Pellicle, exposure master, exposure apparatus, and method for manufacturing pellicle

Abstract

This pellicle is provided with a pellicle frame, a pellicle film which is supported on one end surface of the pellicle frame, and an adhesive layer which is provided on the other end surface of the pellicle frame, and satisfies formula (1).　Formula (1): [A60°C] ≥ 4.0 gf / mm2 In formula (1), [A60°C] indicates a first release strength when the pellicle is on a test laminate. The test laminate is obtained by placing the pellicle on a quartz glass substrate such that the adhesive layer is in contact with the surface of the quartz glass substrate, and by maintaining a load on the pellicle under prescribed conditions. The first release strength indicates the load per unit adhesive area required to release the pellicle included in the test laminate from the quartz glass substrate obtained using a standard universal testing machine under prescribed conditions.

Description

[Technical field]

[0001] The present disclosure relates to a pellicle, an exposure master, an exposure apparatus, and a method for manufacturing a pellicle. [Background technology]

[0002] There is a known technology (i.e., photolithography) in which a photosensitive substance is applied to the surface of an object such as an electronic component, a printed circuit board, or a display panel, and then exposed to light in a pattern to form a pattern. In photolithography, a transparent substrate with a pattern formed on one side is used. This transparent substrate is called a photomask (hereinafter, also referred to as an "original"). A pellicle is attached to the photomask to prevent foreign matter such as dust from adhering to the surface of the photomask.

[0003] In recent years, as exposure patterns have become increasingly finer, the use of EUV (Extreme Ultra Violet) light, which has a shorter wavelength, has been expanding as a light source for exposure, instead of DUV (Deep Ultra Violet) light.

[0004] Patent Document 1 discloses a pellicle that leaves little residue after peeling without the addition of compounds such as surface modifiers. The pellicle disclosed in Patent Document 1 comprises a pellicle frame, a pellicle membrane, and a pellicle adhesive. The pellicle membrane is stretched over the upper end surface of the pellicle frame. The pellicle adhesive is attached to the lower end surface of the pellicle frame. The pellicle adhesive has a ratio of peel strength to tensile strength within a specified range. Patent Document 2 discloses that the amount of polymerization initiator in the adhesive layer is set to 8 ppm or less in order to prevent haze, and describes that a (meth)acrylic acid alkyl ester having an alkyl group having 4 to 14 carbon atoms is preferable in order to exhibit appropriate adhesive strength to the mask.

[0005] Patent Document 1: JP 2018-21182 A Patent Document 2: JP 2011-107469 A Summary of the Invention [Problem to be solved by the invention]

[0006] During exposure, the photomask moves at high speed. The pellicle must remain attached to the photomask to prevent foreign matter from adhering to it. Therefore, the adhesive layer of the pellicle must have a peel strength that prevents the pellicle from peeling off from the photomask during exposure. EUV light is easily absorbed by photomasks. Therefore, when exposed to EUV light, the photomask is likely to become hot. The heat of the photomask is thermally conducted to the pellicle. The adhesive layer of the pellicle is likely to absorb scattered EUV light. Furthermore, practical high-output EUV light sources have been developed. As a result, when exposed to EUV light, the pellicle is exposed to high temperatures. Specifically, it is expected that the pellicle will be exposed to a temperature of 60°C. However, the peel strength of the pellicle described in Patent Document 1 may decrease when exposed to a high-temperature environment, and as a result, the pellicle described in Patent Document 1 may peel off from the photomask during EUV exposure. Furthermore, in conventional pellicles, a soft adhesive layer is often used as the adhesive layer of the pellicle in order to suppress distortion of the photomask when the pellicle is attached to the photomask. However, the peel strength of the soft adhesive may decrease when exposed to a high temperature environment. For these reasons, pellicles used in EUV light exposure are required to be able to maintain their peel strength so that they do not peel off from the photomask even in high-temperature environments. For pellicles used in exposure to light other than EUV light, such as ArF, high reliability is also required to extend usable life.

[0007] The present disclosure has been made in consideration of the above circumstances. An object of the present disclosure is to provide a pellicle, an exposure master, an exposure apparatus, and a method for manufacturing a pellicle, which are unlikely to peel off from a photomask even when exposed to a high-temperature environment. "High temperature environment" refers to a temperature of 60°C. [Means for solving the problem]

[0008] Means for solving the above problems include the following embodiments. <1> A pellicle frame; A pellicle membrane supported on one end surface of the pellicle frame; an adhesive layer provided on the other end surface of the pellicle frame; Equipped with A pellicle that satisfies the following formula (1): Formula (1):[A 60℃ ]≧4.0gf / mm 2 (In the above formula (1), [A 60℃ ] indicates a first peel strength when the pellicle is used as a test laminate, The test laminate was obtained by placing the pellicle on a quartz glass substrate so that the adhesive layer was in contact with the surface of the quartz glass substrate, holding a load of 5 kgf on the pellicle for 30 seconds, removing the load, and then leaving the pellicle at 23° C. for 24 hours. The first peel strength indicates the load per unit adhesive area required to peel the pellicle included in the test laminate from the quartz glass substrate when the pellicle frame is pulled in the height direction of the pellicle frame against the quartz glass substrate at a speed of 0.1 mm / sec using a standard universal testing machine under the condition that the temperature of the quartz glass substrate is 60°C. <2> The above-mentioned satisfies the following formula (2): <1> The pellicle described in Equation (2):([A 60℃ ] / [A 23℃ ])>0.35 (In the formula (2), [A 23℃ ] indicates a second peel strength when the pellicle is used as the test laminate, The second peel strength indicates the load per unit adhesive area required to peel the pellicle included in the test laminate from the quartz glass substrate when the pellicle frame is pulled in the height direction of the pellicle frame against the quartz glass substrate at a speed of 0.1 mm / sec using a standard universal testing machine under the condition that the temperature of the quartz glass substrate is 23° C.) <3> The above satisfies the following formula (3): <1> or <2> The pellicle described in Formula (3):[A 23℃ ]≦30.0gf / mm 2 <4> The adhesive layer has a glass transition temperature Tg of more than -25°C and less than 10°C. <1> ~ <3> 2. A pellicle according to any one of claims 1 to 11. <5> The adhesive layer includes a copolymer of a (meth)acrylic acid alkyl ester monomer and a monomer having a functional group reactive with at least one of an isocyanate group, an epoxy group, and an acid anhydride. <1> ~ <4> 2. A pellicle according to any one of claims 1 to 11. <6> The (meth)acrylic acid alkyl ester monomer has at least one of an alkyl group having 1 to 3 carbon atoms and an alicyclic alkyl group. <5> The pellicle described in <7> The adhesive layer includes a copolymer of a (meth)acrylic acid alkyl ester monomer and a monomer having a functional group reactive with at least one of an isocyanate group, an epoxy group, and an acid anhydride, The (meth)acrylic acid alkyl ester monomer has at least one of an alkyl group having 1 to 3 carbon atoms and an alicyclic alkyl group. <4> The pellicle described in <8> The content of the (meth)acrylic acid alkyl ester monomer is 80 parts by mass to 99.5 parts by mass with respect to 100 parts by mass of the total amount of the monomers constituting the copolymer. <5> ~ <7> 2. A pellicle according to any one of claims 1 to 11. <9> The content of the monomer having a functional group is 0.5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of the monomers constituting the copolymer. <5> ~ <8> 2. A pellicle according to any one of claims 1 to 11. <10> the adhesive layer comprises a reaction product of the copolymer and a crosslinking agent, The content of the crosslinking agent is 0.002 parts by mass to 3,000 parts by mass with respect to 100 parts by mass of the total amount of the monomers constituting the copolymer. <5> ~ <9> 2. A pellicle according to any one of claims 1 to 11. <11> A master having a pattern, and the above-mentioned mounting member attached to a surface of the master having the pattern. <1> ~ <10> and a pellicle according to any one of the above. <12> A light source that emits exposure light; The above <11> and an optical system for guiding the exposure light emitted from the light source to the exposure master; having An exposure apparatus, wherein the original plate is positioned such that exposure light emitted from the light source is transmitted through the pellicle film and irradiated onto the original plate. <13> The above <1> ~ <10> A method for producing a pellicle according to any one of the above, attaching a pellicle membrane to one end surface of the pellicle frame; applying a coating composition to the other end surface of the pellicle frame and heating the composition to form the adhesive layer; Including, The coating composition comprises a copolymer of an alkyl (meth)acrylate monomer and a monomer having a functional group reactive with at least one of an isocyanate group, an epoxy group, and an acid anhydride. Effect of the Invention

[0009] The present disclosure provides a pellicle that is not easily peeled off from an original even when exposed to a high-temperature environment, an exposure original, an exposure apparatus, and a method for manufacturing a pellicle. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view showing a cross section of a pellicle according to an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] In the present disclosure, a numerical range indicated using "~" means a range that includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. 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 the upper or lower limit value of another numerical range described in the present disclosure. 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, combinations of two or more preferred embodiments are more preferred embodiments. In the present disclosure, when there are multiple substances corresponding to each component, the amount of each component means the total amount of the multiple substances, unless otherwise specified. In the present disclosure, the term "step" refers not only to an independent step, but also to a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved. In the present disclosure, when the expression "(meth)acrylic" is used, it is intended to mean either or both of "acrylic" and "methacrylic".

