a cut piece obtained by cutting a portion of a clip is evaluated as the specimen, the total outgassing amount may be calculated using the following formula I: [(Amount of outgassing from the specimen) × (mass of the clip)] / (mass of the specimen) = total amount of outgassing (Equation I)

[0034] The clips used in the pellicle container of the present disclosure preferably have a total outgassing amount of organic gases having 20 or less carbon atoms measured under the above condition 3 of 1500 μg or less, more preferably 1000 μg or less, even more preferably 500 μg or less, and particularly preferably 350 μg or less, and may be below the measurement limit.

[0035] The pellicle container may be a known pellicle container, and examples of the material for the pellicle container include resins such as polycarbonate, and conductive materials such as carbon nanotubes, conductive carbon black, and inorganic particles.

[0036] The pellicle used in the pellicle container can be a known pellicle. The pellicle is configured to include, for example, a pellicle membrane and a support frame that supports the pellicle membrane. The shape of the pellicle container is not particularly limited, but may be, for example, a box shape.

[0037] One embodiment of a pellicle will be described below with reference to the drawings. FIG. 4 is a schematic cross-sectional view showing a pellicle 10. In the pellicle 10, a pellicle membrane 12 and a support frame 14 are bonded via a membrane adhesive layer 13. The support frame 14 has an air vent 16 and a master adhesive layer 15 formed thereon. Although not shown, a release sheet (e.g., a separator) for protecting the master adhesive layer 15 may be further disposed on the surface of the master adhesive layer 15. The support frame 14 does not necessarily have to have an air vent 16, and may have a structure in which multiple layers are laminated together.

[0038] The pellicle film 12 is supported by a support frame 14. Examples of materials for the pellicle film 12 include transparent materials such as quartz glass, fluorine-based resins, cellulose acetate, and carbon nanotubes. Examples of materials for the support frame 14 include an anodized aluminum frame, a titanium frame, and a silicon frame. The support frame 14 is preferably black to prevent reflection of exposure light and facilitate inspection for the presence of attached foreign matter. The film adhesive layer 13 bonds the support frame and the pellicle film. Materials for the film adhesive layer 13 include, but are not limited to, fluoropolymers such as acrylic resin adhesives, epoxy resin adhesives, silicone resin adhesives, and fluorine-containing silicone adhesives. Note that if the pellicle film 12 and the support frame 14 can be bonded together without the film adhesive layer 13, the film adhesive layer 13 may be omitted. The master adhesive layer 15 can be formed by applying and drying a known adhesive. The material of the master adhesive layer 15 (hereinafter also referred to as master adhesive) is not particularly limited, but examples include acrylic, silicone, styrene butadiene, urethane, and olefin adhesives.

[0039] The pellicle in the pellicle container of the present disclosure may include an original plate adhesive, and the original plate adhesive may be a styrene-butadiene adhesive.

[0040] Styrene-butadiene adhesives are preferred as materials for the master adhesive layer 15 that bonds the support frame 14 and the master, because they facilitate suppressing distortion of the master. Styrene-butadiene adhesives are more likely to be outgassed from the pellicle after volatile organic component outgassing from the pellicle package adheres to the pellicle. By having the above-described configuration, the pellicle package according to the present disclosure reduces the amount of outgassing from the pellicle due to the adhesion of volatile organic component outgassing from the pellicle package, even when a styrene-butadiene adhesive is used as the material for the master adhesive layer 15.

[0041] In the present disclosure, the term "adhesive" is a concept that encompasses adhesives and pressure-sensitive adhesives. In the present disclosure, the term "adhesive layer" is a concept that encompasses adhesive layers and pressure-sensitive adhesive layers.

[0042] Examples of materials for the release sheet include polyethylene terephthalate film, polypropylene film, etc. As mentioned above, depending on the materials of the pellicle membrane 12 and the support frame 14, the support frame and the pellicle membrane may be bonded together without the membrane adhesive layer 13.