[0012] (1) Implementation form (1.1) Pellicle A pellicle according to an embodiment of the present disclosure comprises a pellicle frame, a pellicle membrane, and an adhesive layer. The pellicle membrane is supported on one end surface of the pellicle frame. The adhesive layer is provided on the other end surface of the pellicle frame. The pellicle according to the embodiment satisfies the following formula (1).

[0013] Formula (1): [A 60℃ ]≧4.0gf / mm 2 In the formula (1), [A 60℃ ] indicates the first peel strength when the pellicle was used as a test laminate. The test laminate was obtained by placing the pellicle on a quartz glass substrate so that the adhesive layer was in contact with the surface of the quartz glass substrate, holding a load of 5 kgf on the pellicle for 30 seconds, removing the load, and then leaving it at 23°C for 24 hours. The first peel strength indicates the load per unit adhesive area required to peel the pellicle contained in the test laminate from the quartz glass substrate when the pellicle frame is pulled in the height direction of the pellicle frame against the quartz glass substrate at a speed of 0.1 mm / sec using a standard universal testing machine under conditions where the temperature of the quartz glass substrate is 60°C. The method for measuring the first peel strength will be described in detail later in the Examples.

[0014] In the present disclosure, the temperature of the quartz glass substrate when measuring the first peel strength is set to 60°C because it is expected that the pellicle will be exposed to a temperature of 60°C during exposure to EUV light.

[0015] Since the pellicle according to the embodiment has the above-mentioned configuration, it is unlikely to peel off from the master even when exposed to a high-temperature environment (for example, 60° C.). The master will be described later. DUV light is not easily absorbed by an original plate or the like. Therefore, in exposure to DUV light, it is predicted that the temperature to which the pellicle is exposed will be approximately room temperature (23°C). However, even when the pellicle according to the embodiment is used for exposure to DUV light, there is a need to increase the first peel strength in a high-temperature environment. The pellicle according to the embodiment can meet such a need. In other words, the pellicle according to the embodiment has excellent reliability.

[0016] (1.1.1) First peel strength The pellicle according to the embodiment satisfies formula (1). [A 60℃ The lower limit is 4.0gf / mm 2 or more, preferably 5.0 gf / mm 2 More preferably, 8.0gf / mm 2 More preferably, 10.0 gf / mm 2That's all. [A 60℃ ] lower limit is 5.0gf / mm 2 If this is the case, the pellicle will be less likely to peel off from the master even when exposed to a high-temperature environment, and higher reliability can be expected. [A 60℃ The upper limit of is not limited, but may be, for example, 30.0 gf / mm 2 It can be made to be less than 25.0gf / mm 2 below can be set to 20.0gf / mm 2 It can be the following: From these perspectives, [A 60℃ ] is preferably 4.0gf / mm 2 ~30.0gf / mm 2 , more preferably 5.0 gf / mm 2 ~30.0gf / mm 2 , and more preferably 8.0 gf / mm 2 ~30.0gf / mm 2 , and particularly preferably 10.0 gf / mm 2 ~30.0gf / mm 2 [A 60℃ ] is preferably 8.0gf / mm 2 ~25.0gf / mm 2 , more preferably 8.0 gf / mm 2 ~20.0gf / mm 2 It is.

[0017] [A 60℃ ] is lowest when there is no exposure history, and tends to increase as the number of exposures increases. [A 60℃ It is preferable to evaluate in a state without any exposure history, but it may be evaluated after exposure.

[0018] (1.1.2) Peel strength ratio The pellicle according to the embodiment preferably satisfies the following formula (2).

[0019] Equation (2):([A 60℃ ] / [A 23℃ ])>0.35 In the formula (2), [A 23℃ ] indicates the second peel strength when the pellicle is used as the test laminate. The second peel strength indicates the load per unit adhesive area required to peel the pellicle contained in the test laminate from the quartz glass substrate when the pellicle frame is pulled in the height direction of the pellicle frame against the quartz glass substrate at a speed of 0.1 mm / sec using a standard universal testing machine under conditions where the temperature of the quartz glass substrate is 23°C. The method for measuring the second peel strength will be described in detail later in the Examples.

[0020] In the present disclosure, the temperature of the quartz glass substrate when measuring the second peel strength was set to 23°C because this is the temperature when the pellicle is peeled off from the original plate in order to replace the pellicle attached to the original plate.

[0021] By satisfying formula (2) in the pellicle according to the embodiment, the occurrence of adhesive residue can be suppressed. In particular, formula (1) is also satisfied at the same time. Full By adding this, the pellicle will not peel off from the master even when exposed to a high temperature environment (e.g., 60°C). To This makes it possible to achieve both adhesion and prevention of residual glue. "Adhesive residue" refers to at least a portion of the adhesive layer remaining on the master after the pellicle is peeled off from the master. A possible method to simply improve the first peel strength is to raise the glass transition temperature of the adhesive. However, simply raising the glass transition temperature requires a large second peel strength when peeling the pellicle from the master, which makes it more likely that adhesive residue will remain. If the pellicle satisfies formula (2), the pellicle will not peel easily from the master even when exposed to a high-temperature environment, and the occurrence of adhesive residue can be suppressed.

[0022] ([A 60℃ ] / [A 23℃ The lower limit of ]) is preferably 0.40 or more, more preferably 0.45 or more, even more preferably 0.48 or more, and particularly preferably 0.50 or more. ([A 60℃ ] / [A 23℃ When the lower limit of [ratio] is 0.35 or more, the amount of adhesive residue at room temperature can be reduced while making it difficult to peel the pellicle from the master in a high-temperature environment (for example, 60° C.). ([A 60℃ ] / [A 23℃ The upper limit of ]) is not limited, but can be, for example, 2.00 or less, preferably 1.00 or less, more preferably 0.80 or less, and even more preferably 0.70 or less. From these perspectives, ([A 60℃ ] / [A 23℃ ]) is preferably 0.40 to 2.00, more preferably 0.45 to 2.00, further preferably 0.48 to 2.00, and particularly preferably 0.50 to 2.00. 60℃ ] / [A 23℃ ]) is preferably 0.45 to 1.00, more preferably 0.45 to 0.80, and even more preferably 0.45 to 0.70.

[0023] [A 23℃ ] is lowest when there is no exposure history, and tends to increase as the number of exposures increases. [A 23℃ It is preferable to evaluate in a state without any exposure history, but it may be evaluated after exposure.

[0024] As a method for satisfying formula (2), for example, a method of adjusting the content of the crosslinking agent described later can be mentioned. Specifically, a method of adjusting the content of the crosslinking agent to 0.002 parts by mass or more and 3,000 parts by mass or less with respect to 100 parts by mass of the total amount of the monomers constituting the copolymer described later can be mentioned.

[0025] (1.1.3) Secondary Peel Strength [A 23℃ The lower limit of the pressure is not limited, but is preferably 4.0 gf / mm 2 More preferably, 6.0gf / mm 2 More preferably, 10.0 gf / mm 2 More than 15.0 gf / mm2 That's all. [A 23℃ The upper limit of the pressure is not limited, but is preferably 40.0 gf / mm in order to prevent damage to the master and the occurrence of adhesive residue when peeling the pellicle from the master. 2 Less than or equal to 30.0gf / mm 2 Less than or equal to 26.0gf / mm 2 Less than 20.0 gf / mm 2 The following is the result. From these perspectives, [A 23℃ ] is preferably 4.0gf / mm 2 ~40.0gf / mm 2 , more preferably 4.0 gf / mm 2 ~30.0gf / mm 2 , and more preferably 4.0 gf / mm 2 ~26.0gf / mm 2 , and particularly preferably 4.0 gf / mm 2 ~20.0gf / mm 2 [A 23℃ ] is preferably 6.0gf / mm 2 ~26.0gf / mm 2 , more preferably 10.0 gf / mm 2 ~26.0gf / mm 2 , and more preferably 15.0 gf / mm 2 ~26.0gf / mm 2 It is.

[0026] (1.1.4) Adhesive layer The pellicle according to the embodiment includes an adhesive layer. The adhesive layer enables the pellicle according to the embodiment to be adhered to the master.

[0027] The adhesive layer is a gel-like viscoelastic material. The adhesive layer has viscosity and cohesive strength. "Viscosity" refers to the liquid-like property of wetting the adherend when it comes into contact with the master plate. "Cohesive strength" refers to the solid-like property of resisting peeling from the master plate.

[0028] The adhesive layer is formed by applying a coating composition, heating, drying, curing, and other processes, as described below.

[0029] (1.1.4.1) Glass transition temperature The glass transition temperature Tg of the adhesive layer is preferably greater than −25° C. and less than 10° C. This allows the adhesive layer to have adhesive strength in the operating temperature range of the pellicle (e.g., 20° C. or higher), and makes the pellicle less likely to peel off from the master even when exposed to a high-temperature environment. In order to make it more difficult for the pellicle to peel off from the original plate even when exposed to a high-temperature environment, the lower limit of the glass transition temperature Tg of the adhesive layer is preferably above -25°C, more preferably -22°C or higher, even more preferably -20°C or higher, and most preferably -18°C or higher. From the viewpoint of imparting adhesiveness at room temperature, the upper limit of the glass transition temperature Tg of the adhesive layer is preferably less than 10°C, more preferably 5°C or lower, and even more preferably 0°C or lower. From the viewpoint of making it easier to suppress distortion of the master plate due to distortion of the pellicle frame, the upper limit of the glass transition temperature Tg of the adhesive layer is preferably −5° C. or lower, and more preferably −10° C. or lower. From these viewpoints, the glass transition temperature Tg is preferably from -25°C to 5°C, more preferably from -25°C to 0°C, more preferably from -25°C to -5°C, more preferably from -25°C to -10°C, even more preferably from -22°C to -10°C, particularly preferably from -20°C to -10°C, and even more preferably from -18°C to -10°C. The glass transition temperature Tg of the adhesive layer is measured in the same manner as in the examples.

[0030] (1.1.4.2) Coating composition The coating composition contains compounds selected from various polymers, solvents, crosslinkers, catalysts, initiators, etc. depending on the adhesive layer to be formed. The coating composition is a precursor of the adhesive composition, i.e., when the coating composition is cured, it becomes the adhesive composition.

[0031] (1.1.4.3) Adhesive composition The adhesive composition is not particularly limited, and examples thereof include acrylic, silicone, styrene butadiene, urethane, and olefin adhesives. Among them, from the viewpoint of reducing the amount of outgassing generated from the pellicle, the adhesive composition is preferably an acrylic adhesive.

[0032] The acrylic pressure-sensitive adhesive will now be described.

[0033] (1.1.4.4) Acrylic adhesives The acrylic pressure-sensitive adhesive preferably contains a (meth)acrylic acid alkyl ester copolymer.

[0034] (1.1.4.4.1) (Meth)acrylic acid alkyl ester copolymer The (meth)acrylic acid alkyl ester copolymer is a (meth)acrylic acid alkyl ester monomer; It is preferable that the resin contains a copolymer with a monomer having a functional group reactive with at least one of an isocyanate group, an epoxy group, and an acid anhydride (hereinafter also referred to as a "functional group-containing monomer").

[0035] Hereinafter, the copolymer of the (meth)acrylic acid alkyl ester monomer and the functional group-containing monomer will also be referred to as "the copolymer".

[0036] Since the acrylic pressure sensitive adhesive contains an alkyl (meth)acrylic acid ester copolymer, the pellicle has a sufficient first peel strength and can suppress the occurrence of adhesive residue.

[0037] The weight average molecular weight (Mw) of the (meth)acrylic acid alkyl ester copolymer is preferably from 30,000 to 2.5 million, more preferably from 50,000 to 1.5 million, and even more preferably from 70,000 to 1.2 million. If the upper limit of the weight average molecular weight (Mw) of the (meth)acrylic acid alkyl ester copolymer is 2.5 million or less, the solution viscosity can be controlled within a range that allows easy processing even if the solid content of the coating composition is increased. The upper limit of the weight average molecular weight (Mw) of the (meth)acrylic acid alkyl ester copolymer is preferably 2.5 million or less, more preferably 1.5 million or less, and even more preferably 1.2 million or less. If the lower limit of the weight average molecular weight (Mw) of the (meth)acrylic acid alkyl ester copolymer is 30,000 or more, the pellicle has an appropriate first peel strength and the occurrence of adhesive residue can be suppressed. The lower limit of the weight average molecular weight (Mw) of the (meth)acrylic acid alkyl ester copolymer is preferably 30,000 or more, more preferably 50,000 or more, and even more preferably 70,000 or more. The weight average molecular weight (Mw) of the (meth)acrylic acid alkyl ester copolymer is measured by GPC (gel permeation chromatography), and the details of the measurement method will be described later in the Examples. For example, in general, the higher the monomer concentration during the polymerization reaction, the larger the weight average molecular weight (Mw) tends to be, and the smaller the amount of the polymerization initiator and the lower the polymerization temperature, the larger the weight average molecular weight (Mw) tends to be. The weight average molecular weight can be adjusted by adjusting the monomer concentration, the amount of the polymerization initiator and the polymerization temperature. Restriction It can be controlled.

[0038] The number average molecular weight (Mn) of the (meth)acrylic acid alkyl ester copolymer is preferably 5,000 to 500,000, more preferably 8,000 to 300,000, further preferably 10,000 to 200,000, and most preferably 20,000 to 200,000. If the upper limit of the number average molecular weight (Mn) of the (meth)acrylic acid alkyl ester copolymer is 500,000 or less, the solution viscosity can be controlled within a range that allows easy processing even if the solid content of the coating composition is increased. The upper limit of the number average molecular weight (Mn) of the (meth)acrylic acid alkyl ester copolymer is preferably 500,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less. If the lower limit of the number average molecular weight (Mn) of the (meth)acrylic acid alkyl ester copolymer is 5,000 or more, the first peel strength is adequate and the occurrence of adhesive residue can be suppressed. The lower limit of the number average molecular weight (Mn) of the (meth)acrylic acid alkyl ester copolymer is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and most preferably 20,000 or more. The number average molecular weight (Mn) of the (meth)acrylic acid alkyl ester copolymer is measured by gel permeation chromatography (GPC), and the details of the measurement method will be described later in the Examples.

[0039] The "weight average molecular weight (Mw) / number average molecular weight (Mn)" (hereinafter also referred to as "Mw / Mn") of the (meth)acrylic acid alkyl ester copolymer is preferably 1.0 to 10.0, more preferably 2.0 to 9.0, even more preferably 2.5 to 8.0, and most preferably 3.0 to 7.0. If the Mw / Mn is within the above range, the (meth)acrylic acid alkyl ester copolymer can be easily produced and adhesive residue can be reduced. If the upper limit of Mw / Mn is 10.0 or less, the occurrence of adhesive residue can be suppressed. The upper limit of Mw / Mn is preferably 10.0 or less, more preferably 9.0 or less, even more preferably 8.0 or less, and most preferably 7.0 or less. If the lower limit of Mw / Mn is 1.0 or more, the (meth)acrylic acid alkyl ester copolymer can be easily produced. The lower limit of Mw / Mn is preferably 1.0 or more, more preferably 2.0 or more, even more preferably 2.5 or more, and most preferably 3.0 or more.

[0040] The (meth)acrylic acid alkyl ester monomer preferably contains a (meth)acrylic acid alkyl ester monomer having an alkyl group having 1 to 14 carbon atoms. Examples of the (meth)acrylic acid alkyl ester monomer having an alkyl group having 1 to 14 carbon atoms include a (meth)acrylic acid ester monomer of a linear aliphatic alcohol, a (meth)acrylic acid ester monomer of a branched aliphatic alcohol, and a (meth)acrylic acid ester monomer of a cyclic aliphatic alcohol. Examples of (meth)acrylic acid ester monomers of linear aliphatic alcohols include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and lauryl (meth)acrylate. Examples of the (meth)acrylic acid ester monomer of a branched chain aliphatic alcohol include isobutyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, etc. These may be used alone or in combination of two or more. Examples of the (meth)acrylic acid ester monomer of a cyclic aliphatic alcohol include cyclohexyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate.

[0041] Among these, it is preferable that the (meth)acrylic acid alkyl ester monomer has at least one of an alkyl group having 1 to 3 carbon atoms and an alicyclic alkyl group. Hereinafter, a (meth)acrylic acid alkyl ester monomer having at least one of an alkyl group having 1 to 3 carbon atoms and an alicyclic alkyl group is also referred to as a “high Tg monomer.” “Tg” refers to the glass transition temperature. In order to further reduce the amount of outgassing, the (meth)acrylic acid alkyl ester monomer is more preferably an acrylic acid alkyl ester monomer having an alkyl group or an alicyclic alkyl group having a carbon number of 1 to 3, and even more preferably an acrylic acid alkyl ester monomer having an alkyl group having a carbon number of 1 to 3. When the (meth)acrylic acid alkyl ester monomer is an acrylic acid alkyl ester monomer having an alicyclic alkyl group, from the viewpoint of availability, the number of carbon atoms in the alicyclic alkyl group is preferably 5 to 10. When the (meth)acrylic acid alkyl ester monomer contains a high Tg monomer, a high first peel strength can be maintained even in a high temperature atmosphere. Specifically, examples of high Tg monomers include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, and dicyclopentanyl methacrylate. Among these, in order to more easily maintain a high first peel strength even in a high temperature atmosphere, it is preferable that the (meth)acrylic acid alkyl ester monomer has at least one of an alkyl group having 1 to 2 carbon atoms and an alicyclic alkyl group, and it is more preferable that the (meth)acrylic acid alkyl ester monomer has an alkyl group having 1 to 2 carbon atoms.

[0042] The (meth)acrylic acid alkyl ester copolymer includes a copolymer of a (meth)acrylic acid alkyl ester monomer and a monomer having a functional group reactive with at least one of an isocyanate group, an epoxy group, and an acid anhydride; The (meth)acrylic acid alkyl ester monomer preferably has at least one of an alkyl group having 1 to 3 carbon atoms and an alicyclic alkyl group. This allows the pellicle to have sufficient first peel strength, and can suppress the occurrence of adhesive residue, while further suppressing the amount of outgassing.