[0043] The pellicle of the present disclosure has a pellicle membrane, a master adhesive, and a pellicle frame, and exhibits an outgassing amount of 2.9 μg or less when measured under the following condition 4. -Condition 4- The pellicle is heated at 50°C for 4 hours, and the outgassing generated is adsorbed onto 150 mg of adsorbent. Then, 150 mg of adsorbent is placed in a gas chromatograph mass spectrometer (GCMS), and the total amount of outgassing of volatile organic components generated from the pellicle is measured under heating conditions of 280°C for 10 minutes. Here, the total amount of outgassing is calculated in n-decane equivalent. The method for measuring the outgassing of volatile organic components under condition 4 is the same as that under condition 2 described above, except that the specimen is replaced by a pellicle instead of a clip, and the GCMS measurement conditions applied are also the same.

[0044] The pellicle of the present disclosure is a pellicle container comprising a pellicle container for housing a pellicle, a pellicle container clip of the present disclosure for fixing the pellicle container, and a pellicle packaging body for packaging the pellicle container. The pellicle disposed in the pellicle container has a pellicle membrane, a master adhesive, and a pellicle frame, and exhibits an outgassing amount of 2.9 μg or less when measured under the following condition 4. -Condition 4- The pellicle is heated at 50°C for 4 hours, and the outgassing generated is adsorbed onto 150 mg of adsorbent. Then, 150 mg of adsorbent is placed in a gas chromatograph mass spectrometer, and the total amount of outgassing of volatile organic components generated from the pellicle is measured under heating conditions of 280°C for 10 minutes. Here, the total amount of outgassing is calculated in n-decane equivalent. The method for measuring the outgassing of volatile organic components under the above condition 4 is the same as that under the above condition 2, except that the specimen is replaced by a pellicle instead of a clip. The GCMS measurement conditions applied are also the same.

[0045] The pellicle package for packaging the pellicle container may be a known one. For example, the pellicle package may be a laminate including at least two layers, a sealant layer and a base layer.

[0046] From the viewpoint of strength in use, the pellicle packaging preferably has a breaking strength of 5N or more and 50N or less, more preferably 7N or more and 45N or less, and even more preferably 10N or more and 40N or less.

[0047] The breaking strength is measured in accordance with JIS-K7127-5 (1999) (corresponding to ISO527-3:1995). Both ends of a JIS-K7127 test piece type 5 (dumbbell-shaped with a total length of 115 mm, a width of the parallel portion of 6 mm, a gauge length of 25 mm, and a grip width of 25 mm) are pulled to measure the breaking strength.

[0048] There are no particular limitations on the specific method for achieving the breaking strength within the above range, but examples include a method of adjusting the material or thickness of the substrate layer.

[0049] The pellicle package preferably includes at least two layers: a sealant layer and a base layer, and more preferably includes a sealant layer, an adhesive layer, and a base layer in this order. When the pellicle package is a laminate including at least two layers: a sealant layer and a base layer, or when the pellicle package is a laminate including a sealant layer, an adhesive layer, and a base layer in this order, the outermost surface on the pellicle side may be the sealant layer, and the outermost surface on the outer peripheral surface side may be the base layer. When the pellicle package is configured with at least two layers: a sealant layer and a base layer, or when the pellicle package is a laminate including a sealant layer, an adhesive layer, and a base layer in this order, it is believed that outgassing of volatile organic components in the pellicle package is likely to occur from the sealant layer. Therefore, when the outermost surface on the pellicle side is a sealant layer, adhesion of outgassing of volatile organic components generated from the pellicle package also becomes significant. In contrast, the pellicle packaging of the present disclosure has the above-mentioned configuration, which makes it easier to maintain a low amount of outgassing from the pellicle, which is caused by the adhesion of volatile organic components outgassed from the pellicle packaging.

[0050] (Sealant Layer) The sealant layer may be a single layer or a laminate consisting of two or more layers. The material of the sealant layer is not particularly limited, and compositions containing known resins can be used. Examples of the resin include polyolefin resins, which are homopolymers such as polyethylene (PE) (including high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), etc.), polypropylene (PP), polybutene, and polymethylpentene; copolymers of two or more types selected from the group consisting of olefins such as ethylene, propylene, butene, and methylpentene; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; polyamide resins such as nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensation polymer, and polymethylmethacrylimide; and ethylene-vinyl alcohol copolymers. The resins used to form the sealant layer may be used alone or in combination of two or more types.

[0051] Among the above, from the viewpoint of further reducing the amount of outgassing from the pellicle due to the adhesion of outgassed volatile organic components generated from the pellicle packaging, it is preferable that the material of the sealant layer contains at least one selected from the group consisting of polyester resin, polyamide resin, and ethylene-vinyl alcohol copolymer, more preferably at least one selected from the group consisting of polyester resin and ethylene-vinyl alcohol copolymer, and even more preferably ethylene-vinyl alcohol copolymer.