[0043] The content of the (meth)acrylic acid alkyl ester monomer is preferably 80 parts by mass to 99.5 parts by mass, more preferably 85 parts by mass to 99.5 parts by mass, and even more preferably 87 parts by mass to 99.5 parts by mass, relative to 100 parts by mass of the total amount of the monomers constituting the copolymer. If the content of the (meth)acrylic acid alkyl ester monomer is within the range of 80 parts by mass to 99.5 parts by mass, an appropriate adhesive strength can be achieved. From the viewpoint of realizing an appropriate adhesive strength and more easily maintaining a high first peel strength even in a high temperature atmosphere, the content of the (meth)acrylic acid alkyl ester monomer, which is at least one of an alkyl group having 1 to 3 carbon atoms and an alicyclic alkyl group, is preferably within the range of 80 parts by mass to 99.5 parts by mass. From the same viewpoint, the content of the (meth)acrylic acid alkyl ester monomer, which is at least one of an alkyl group having 1 to 2 carbon atoms and an alicyclic alkyl group, is more preferably within the range of 80 parts by mass to 99.5 parts by mass. From the same viewpoint, the content of the (meth)acrylic acid alkyl ester monomer, which is an alkyl group having 1 to 2 carbon atoms, is more preferably within the range of 80 parts by mass to 99.5 parts by mass.

[0044] The functional group-containing monomer is a monomer copolymerizable with the (meth)acrylic acid alkyl ester monomer, and has a functional group reactive with at least one of an isocyanate group, an epoxy group, and an acid anhydride. Examples of functional group-containing monomers include carboxy group-containing monomers, hydroxy group-containing monomers, and epoxy group-containing monomers. Examples of the carboxy group-containing monomer include (meth)acrylic acid, itaconic acid, (meth)acrylic acid / itaconic acid, maleic acid, and crotonic acid. Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. An example of the epoxy group-containing monomer is glycidyl (meth)acrylate. These may be used alone or in combination of two or more. In particular, from the viewpoints of copolymerizability, versatility, etc., the functional group-containing monomer preferably contains a hydroxy group-containing (meth)acrylic acid having a hydroxyalkyl group having 2 to 4 carbon atoms, or glycidyl (meth)acrylate, which is an epoxy group-containing monomer. Examples of the hydroxy group-containing (meth)acrylic acid having a hydroxyalkyl group having 2 to 4 carbon atoms include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0045] The content of the functional group-containing monomer is preferably, for example, 0.5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of the monomers constituting the copolymer. From the viewpoint of improving the adhesive strength of the adhesive layer, the lower limit of the content of the functional group-containing monomer is more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, and particularly preferably 3 parts by mass or more, per 100 parts by mass of the total amount of the monomers constituting the (meth)acrylic acid alkyl ester copolymer. In order to ensure that the adhesive layer has an appropriate adhesive strength, the upper limit of the content of the functional group-containing monomer is more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the total amount of monomers constituting the (meth)acrylic acid alkyl ester copolymer.

[0046] (1.1.4.4.2) Polymerization method The polymerization method for the (meth)acrylic acid alkyl ester copolymer is not particularly limited, and examples thereof include solution polymerization, bulk polymerization, emulsion polymerization, various radical polymerizations, and the like. The (meth)acrylic acid alkyl ester copolymer obtained by these polymerization methods may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

[0047] (1.1.4.4.3) Polymerization solvent The reaction solution comprises a polymerization solvent. In the solution polymerization, for example, propyl acetate, ethyl acetate, toluene, etc. can be used as a polymerization solvent. This allows the viscosity of the copolymer solution to be adjusted. As a result, the thickness and width of the coating composition can be easily controlled during polymerization. Examples of dilution solvents include propyl acetate, acetone, ethyl acetate, and toluene. The viscosity of the copolymer solution is preferably 1000 Pa·s or less, more preferably 500 Pa·s or less, and further preferably 200 Pa·s or less. The viscosity of the coating composition is the viscosity when the temperature of the coating composition is 25° C., and can be measured by an E-type viscometer.

[0048] (1.1.4.4.4) Solution polymerization An example of solution polymerization is a method in which a polymerization initiator is added to a mixed solution of monomers under a stream of an inert gas such as nitrogen, and a polymerization reaction is carried out at 50° C. to 100° C. for 4 hours to 30 hours.

[0049] Examples of the polymerization initiator include azo-based polymerization initiators and peroxide-based polymerization initiators. Examples of the azo-based polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionate) dimethyl, and 4,4'-azobis-4-cyanovaleric acid. Examples of the peroxide-based polymerization initiator include benzoyl peroxide. The content of the polymerization initiator is preferably 0.01 parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the total amount of all monomers constituting the (meth)acrylic acid alkyl ester copolymer. In the solution polymerization, in addition to the polymerization initiator, a chain transfer agent, an emulsifier, etc. may be added to the monomer mixture solution. As the chain transfer agent, emulsifier, etc., any known agent may be appropriately selected and used.

[0050] It is preferable that the amount of the polymerization initiator remaining in the adhesive layer is small, so that the amount of outgassing generated during exposure can be reduced. Methods for reducing the amount of polymerization initiator remaining in the adhesive layer include a method of minimizing the amount of polymerization initiator added when polymerizing the (meth)acrylic acid alkyl ester copolymer, a method of using a polymerization initiator that is easily thermally decomposed, and a method of heating the adhesive at high temperatures for a long period of time during the adhesive application and drying process to decompose the polymerization initiator during the drying process.

[0051] The 10-hour half-life temperature is used as an index to express the thermal decomposition rate of a polymerization initiator. "Half-life" refers to the time it takes for half of the polymerization initiator to decompose. "10-hour half-life temperature" refers to the temperature at which the half-life is 10 hours. It is preferable to use a polymerization initiator having a low 10-hour half-life temperature. The lower the 10-hour half-life temperature, the easier the polymerization initiator is to thermally decompose. As a result, it is less likely to remain in the adhesive layer. The 10-hour half-life temperature of the polymerization initiator is preferably 80° C. or lower, more preferably 75° C. or lower.

[0052] Examples of azo-based polymerization initiators with a low 10-hour half-life temperature include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (10-hour half-life temperature: 30°C), 2,2'-azobisisobutyronitrile (10-hour half-life temperature: 65°C), and 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile) (10-hour half-life temperature: 30°C). Dimethyl 2,2'-azobis(2-methylpropionate) (10-hour half-life temperature: 66°C), and 2,2'-azobis(2-methylbutyronitrile) (10-hour half-life temperature: 67°C). Examples of peroxide-based polymerization initiators having a low 10-hour half-life temperature include dibenzoyl peroxide (10-hour half-life temperature: 74° C.) and dilauroyl peroxide (10-hour half-life temperature: 62° C.).

[0053] (1.1.4.4.5) Crosslinking agents The crosslinking agent is a compound that contributes to the formation of a three-dimensional network structure by reacting the functional group of the compound with the copolymer. The acrylic adhesive preferably contains a reaction product of a (meth)acrylic acid alkyl ester copolymer and a crosslinking agent. This can improve the cohesive strength of the resulting adhesive layer, suppress adhesive residue, and improve adhesive strength at high temperatures. The crosslinking agent has at least one of an isocyanate group, an epoxy group, an acid anhydride group, and a radical generating group.

[0054] Examples of the crosslinking agent include monofunctional epoxy compounds, polyfunctional epoxy compounds, acid anhydride compounds, metal salts, metal alkoxides, aldehyde compounds, non-amino resin amino compounds, urea compounds, isocyanate compounds, metal chelate compounds, melamine compounds, aziridine compounds, azo radical generators, and organic peroxides. Among these, in terms of excellent reactivity with the functional group component of the (meth)acrylic acid alkyl ester copolymer, the crosslinking agent is more preferably at least one of a monofunctional epoxy compound, a polyfunctional epoxy compound, an isocyanate-based compound, and an acid anhydride-based compound, and is more preferably an acid anhydride-based compound.

[0055] Examples of monofunctional epoxy compounds include glycidyl (meth)acrylate, glycidyl acetate, butyl glycidyl ether, and phenyl glycidyl ether. Examples of polyfunctional epoxy compounds include neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phthalic acid diglycidyl ester, dimer acid diglycidyl ester, triglycidyl isocyanurate, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, N,N,N',N'-tetraglycidyl m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyldiaminodiphenylmethane. Examples of the acid anhydride compound include aliphatic dicarboxylic acid anhydrides and aromatic polycarboxylic acid anhydrides. Examples of the aliphatic dicarboxylic anhydride include maleic anhydride, hexahydrophthalic anhydride, hexahydro-4-methylphthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, 2-methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, and tetrahydrophthalic anhydride. Examples of the aromatic polycarboxylic acid anhydride include phthalic anhydride and trimellitic anhydride. Examples of the isocyanate compound include xylylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, and multimers, derivatives, polymers, etc. These may be used alone or in combination of two or more.

[0056] The crosslinking agent may be a product, such as "RIKACID MH-700G" manufactured by New Japan Chemical Co., Ltd.

[0057] The adhesive layer contains a reaction product of the copolymer and a crosslinking agent, and the content of the crosslinking agent is preferably 0.002 parts by mass to 3,000 parts by mass per 100 parts by mass of the total amount of monomers constituting the copolymer. The content of the crosslinking agent is preferably 0.002 parts by mass to 3,000 parts by mass relative to 100 parts by mass of the total amount of the monomers constituting the copolymer, and from the viewpoint of obtaining an adhesive layer that is less likely to leave adhesive residue and reduces the stress that affects the flatness of the original plate, the content is more preferably 0.002 parts by mass to 2,000 parts by mass, even more preferably 0.005 parts by mass to 2.000 parts by mass, even more preferably 0.01 parts by mass to 1.000 parts by mass, and particularly preferably 0.1 parts by mass to 0.500 parts by mass. If the upper limit of the content of the crosslinking agent is 3.000 parts by mass or less, the crosslinking density of the (meth)acrylic acid alkyl ester copolymer is not too high. Therefore, it is considered that the pressure-sensitive adhesive absorbs the stress applied to the master plate, and the influence of the pressure-sensitive adhesive layer on the flatness of the master plate is mitigated. The upper limit of the content of the crosslinking agent is preferably 2.000 parts by mass or less, more preferably 1.000 parts by mass or less. On the other hand, if the lower limit of the crosslinking agent content is 0.002 parts by mass or more, the crosslink density will not become too small, so that handleability during the manufacturing process is maintained and glue residue is less likely to occur when the pellicle is peeled off from the master plate. If the content of the crosslinking agent is within the range of 0.002 parts by mass to 3,000 parts by mass, a pellicle that satisfies formula (2) can be obtained.

[0058] (1.1.4.4.6) Catalyst The coating composition may further contain a catalyst, which can further accelerate the curing of the (meth)acrylic acid alkyl ester copolymer. Examples of the catalyst include amine catalysts. Examples of the amine catalyst include octylate salt of (1,8-diazabicyclo-(5.4.0)undecene-7), triethylenediamine, etc. The amine catalyst may be a product of San-Apro Co., Ltd., such as "DBU", "DBN", "U-CAT", "U-CAT SA1", or "U-CAT SA102". The content of the catalyst is preferably 0.002 parts by mass to 3.000 parts by mass, and more preferably 0.10 parts by mass to 1.00 parts by mass, based on 100 parts by mass of the (meth)acrylic acid alkyl ester copolymer.

[0059] (1.1.4.4.7) Surface modifiers It is preferable that the coating composition does not contain a surface modifier, which can suppress the amount of outgassing.

[0060] (1.1.4.4.8) Additives The coating composition may contain additives such as fillers, pigments, diluents, antioxidants, tackifiers, etc., as necessary. These additives may be used alone or in combination of two or more kinds.

[0061] (1.1.4.4.9) Diluent The coating composition may contain a dilution solvent. This allows the viscosity of the coating composition to be adjusted. As a result, when the coating composition is applied to the other end surface of the pellicle frame, the thickness and width of the coating composition are easily controlled. Examples of dilution solvents include propyl acetate, acetone, ethyl acetate, and toluene. The viscosity of the coating composition is preferably 50 Pa·s or less, more preferably 10 Pa·s to 40 Pa·s, and even more preferably 20 Pa·s to 30 Pa·s. The viscosity of the coating composition is the viscosity when the temperature of the coating composition is 25° C., and can be measured by an E-type viscometer.

[0062] (1.1.4.5) Properties of the adhesive layer From the viewpoints of suppressing deterioration of the adhesive layer and suppressing the amount of outgassing, it is preferable that the adhesive layer is water-insoluble. The deterioration of the adhesive layer occurs when the adhesive layer is exposed to moisture in the atmosphere. To These include deterioration of adhesive strength and deterioration of mask distortion due to the presence of water. When moisture in the atmosphere is adsorbed to the adhesive layer, outgassing due to the moisture adsorbed to the adhesive layer is likely to occur in a vacuum environment such as EUV exposure. The fact that the adhesive layer is water-insoluble indicates that moisture in the atmosphere is unlikely to be adsorbed to the adhesive layer. Therefore, a water-insoluble adhesive layer can suppress the amount of outgassing. From the same viewpoint, it is preferable that the raw material of the adhesive layer contains the copolymer, and that the copolymer is water-insoluble.

[0063] Whether or not the adhesive layer is water-insoluble may be evaluated using the first gel fraction. The first gel fraction indicates the ratio (mass %) of the mass of the adhesive layer after the first treatment to the mass of the adhesive layer before the first treatment. The first treatment refers to a treatment in which the adhesive layer is immersed in water, heated and stirred at 60°C for 3 hours to obtain a residue of the adhesive layer that is not soluble in water, and the obtained residue is dried at 100°C for 3 hours. In the first treatment, the amount of water used is 100 parts by mass per part by mass of the adhesive layer. The mass of the adhesive layer after the first treatment is the ratio (mass %) of the residue of the adhesive layer. residue The adhesive layer used for the evaluation may be a test piece taken from the adhesive layer. If the first gel fraction is 70% by mass or less, the adhesive layer may be determined to be water-soluble. If the first gel fraction is 80% by mass or less, the adhesive layer may be determined to be water-soluble. If the first gel fraction is 90% by mass or less, the adhesive layer may be determined to be water-soluble.

[0064] Whether the copolymer is water-insoluble or not may be evaluated using a second gel fraction. The second gel fraction indicates the ratio (mass %) of the mass of the copolymer after the second treatment to the mass of the copolymer before the second treatment. The second treatment refers to a treatment in which the copolymer is immersed in water, heated and stirred at 60°C for 3 hours to obtain a residue of the copolymer that is not soluble in water, and the obtained residue is dried at 100°C for 3 hours. In the second treatment, the amount of water used is 100 parts by mass relative to 1 part by mass of the copolymer. The mass of the copolymer after the second treatment is the ratio (mass %) of the mass of the copolymer residue. residue The mass after drying is shown. The copolymer used for evaluation may be a test piece taken from the copolymer. If the second gel fraction is 70% by mass or less, the copolymer may be determined to be water soluble. If the second gel fraction is 80% by mass or less, the copolymer may be determined to be water soluble. If the second gel fraction is 90% by mass or less, the copolymer may be determined to be water soluble.

[0065] The adhesive layer may contain metal ions and ammonium ions from the viewpoints of suppressing deterioration of the adhesive layer, suppressing the amount of outgassing, etc. Examples of the metal ions include sodium ions, potassium ions, and calcium ions. The total content of metal ions and ammonium ions is preferably 4 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, particularly preferably 1 mass% or less, and even more preferably 0.5 mass% or less, relative to the total amount of the adhesive layer. The total content of metal ions and ammonium ions is preferably 4 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, particularly preferably 1 mass% or less, and even more preferably 0.5 mass% or less, based on the total amount of monomers constituting the copolymer. Furthermore, in order to suppress contamination of the device by components derived from ions such as metal ions, the content ratio of the total amount of metal ions and ammonium ions is preferably 4 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, particularly preferably 1 mass% or less, and even more preferably 0.5 mass% or less, relative to the mass of the adhesive layer. In order to suppress contamination of the device by components derived from ions such as metal ions, the total content of metal ions and ammonium ions is preferably 4 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, particularly preferably 1 mass% or less, and even more preferably 0.5 mass% or less, based on the total amount of monomers constituting the copolymer.

[0066] (1.1.4.6) Thickness The thickness of the adhesive layer is not particularly limited, and is preferably 0.01 mm to 1 mm, more preferably 0.1 mm to 0.8 mm. If the thickness of the adhesive layer is within the above range, the adhesive layer can ensure adhesion to the original plate while reducing distortion of the original plate after attachment, and errors during exposure can be eliminated.

[0067] (1.1.5) Pellicle frame The pellicle according to the embodiment includes a pellicle frame. The pellicle frame supports the pellicle membrane.

[0068] The pellicle frame is a cylindrical object. The pellicle frame has a through hole. The through hole represents a space through which the exposed light that has passed through the pellicle film passes to reach the original. The pellicle frame may have an air vent. When the pellicle frame is attached to the master, the air vent communicates the internal space of the pellicle with the external space of the pellicle. The "internal space of the pellicle" refers to the space surrounded by the pellicle and the master. The "external space of the pellicle" refers to the space not surrounded by the pellicle and the master.

[0069] The rectangular pellicle frame is composed of four sides when viewed in the thickness direction. The length of one side in the longitudinal direction is preferably 200 mm or less. The size of the pellicle frame is standardized according to the type of exposure device. The length of one side of the pellicle frame in the longitudinal direction being 200 mm or less satisfies the standardized size for exposure using EUV light. The length of one side in the short direction can be, for example, 5 mm to 180 mm, preferably 80 mm to 170 mm, and more preferably 100 mm to 160 mm. The height of the pellicle frame (i.e., the length of the pellicle frame in the thickness direction) is not particularly limited, but is preferably 3.0 mm or less, more preferably 2.4 mm or less, and even more preferably 2.375 mm or less. This allows the pellicle frame to meet the size standardized for EUV exposure. The height of the pellicle frame standardized for EUV exposure is, for example, 2.375 mm. The mass of the pellicle frame is not particularly limited, but is preferably 20 g or less, and more preferably 15 g or less, which makes the pellicle frame suitable for use in EUV exposure.

[0070] Examples of materials for the pellicle frame include aluminum, titanium, stainless steel, ceramic materials (eg, silicon, glass, etc.), and resins such as polyethylene. The shape of the pellicle frame corresponds to the shape of the master plate, and examples of the shape of the pellicle frame include a rectangular frame shape and a square frame shape.

[0071] (1.1.6) Pellicle membrane The pellicle according to the embodiment includes a pellicle membrane. The pellicle film prevents foreign matter from adhering to the surface of the original plate and transmits the exposure light during exposure. Foreign matter includes dust. Examples of the exposure light include deep ultraviolet (DUV: Deep UltraViolet) light and EUV. EUV refers to light with a wavelength of 5 nm to 30 nm.