[0052] The thickness of the sealant layer (total thickness when it has a laminated structure consisting of two or more layers) is preferably 500 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 40 μm or less. When the thickness of the sealant layer is within the above range, the amount of outgassing from the pellicle due to adhesion of volatile organic components outgassed from the pellicle package is further reduced.

[0053] From the viewpoint of sealing property, the thickness of the sealant layer (total thickness when the sealant layer has a laminate structure consisting of two or more layers) may be 3 μm or more, 5 μm or more, or 15 μm or more. From the above viewpoint, the thickness of the sealant layer (total thickness when the sealant layer has a laminate structure consisting of two or more layers) may be 3 μm or more and 500 μm or less, or 3 μm or more and 40 μm or less.

[0054] As described above, when a pellicle package is composed of at least two layers, a sealant layer and a base layer, it is believed that outgassing of volatile organic components in the pellicle package is likely to occur from the sealant layer. Therefore, as the thickness of the sealant layer increases, the adhesion of outgassing of volatile organic components generated from the pellicle package also tends to become more pronounced. In contrast, the pellicle package of the present disclosure, by having the above-described configuration, tends to maintain a low amount of outgassing from the pellicle due to the adhesion of outgassing of volatile organic components generated from the pellicle package, even when the thickness of the sealant layer is within the above range.

[0055] (Base Layer) The base layer may be a single layer or a laminate consisting of two or more layers.

[0056] The material of the substrate layer is not particularly limited, and compositions containing known resins can be used. Examples of the resin include polyolefin resins such as polyethylene (including high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), etc.), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene (PP), ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and ionomer resin; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; and amide resins such as nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensation polymer, and polymethyl methacrylimide. acrylic resins such as polymethyl methacrylate; styrene-acrylonitrile resins such as polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, and polyacrylonitrile; hydrophobic cellulose resins such as cellulose triacetate and cellulose diacetate; halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and Teflon (registered trademark); highly hydrogen-bonding resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and cellulose derivatives; engineering plastic resins such as polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyphenylene oxide resin, polymethylene oxide resin, and liquid crystal resin; and the like. The resins may be used alone or in combination of two or more.

[0057] Among the above, from the viewpoint of preventing dust and other debris from adhering to the surface of the pellicle packaging body, materials that are less likely to generate static electricity (preferably containing a resin that has been treated with an antistatic agent, more preferably a resin that contains either polyethylene terephthalate or polyethylene naphthalate) are preferred as materials for the base layer.

[0058] The thickness of the base layer (total thickness when it has a laminated structure consisting of two or more layers) is not particularly limited, but is, for example, preferably 0.1 μm or more and 500 μm or less, more preferably 1 μm or more and 100 μm or less, and even more preferably 5 μm or more and 30 μm or less.

[0059] (Adhesive Layer) The pellicle packaging of the present disclosure may have an adhesive layer between the sealant layer and the base layer, if necessary. The adhesive layer may be a single layer or a laminate consisting of two or more layers.

[0060] The material of the adhesive layer is not particularly limited, and a composition containing a known resin can be used, such as a polyurethane resin, a polyester resin, a polyether resin, or a mixture thereof.

[0061] The thickness of the adhesive layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesive strength, for example, and is not particularly limited, but is preferably 5 μm or less, more preferably 4 μm or less, from the viewpoint of shortening the curing reaction time when forming the adhesive layer and reducing the proportion of unreacted materials and residual solvents during the curing reaction, for example.

[0062] (Shape and Properties of Pellicle Package) The shape of the pellicle package is not particularly limited. Examples of the shape of the pellicle package include sheet, bag, pack, and box shapes. As long as the effects of the present disclosure are achieved, the pellicle package may be configured to include, as part of the package, a packaging member having a total outgassing amount of volatile organic components exceeding 90 ppm when heated at 100°C for 30 minutes. Meanwhile, the proportion of packaging members having a total outgassing amount exceeding 90 ppm in the pellicle package is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, of the entire pellicle package. It is preferable that the pellicle package does not include any packaging members having a total outgassing amount exceeding 90 ppm.