[0072] The pellicle membrane covers the entire opening on one end face side of the through hole of the pellicle frame. The pellicle membrane may be supported directly on one end face of the pellicle frame, or may be supported via an adhesive layer (hereinafter also referred to as "membrane adhesive layer"). The membrane adhesive layer may be a cured product of a known adhesive.

[0073] The thickness of the pellicle membrane is preferably 1 nm to 200 nm. The material of the pellicle film is not particularly limited, and examples thereof include carbon-based materials, SiN, polysilicon, and the like. Carbon-based materials include carbon nanotubes (hereinafter also referred to as "CNTs"). In particular, it is preferable that the material of the pellicle film 12 includes CNTs. The CNTs may be single-wall CNTs or multi-wall CNTs, or may include single-wall CNTs and multi-wall CNTs. The pellicle membrane may be a nonwoven structure, for example, formed of fiber-shaped CNTs.

[0074] (1.1.7) Protective film The pellicle according to the embodiment may include a protective film (liner) as necessary. The protective film protects at least the surface of the adhesive layer that comes into contact with the original plate. The protective film is peelable from the adhesive layer. The thickness of the protective film is preferably 5 μm to 500 μm, more preferably 30 μm to 200 μm. Examples of the material for the protective film include polyester. The surface of the protective film that comes into contact with the adhesive layer may be coated with a release agent, such as a silicone-based release agent or a fluorine-based release agent.

[0075] (1.1.8) Exposed master The exposure master according to the embodiment includes a master and a pellicle according to the embodiment. The master has a pattern. The pellicle according to the embodiment is attached to the surface of the master that has the pattern. Since the exposure master according to the embodiment includes the pellicle according to the embodiment, the pellicle is unlikely to peel off from the master even when exposed to a high-temperature environment (for example, 60° C.).

[0076] The master may be, for example, a support substrate, a reflective layer, and an absorber layer laminated in this order. The absorber layer partially absorbs light (e.g., EUV), forming a desired image on a sensitive substrate (e.g., a semiconductor substrate with a photoresist film). The reflective layer may be a multilayer film of molybdenum (Mo) and silicon (Si). The absorber layer may be made of a material that is highly absorbent of EUV, etc. Examples of materials that are highly absorbent of EUV, etc. include chromium (Cr) and tantalum nitride.

[0077] (1.1.9) Exposure equipment The exposure apparatus according to the embodiment includes a light source, an exposure master according to the embodiment, and an optical system. The light source emits exposure light. The optical system guides the exposure light emitted from the light source to the exposure master. The exposure master is disposed such that the exposure light emitted from the light source passes through a pellicle film and is irradiated onto the master. The exposure equipment is capable of forming fine patterns (e.g., line widths of 32 nm or less) using EUV and other techniques, and can perform pattern exposure with reduced resolution problems caused by foreign matter, even when using EUV, for which resolution problems caused by foreign matter are likely to be an issue. The exposure light is preferably EUV. Since EUV has a short wavelength, it is easily absorbed by gases such as oxygen or nitrogen. Therefore, exposure to EUV light is performed in a vacuum environment.

[0078] (1.2) Manufacturing method of pellicle The method for producing a pellicle according to an embodiment of the present disclosure is a method for producing a pellicle according to an embodiment, and includes a pellicle film attaching step and an adhesive layer forming step, which will be described later. This produces a pellicle that satisfies formula (1). The order in which the pellicle film attaching step and the adhesive layer forming step are performed is not particularly limited.

[0079] (1.2.1) Pellicle membrane attaching process In the pellicle film attachment step, a pellicle film is attached to one end face of the pellicle frame. The method for attaching the pellicle membrane to one end surface of the pellicle frame is not particularly limited, and examples include a method in which a known adhesive is applied to one end surface of the pellicle frame to form a membrane adhesive layer, and the pellicle membrane is then placed on the membrane adhesive layer.

[0080] (1.2.2) Adhesive layer formation process In the adhesive layer forming step, the above-mentioned coating composition is applied to the other end surface of the pellicle frame and heated to form an adhesive layer. This causes the coating composition to dry and harden, resulting in an adhesive composition (adhesive layer).

[0081] (1.2.2.1) Application method The method for applying the coating composition to the other end surface of the pellicle frame is not particularly limited, and examples thereof include a method using a dispenser. The thickness of the coating composition is preferably 0.1 mm to 4.5 mm, more preferably 0.1 mm to 3.5 mm, and even more preferably 0.2 mm to 2 mm.

[0082] (1.2.2.2) Heat drying The method for heating the coating composition is not particularly limited, and known methods can be used. The temperature for heating the coating composition is appropriately selected depending on the boiling points of the solvent and residual monomers, the decomposition temperature of the (meth)acrylic acid alkyl ester copolymer, etc., and is preferably 50°C to 200°C, more preferably 60°C to 190°C.

[0083] The coating composition is heated to remove volatile compounds such as solvents and residual monomers from the adhesive layer. When the coating composition contains a crosslinking agent, the functional group of the (meth)acrylic acid alkyl ester copolymer reacts with the crosslinking agent by heating to form a crosslinked structure in the adhesive layer, resulting in a reaction product of the (meth)acrylic acid alkyl ester copolymer and the crosslinking agent. This heat drying causes the adhesive layer to adhere to the surface of the pellicle frame, and the pellicle frame and the adhesive layer become integrated.

[0084] (2) Variations (2.1) Pellicle A pellicle according to a modified example of the present disclosure comprises a pellicle frame, a pellicle membrane supported on one end surface of the pellicle frame, and an adhesive layer provided on the other end surface of the pellicle frame, and the glass transition temperature Tg of the adhesive layer may be greater than -25°C and less than 10°C. The glass transition temperature Tg of the adhesive layer is measured in the same manner as in the examples.

[0085] In the modified example, the pellicle has the above-mentioned configuration, and therefore is unlikely to peel off from the original even when exposed to a high-temperature environment (for example, 60° C.).

[0086] The pellicle according to the modified example is similar to the pellicle according to the embodiment, except that the adhesive layer has a glass transition temperature Tg of more than -25°C and less than 10°C, and does not have to satisfy the above formula (1). The description of the modified example of the present disclosure can be cited from the description of the embodiment of the present disclosure.

[0087] The preferred range of the glass transition temperature Tg of the adhesive layer and the like are the same as those in the embodiment.

[0088] (2.1.1) First peel strength In the modified example, it is preferable that the pellicle satisfies the above formula (1). As a result, as described above, the pellicle according to the modified example is unlikely to peel off from the master even when exposed to a high-temperature environment (for example, 60° C.). The preferred range of the first peel strength and the like are the same as those in the embodiment.

[0089] (2.1.2) Peel strength ratio It is preferable that the pellicle according to the modified example satisfies the above formula (2), which makes it possible to suppress the occurrence of adhesive residue, as described above. Peel strength ratio ([A 60℃ ] / [A 23℃ ]) and a method for satisfying formula (2) etc. , as in the embodiment.

[0090] (2.1.3) Secondary Peel Strength The preferred range of the second peel strength is the same as in the embodiment.

[0091] (2.1.4) Adhesive layer The pellicle of the modified example includes an adhesive layer. The adhesive layer enables the pellicle of the modified embodiment to be adhered to the master. The adhesive layer is a gel-like viscoelastic body, as in the embodiment. The adhesive layer is formed by applying a coating composition, heating, drying, curing, and other processes, as described below.

[0092] (2.1.4.1) Coating composition The coating composition is a precursor of the adhesive composition, including a composition containing compounds selected from various polymers, solvents, crosslinkers, catalysts, initiators, etc., depending on the adhesive layer to be formed. In other words, when the coating composition is cured, it becomes an adhesive composition.

[0093] (2.1.4.2) Adhesive composition The adhesive composition is not particularly limited, and examples thereof include acrylic, silicone, styrene butadiene, urethane, and olefin adhesives. Among them, from the viewpoint of reducing the amount of outgassing generated from the pellicle, the adhesive composition is preferably an acrylic adhesive.

[0094] The acrylic adhesive will be described below. The acrylic adhesive and the like according to the modified example are the same as those in the embodiment.

[0095] (2.1.4.3) Acrylic adhesives The acrylic pressure-sensitive adhesive preferably contains a (meth)acrylic acid alkyl ester copolymer.

[0096] The (meth)acrylic acid alkyl ester copolymer is a (meth)acrylic acid alkyl ester monomer; It is preferable that the resin contains a copolymer with a monomer having a functional group reactive with at least one of an isocyanate group, an epoxy group, and an acid anhydride. Since the acrylic pressure sensitive adhesive contains an alkyl (meth)acrylic acid ester copolymer, the pellicle has a sufficient first peel strength and can suppress the occurrence of adhesive residue.

[0097] The (meth)acrylic acid alkyl ester monomer preferably has at least one of an alkyl group having 1 to 3 carbon atoms and an alicyclic alkyl group. This makes it easier to have a sufficient first peel strength.

[0098] The (meth)acrylic acid alkyl ester copolymer includes a copolymer of a (meth)acrylic acid alkyl ester monomer and a monomer having a functional group reactive with at least one of an isocyanate group, an epoxy group, and an acid anhydride; The (meth)acrylic acid alkyl ester monomer preferably has at least one of an alkyl group having 1 to 3 carbon atoms and an alicyclic alkyl group. This allows the pellicle to have sufficient first peel strength, and can suppress the occurrence of adhesive residue, while further suppressing the amount of outgassing.