[0063] The volume of the pellicle package is not particularly limited and can be set appropriately depending on the size of the pellicle and the packaging form. The volume of the package is, for example, 2000 cm ３ ~70,000 cm ３ Preferably, ３ ~30,000 cm ３ More preferably, it is 5000 cm ３ ~10,000 cm ３ It is more preferable that:

[0064] When the volume of the pellicle package is within the above range, the balance between the volume of the pellicle or pellicle storage container packaged in the pellicle package and the surface area of ​​the pellicle package is easily optimized, which reduces the proportion of outgassing of volatile organic components generated from the pellicle package and further reduces the amount of outgassing from the pellicle due to adhesion of outgassing derived from the pellicle package.

[0065] The present disclosure will be described in more detail below with reference to examples, but the invention of the present disclosure is not limited to these examples.

[0066] <Experimental Examples 1 to 3 and Comparative Examples 1 to 2> Pellicle containers were obtained using the clips shown in the table, and the total amount of outgassing of volatile organic components from the clips and the pellicle packaged in the container was measured.

[0067] Example 1 (1) Preparation of Various Components as Raw Materials for Mask Adhesive Thermoplastic elastomer (A) Styrene-hydrogenated isoprene-styrene block copolymer (trade name "Hybrar 7125" (manufactured by Kuraray Co., Ltd.), tan δ peak temperature: -5°C, styrene content: 20% by mass)

[0068] Tackifying resin (B) Hydrogenated alicyclic petroleum resin: C9 hydrogenated petroleum resin (trade name "Arcon P-100" (manufactured by Arakawa Chemical Industries, Ltd.), softening point: 100±5°C, number average molecular weight (Mn): 610) Rosin ester resin (trade name "Pine Crystal KE-311" (manufactured by Arakawa Chemical Industries, Ltd.), softening point: 100±5°C)

[0069] Softener: Polybutene (product name "Nissan Polybutene 30N" (NOF Corporation))

[0070] Wax: Polypropylene pyrolysis wax (product name "Hiwax NP055" (manufactured by Mitsui Chemicals, Inc.))

[0071] (2) Pellicle Production A raw material mixture was obtained by mixing 100 parts by weight of thermoplastic elastomer (A), 100 parts by weight of tackifier resin (B), and 200 parts by weight of softener to a total weight of 48 g. The resulting raw material mixture was placed in a Labo Plastomill (manufactured by Toyo Seiki Seisakusho, Ltd., capacity: 60 mL) and sealed. The mixture was kneaded at 200°C and 100 rpm (revolutions per minute) for 20 minutes to obtain a block of mask adhesive. Approximately 10 g of mask adhesive was placed in a heating tank (internal temperature: 200°C) and melted. Meanwhile, an anodized aluminum support frame 14 (external dimensions: 148.77 mm x 114.9 mm, frame height H: 2.5 mm, frame width W: 2 mm) was prepared as shown in Figure 4. Molten mask adhesive was extruded from a needle tip connected to the heating tank and applied to one end face of the support frame 14 to form a master adhesive layer 15. The thickness of the formed master plate adhesive layer 15 was 0.6 mm. A separator was placed on the surface of the master plate adhesive layer 15. A pellicle membrane 12 was attached to the other end face of the support frame 14 (i.e., the end face on the side where the master plate adhesive layer 15 was not formed) via a membrane adhesive layer 13 (fluoropolymer (AGC Corporation, CYTOP A type)), to obtain a pellicle 10.

[0072] (3) Fabrication of Pellicle Container The prepared pellicle was placed in a polycarbonate container. Four polyethylene clips were prepared, which had been heat-treated at 90°C for 24 hours in an air atmosphere. Each clip had a mass of 2.9 g. The four corners of the polycarbonate container were fixed with the four prepared clips. The polycarbonate container fixed with the clips was stored at 23°C for two months in a state packaged in a pellicle package. The pellicle package was a laminate of a base material: polyethylene terephthalate and a sealant layer: ethylene-vinyl alcohol copolymer, and had a thickness of 25 μm.

[0073] (1. Evaluation of the Total Amount of Outgassing from Clips) The total amount of outgassing was measured for clips used in pellicle containers under the following conditions 1 and 2. The measurements were performed three times for each different specimen, and the average values ​​are shown in Table 1.

[0074] - Condition 1 - 1 g of a cut piece of paperclip was placed in a container as a test sample, and an extract was obtained by Soxhlet extraction for 6 hours in a water bath at 80°C using 200 ml of hexane as the extraction solvent. The obtained extract was analyzed by gas chromatography. In the gas chromatography, a flame ionization detector was used as the detector to detect the amount of components with a carbon number of 20 or less, and the total amount of the detected components with a carbon number of 20 or less was taken as the outgassing amount of organic gas with a carbon number of 20 or less. In condition 1, the organic gas components with a carbon number of 20 or less were determined by identifying the peak position of the corresponding carbon number in gas chromatography using an n-paraffin mixed standard solution, and then analyzing the n-C ２０ H ４２ The value was derived from a calibration curve obtained by gas chromatography GC-FID when a standard solution of

[0075] Condition 2: A clip was placed in a container as a test specimen and heated at 50°C for 4 hours, and the generated outgassing was adsorbed onto 150 mg of adsorbent. 150 mg of the adsorbent was then placed in a gas chromatograph mass spectrometer (GCMS), and the total amount of outgassing of volatile organic components generated from the clip was measured under heating conditions of 280°C for 10 minutes. The total amount of outgassing was calculated in n-decane terms, and the resulting total amount was divided by the number of test clips to determine the amount of outgassing per clip.

[0076] The GCMS measurement conditions applied in this disclosure are as follows: Measurement device name: GCMS-QP2010plus (Shimadzu Corporation) Column: DB-1 (inner diameter: 0.32 mm, length: 60 m, thickness: 1.00 μm) Scan range: 35 m / Z to 450 m / Z Ionization: 0.78 kV Measurement method: The amount of gas generated at 280°C for 5 minutes was calculated in n-decane equivalent.

[0077] (2. Evaluation of the Total Amount of Outgassing from a Pellicle) A pellicle stored in a pellicle container was placed in a clean oven under atmospheric conditions and heated at 70°C to 80°C for 20 hours to prepare a pellicle that had been degassed. The pellicle was packaged using the pellicle packaging and stored at 23°C for one week. After storage, the pellicle was removed from the pellicle packaging and placed in the oven. The outgassing generated under heating conditions of 50°C for four hours was adsorbed onto Tenax (trademark, manufactured by GL Sciences Inc.), a powdered adsorbent. The Tenax was then placed in a GCMS, and the total amount (μg) of outgassing of volatile organic components generated from the pellicle under heating conditions of 280°C for 10 minutes was measured (converted to n-decane), and this was defined as the "total amount of outgassing from a pellicle (μg / pellicle)." Measurements were performed twice for each different specimen, and the average values ​​are shown in Table 1.

[0078] [Example 2] A clip was made from the same polyethylene resin as in Example 1, and a clip and a pellicle container were made in the same manner as in Example 1, except that the heating conditions were 60°C for 24 hours, and then evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0079] [Example 3] A clip and a pellicle container were produced in the same manner as in Example 1, except that the clip was made of polypropylene resin and heated at 90°C for 24 hours, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0080] Comparative Example 1 A clip was made from the same polyethylene resin as in Example 1, and except that heating was not performed, a clip and a pellicle container were produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0081] Comparative Example 2 A clip was made from the same polypropylene resin as in Example 2, and except that heating was not performed, a clip and a pellicle container were produced in the same manner as in Example 2, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0082] In the following Table 1, PE represents polyethylene and PP represents polypropylene. The durometer hardness of the resins contained in the clips of Examples 1 to 3 and Comparative Examples 1 and 2, measured in accordance with JIS K7215-1986, was in the range of D55 to D69.

[0083]

[0084] As shown in Table 1, it was found that the amount of outgassing from the pellicle due to the adhesion of outgassing volatile organic components was reduced in the clips of Examples 1 to 3 and in the pellicle packaging using the clips of Examples 1 to 3, compared to the amount of outgassing from the pellicle due to the adhesion of outgassing volatile organic components that was generated in the pellicle packaging using the clips of Comparative Examples 1 to 2 and the pellicle packaging using the clips of Comparative Examples 1 to 2.