[0099] The content of the (meth)acrylic acid alkyl ester monomer is preferably 80 parts by mass to 99.5 parts by mass with respect to 100 parts by mass of the total amount of the monomers constituting the copolymer. If the content of the (meth)acrylic acid alkyl ester monomer is within the range of 80 parts by mass to 99.5 parts by mass, an appropriate adhesive strength can be achieved.

[0100] The content of the functional group-containing monomer is preferably, for example, 0.5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of the monomers constituting the copolymer.

[0101] (2.1.5) Pellicle Frame and Pellicle Film In the modified example, the pellicle frame, pellicle membrane, etc. are the same as in the embodiment.

[0102] (2.1.6) Protective film The pellicle according to the modified example may include a protective film (liner) as necessary. The protective film and the like are the same as those in the embodiment.

[0103] (2.1.7) Exposure master The exposure master according to the modified example includes a master and a pellicle according to the modified example. The master has a pattern. The pellicle according to the modified example is attached to the surface of the master that has the pattern. The exposure master according to the modified example includes the pellicle according to the modified example, so that the pellicle is unlikely to peel off from the master even when exposed to a high-temperature environment (for example, 60° C.). The master and the like are the same as those in the embodiment.

[0104] (2.1.8) Exposure equipment The exposure apparatus according to the modified example includes a light source, an exposure master according to the modified example, and an optical system. The light source emits exposure light. The optical system guides the exposure light emitted from the light source to the exposure master. The exposure master is disposed such that the exposure light emitted from the light source passes through a pellicle film and is irradiated onto the master. The function of the exposure device and the exposure light are the same as those in the embodiment.

[0105] (2.2) Manufacturing method of pellicle The method for producing a pellicle according to the modified example of the present disclosure includes a pellicle film attaching step and an adhesive layer forming step, which results in a pellicle having an adhesive layer with a glass transition temperature Tg in the range of more than -25°C and less than 10°C. The order in which the pellicle film attaching step and the adhesive layer forming step are performed is not particularly limited. The pellicle film attaching step and the adhesive layer forming step are the same as those in the embodiment. EXAMPLES

[0106] 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.

[0107] The components used in the examples and comparative examples are as follows. <(Meth)acrylic acid alkyl ester monomer> EA: Ethyl acrylate (Tg: -24℃) MMA: Methyl methacrylate ·BA: Butyl acrylate <Functional group-containing monomer> 4-HBA: 4-hydroxybutyl acrylate HEMA: 2-hydroxyethyl methacrylate ·GMA: Glycidyl methacrylate <Crosslinking agent> "Rikacid MH-700G" manufactured by New Japan Chemical Co., Ltd. AIBN: 2,2'-azobisisobutyronitrile (10-hour half-life temperature: 65°C) Peroxide radical generator: "Perkadox 12-XL25" manufactured by Kayaku Akzo Co., Ltd. (active ingredient concentration: 25%) Photoradical generator: "Ominirad 1173" from IGM Resins BV <Polymerization solvent> Propyl acetate <Catalyst> Amine catalyst: San-Apro Co., Ltd.'s "U-CAT SA-102" (chemical formula: octylate salt of (1,8-diazabicyclo-(5.4.0)undecene-7))

[0108] Example 1 The (meth)acrylic acid alkyl ester copolymers were prepared by known methods. Specifically, a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube was prepared. A polymerization solvent (180 parts by mass) was placed in the reaction vessel, and a mixture (423.4 parts by mass) of EA / 4-HBA / HEMA / GMA / AIBN (crosslinking agent) was charged in a mass ratio of 378 / 12.6 / 21 / 8.4 / 3.4. In a nitrogen atmosphere, this reaction solution was reacted at 85°C for 6 hours and then at 95°C for 2 hours to obtain an acrylic copolymer solution with a non-volatile content (copolymer) concentration of 70% by mass (weight average molecular weight: 119,000).

[0109] To the obtained acrylic copolymer solution (143 parts by mass), a crosslinking agent ("MH-700G") (0.28 parts by mass) and a catalyst ("U-CAT SA-102") (0.93 parts by mass) were added and mixed by stirring to obtain a coating composition.

[0110] As shown in FIG. 1, a pellicle frame (outer dimensions: 149 mm×115 mm, frame height H: 4.5 mm, frame width W: 2 mm) made of anodized aluminum was prepared as the pellicle frame 14. A prepared coating composition was applied to one end surface of the pellicle frame 14 using a dispenser. This was dried at 100° C. for 120 minutes, and a protective film was placed on the dried coating composition, followed by drying at 120° C. for 20 hours to form an adhesive layer 15 (thickness: 0.2 mm) made of an adhesive composition. A pellicle film 12 was attached to the other end surface of the pellicle frame 14 (the end surface on the side on which the adhesive layer 15 was not formed) via a film adhesive layer 13. This resulted in a pellicle 10. The obtained pellicle 10 was evaluated by the following method.

[0111] [First peel strength measurement] (1) A cleaned quartz glass substrate (type "#6025 substrate", manufactured by HOYA Corporation, size: 152 mm x 152 mm x 6.35 mm) was prepared. (2) The protective film was removed from the adhesive layer 15, and the pellicle 10 was attached to the quartz glass substrate using a pellicle mounter manufactured by Matsushita Seiki Co., Ltd. under a load of 5 kgf for 30 seconds so that the adhesive layer 15 was in contact with the surface of the quartz glass substrate, thereby obtaining a laminate. (3) The obtained laminate was stored (left to stand) at 23° C. for 24 hours to stabilize the adhesive strength, thereby obtaining a test laminate. The test laminate consisted of a quartz glass substrate and a pellicle 10. The pellicle 10 was adhered to the quartz glass substrate by an adhesive layer 15. The test laminate was held at the two long sides of the pellicle frame 14 using a universal material testing machine ("RTG-1310" manufactured by A & D Co., Ltd.) and a jig, and the load measuring load cell of the standard universal testing machine was set to a speed of 0.1 mm / sec. Under the condition that the temperature of the quartz glass substrate was 60° C., the pellicle 10 was lifted vertically upward (along the height direction of the pellicle frame 14), and the "first peel strength (gf / mm 2 ) was calculated. The allowable first peel strength is 4.0gf / mm 2The measurement results are shown in Table 1.

[0112] [Second peel strength measurement] The maximum load until the adhesive layer 15 was peeled off from the quartz glass substrate was measured in the same manner as in the first peel strength measurement, except that the measurement was performed in an air atmosphere of 23° C. and the temperature of the quartz glass substrate was 23° C. From the measured load, the "second peel strength (gf / mm 2 ) was calculated. The acceptable second peel strength is 4.0gf / mm 2 The measurement results are shown in Table 1.

[0113] [Adhesive residue evaluation test] The adhesive residue on the quartz glass substrate after the measurement of the first peel strength and on the quartz glass substrate after the measurement of the second peel strength were evaluated according to the following criteria. An acceptable rating is either "A" or "B." The measurement results are shown in Table 1. In the following criteria, the "area of ​​residual adhesive" refers to the area of ​​the adhesive layer 15 remaining on the quartz glass substrate after peeling off the pellicle 10. The "adhesion area" refers to the area of ​​the portion of the surface of the quartz glass substrate that is in contact with the adhesive layer 15.

[0114] A: The ratio of the area of ​​residual glue to the adhesive area is 0% or more and less than 10%. B: The ratio of the area of ​​residual glue to the adhesive area is 10% or more and less than 30% by area. C: The ratio of the area of ​​residual glue to the adhesive area is 30% or more.

[0115] The measurement results are shown in Table 1.

[0116] [Glass transition temperature (Tg)] The glass transition temperature (Tg) of the pressure-sensitive composition (pressure-sensitive adhesive layer) before attaching the pellicle 10 onto the quartz glass substrate was measured in accordance with JIS K7112. Specifically, using a differential scanning calorimeter (DSC), the glass transition temperature (Tg) of the pressure-sensitive composition before attaching the pellicle 10 onto the quartz glass substrate was measured under the conditions of a temperature increase rate of 20°C / min and nitrogen atmosphere. The measurement results are shown in Table 1.

[0117] [Viscosity] The viscosity of the copolymer solution was measured by the method described above. The measurement results are shown in Table 1.

[0118] [Measurement of the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the (meth)acrylic acid alkyl ester copolymer] The conditions of the GPC used to measure the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the (meth)acrylic acid alkyl ester copolymer are as follows. [GPC Conditions] Pump: "LC-10AD" manufactured by Shimadzu Corporation Oven: "CT020A" manufactured by Shimadzu Corporation Detector: "RI-101" manufactured by Showa Denko K.K. Data processing software: "Empower3" manufactured by Waters GPC column: "PLgel MIXED-B" (7.5×300 mm) × 2 columns manufactured by Agilent Technologies, Inc. Column temperature: 40°C Elution solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample concentration: 0.1% (w / v) Sample injection volume: 100 μL Standard substance: Monodisperse polystyrene

[0119] [Example 2] The reaction was carried out under the same conditions as in Example 1, except that EA, 4-HBA, and GMA were charged in the mass ratio shown in Table 1, to obtain an acrylic copolymer solution with a non-volatile content of 70 mass% (weight average molecular weight: 138,000). The obtained solution was applied and processed in the same manner as in Example 1, and various evaluations of the obtained pellicle 10 were carried out.