[0085] [Explanation of symbols] 10 Pellicle, 12 Pellicle film, 13 Film adhesive layer, 14 Support frame 15 Master adhesive layer, 16 Vent, 20 Clip for pellicle container (clip) 22A One opening of clip (narrower opening) 22B Other opening of clip (wider opening) 24 Pellicle container, 26 Convex portion of clip

[0086] The disclosure of Japanese Patent Application No. 2023-95898, filed on June 9, 2023, is incorporated herein by reference. All documents, patent applications, and technical standards mentioned in this disclosure are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A clip for a pellicle storage container, in which the amount of outgassing of organic gases having 20 or less carbon atoms is 150 μg or less per 1 g of the clip, as evaluated under the following condition 1. -Condition 1- 1 g of a cut piece of the paperclip is placed in a container as a test sample, and an extract is obtained by Soxhlet extraction using 200 ml of hexane as an extraction solvent in a water bath at 80° C. for 6 hours. The resulting extract is analyzed by gas chromatography, using a flame ionization detector to detect the amount of components having a carbon number of 20 or less, and the total amount of the detected components having a carbon number of 20 or less is taken as the amount of outgassing.

2. A clip for a pellicle storage container, in which the amount of outgassing generated from one clip is 2.000 μg or less, as evaluated under the following condition 2. -Condition 2- The clip is placed in a container as a test sample and heated at 50°C for 4 hours, and the generated outgassing is adsorbed onto 150 mg of adsorbent. 150 mg of adsorbent is then placed in a gas chromatograph mass spectrometer, and the total amount of outgassing of volatile organic components generated from the clip is measured under heating conditions of 280°C for 10 minutes. Here, the total amount of outgassing is calculated in terms of n-decane, and the total amount obtained is divided by the number of clips used as test clips to determine the amount of outgassing per clip.

3. 3. A clip for a pellicle storage container as described in claim 1 or claim 2, comprising at least one resin selected from the group consisting of urethane resin, polyethylene resin, polyethylene terephthalate resin, polyvinyl chloride resin, polyamide resin, polycarbonate resin, acrylic resin, methacrylic resin, and phenolic resin.

4. A pellicle and a pellicle storage container for storing the pellicle; The clip for a pellicle storage container according to claim 1 or 2, which fixes the pellicle storage container; a pellicle package that packages the pellicle storage container; A pellicle container comprising:

5. A pellicle container as described in claim 4, wherein the total amount of outgassing of organic gases having a carbon number of 20 or less measured under the following condition 3 of a clip for a pellicle container that fixes the pellicle container is 1500 μg or less. -Condition 3- A clip used in a pellicle holder is placed in a container as a test object, and an extract is obtained by Soxhlet extraction using 200 ml of hexane as an extraction solvent in a water bath at 80° C. for 6 hours. The resulting extract is analyzed by gas chromatography, using a flame ionization detector to detect the amount of components having a carbon number of 20 or less, and the total amount of the detected components having a carbon number of 20 or less is taken as the amount of outgassing.

6. A pellicle having a pellicle film, a master adhesive, and a pellicle frame, wherein the amount of outgassing measured under the following condition 4 is 2.9 μg or less. -Condition 4- The pellicle is heated at 50°C for 4 hours, and the outgassing generated is adsorbed onto 150 mg of adsorbent. Then, 150 mg of the adsorbent is set in a gas chromatograph mass spectrometer, and the total amount of outgassing of volatile organic components generated from the pellicle is measured under heating conditions of 280°C for 10 minutes. Here, the total amount of outgassing is calculated in terms of n-decane.

7. a pellicle storage container for storing the pellicle; The clip for a pellicle storage container according to claim 1 or 2, which fixes the pellicle storage container; a pellicle package that packages the pellicle storage container; A pellicle container comprising: the pellicle disposed in the pellicle storage container has a pellicle film, a master adhesive, and a pellicle frame; A pellicle having an outgassing amount of 2.9 μg or less when measured under the following condition 4. -Condition 4- The pellicle is heated at 50°C for 4 hours, and the outgassing generated is adsorbed onto 150 mg of adsorbent. Then, 150 mg of the adsorbent is set in a gas chromatograph mass spectrometer, and the total amount of outgassing of volatile organic components generated from the pellicle is measured under heating conditions of 280°C for 10 minutes. Here, the total amount of outgassing is calculated in terms of n-decane.

8. The pellicle according to claim 6 , wherein the master adhesive is a styrene-butadiene adhesive.

9. The pellicle according to claim 7 , wherein the master adhesive is a styrene-butadiene adhesive.