[0120] Example 3 The reaction was carried out under the same conditions as in Example 1, except that EA, MMA, 4-HBA, HEMA, and GMA were charged in the mass ratios shown in Table 1, to obtain an acrylic copolymer solution with a non-volatile content of 70 mass% (weight average molecular weight: 105,000). The obtained solution was applied and processed in the same manner as in Example 1, and various evaluations of the obtained pellicle 10 were carried out. In Example 3, the quartz glass substrate was broken during the measurement of the second peel strength, and the second peel strength was 26.0 gf / mm 2 became a higher value.

[0121] Example 4 The reaction was carried out under the same conditions as in Example 1, except that EA, BA, 4-HBA, and GMA were charged in the mass ratio shown in Table 1, to obtain an acrylic copolymer solution with a non-volatile content of 70 mass% (weight average molecular weight: 136,000). The obtained solution was applied and processed in the same manner as in Example 1, and various evaluations of the obtained pellicle 10 were carried out.

[0122] Example 5 Crosslinking agent ("Rika S The reaction was carried out under the same conditions as in Example 1, except that the amount of the acrylic copolymer (MH-700G) was changed to the amount shown in Table 1, and an acrylic copolymer solution with a non-volatile content of 70 mass % was obtained (weight average molecular weight: 134,000). The obtained solution was applied and processed in the same manner as in Example 1, and various evaluations of the obtained pellicle 10 were carried out.

[0123] Comparative Example 1 A resin composition was obtained by adding 4 parts by mass of a peroxide radical generator ("Perkadox 12-XL25") and 0.01 parts by mass of a photoradical generator ("Omnirad 1173") to 100 parts by mass of reactive acrylic polymer "Artcure RA-341" (solid content concentration: 100%) manufactured by Negami Chemical Industrial Co., Ltd. The obtained resin composition was applied to one end surface of the pellicle frame 14 with a dispenser to obtain a coated product. The obtained coated product was dried at 60° C. for 30 minutes, and the coated product was exposed to 410 mJ / cm 2 2 The coating was photocured by irradiating ultraviolet (UV) rays of 1000 nm. A protective film was placed on the coating, and then dried at 120°C for 20 hours to form an adhesive layer 15 (thickness: 0.2 mm) made of an adhesive composition. A pellicle film 12 was attached via a film adhesive layer 13 to the other end face (the end face on the side on which the adhesive layer 15 was not formed) of the pellicle frame 14 on which the adhesive layer 15 (thickness: 0.2 mm) was formed. In this way, a pellicle 10 was obtained. Various evaluations of the obtained pellicle 10 were carried out in the same manner as in Examples 1-3.

[0124] Comparative Example 2 A reaction was carried out under the same conditions as in Example 1, except that BA, HEMA, and GMA were charged in the mass ratio shown in Table 1, to obtain an acrylic copolymer solution with a non-volatile content of 70 mass% (weight average molecular weight: 186,000). The obtained solution was applied and processed in the same manner as in Example 1, and various evaluations of the obtained pellicle 10 were carried out.

[0125] [Table 1]

[0126] [Table 2]

[0127] table 2In Table 1, "substrate temperature" refers to the temperature of the quartz glass substrate. In Table 1, "copolymer solution" refers to an acrylic copolymer solution. In Table 1, the "parts" of each monomer in the "copolymer" refers to the mass ratio of each monomer to 100 parts by mass of the total amount of monomers constituting the copolymer. In Table 1, the "parts" of each component in the "additive blend amount" refers to the mass ratio of each component when the mass of the solid content of the copolymer solution (i.e., the total mass of the monomers constituting the copolymer) is 100 parts. In Table 1, "12XL25" refers to "Perkadox 12-XL25", "1173" refers to "omnirad1173", "SA102" refers to "U-CAT SA-102", and "MH700G" refers to "Rikacid MH-700G".

[0128] The pellicle of Comparative Example 1 includes a pellicle frame, a pellicle film, and an adhesive layer. 60℃ ] is 2.3gf / mm 2 and 4 . 0gf / mm 2 Therefore, it was found that the pellicle of Comparative Example 1 was easily peeled off from the photomask when exposed to a high-temperature environment (for example, 60° C.).

[0129] In the pellicle of Comparative Example 2, [A 60℃ ] is 3.25gf / mm 2 and 4 . 0gf / mm 2 Therefore, it was found that the pellicle of Comparative Example 2 was easily peeled off from the photomask when exposed to a high-temperature environment (for example, 60° C.).

[0130] In the pellicles of Examples 1 to 5, [A 60℃ ] is 4.0gf / mm 2 For these reasons, it was found that the pellicles of Examples 1 to 5 were not easily peeled off from the photomask even when exposed to a high-temperature environment (for example, 60° C.).

[0131] In addition, when comparing Examples 1 to 4 with Example 5, in Example 5, [A 60℃ ] / [A 23℃ ] was 0.39, and the adhesive residue at 23° C. was evaluated as “B.” 60℃ ] / [A 23℃ The adhesive residue at 23° C. was rated as “A”. Example 4 Unlike the adhesive composition of Example 5, the adhesive composition of Example 6 contains an appropriate amount of crosslinking agent (MH700G), so the crosslink density is not too small and it is believed that glue residue is less likely to remain when the pellicle is peeled off from the master plate.

[0132] The disclosure of Japanese Patent Application No. 2021-148630, filed on September 13, 2021, is incorporated by reference in its entirety into this specification. All publications, patent applications, and standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A pellicle frame; A pellicle membrane supported on one end surface of the pellicle frame; an adhesive layer provided on the other end surface of the pellicle frame; Equipped with The following formula (1) is satisfied: The glass transition temperature Tg of the adhesive layer is higher than −25° C. and lower than 10° C., The adhesive layer comprises a copolymer of a (meth)acrylic acid alkyl ester monomer and a monomer having a functional group reactive with at least one of an isocyanate group, an epoxy group, and an acid anhydride. Formula (1): [A ６０℃ ]≧4.0gf / mm ２ (In the above formula (1), [A ６０℃ ] indicates a first peel strength when the pellicle is used as a test laminate, The test laminate was obtained by placing the pellicle on a quartz glass substrate so that the adhesive layer was in contact with the surface of the quartz glass substrate, holding a load of 5 kgf on the pellicle for 30 seconds, removing the load, and then leaving the pellicle at 23° C. for 24 hours. The first peel strength indicates a load per unit adhesive area required to peel the pellicle included in the test laminate from the quartz glass substrate when the pellicle frame is pulled in the height direction of the pellicle frame against the quartz glass substrate at a speed of 0.1 mm / sec using a standard universal testing machine under the condition that the temperature of the quartz glass substrate is 60° C.)

2. The pellicle according to claim 1 , which satisfies the following formula (2): Formula (2): ([A ６０℃ ] / [A ２３℃ ])≧0.40 (In the above formula (2), [A ２３℃ ] indicates a second peel strength when the pellicle is used as the test laminate, The second peel strength indicates the load per unit adhesive area required to peel the pellicle included in the test laminate from the quartz glass substrate when the pellicle frame is pulled in the height direction of the pellicle frame against the quartz glass substrate at a speed of 0.1 mm / sec using a standard universal testing machine under the condition that the temperature of the quartz glass substrate is 23° C.)

3. The pellicle according to claim 1 or 2, which satisfies the following formula (3): Formula (3): [A ２３℃ ]≦30.0gf / mm ２

4. The pellicle according to claim 1 or 2, wherein the (meth)acrylic acid alkyl ester monomer has at least one of an alkyl group having 1 to 3 carbon atoms and an alicyclic alkyl group.

5. The pellicle described in claim 4, wherein the content of the (meth)acrylic acid alkyl ester monomer is 80 parts by mass to 99.5 parts by mass per 100 parts by mass of the total amount of monomers constituting the copolymer.

6. The pellicle according to claim 4, wherein the content of the monomer having the functional group is 0.5 parts by mass to 20 parts by mass per 100 parts by mass of the total amount of the monomers constituting the copolymer.

7. the adhesive layer comprises a reaction product of the copolymer and a crosslinking agent, The pellicle according to claim 4, wherein the content of the crosslinking agent is 0.002 parts by mass to 3,000 parts by mass per 100 parts by mass of the total amount of the monomers constituting the copolymer.

8. 3. An exposure master comprising: an original having a pattern; and the pellicle according to claim 1 or 2 attached to a surface of the original having the pattern.

9. A light source that emits exposure light; The exposure master according to claim 8 , an optical system for guiding the exposure light emitted from the light source to the exposure master; having An exposure apparatus, wherein the original plate is positioned such that exposure light emitted from the light source is transmitted through the pellicle film and irradiated onto the original plate.

10. A method for manufacturing the pellicle according to claim 1 or 2, comprising the steps of: attaching a pellicle membrane to one end surface of the pellicle frame; applying a coating composition to the other end surface of the pellicle frame and heating the composition to form the adhesive layer; Including, The coating composition comprises a copolymer of an alkyl (meth)acrylate monomer and a monomer having a functional group reactive with at least one of an isocyanate group, an epoxy group, and an acid anhydride.

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