Pellicle, exposure master, exposure device, method for producing pellicle, and method for testing adhesive layer for mask

Abstract

A pellicle 5 comprising a frame 12 in which a pellicle film 11 is disposed and a pressure-sensitive adhesive layer 13 for a mask disposed on the frame 12, wherein, when the pellicle 5 is peeled off after an attachment section S1 that is on a mask 4 made from quartz and to which the pressure-sensitive adhesive layer 13 is attached is irradiated from the back side of the mask 4 with a xenon (Xe) excimer lamp for two minutes, the remaining rate of the pressure-sensitive adhesive layer 13 ((the remaining area of the pressure-sensitive adhesive layer 13 on the mask 4 made from quartz) / (the area of the attachment section S1 for the pressure-sensitive adhesive layer 13)) is 0.001-5.0%.

Description

[Technical field]

[0001] The present invention relates to a pellicle, an exposure master, an exposure apparatus, a method for producing a pellicle, and a method for testing an adhesive layer for a mask. [Background technology]

[0002] In a lithography process for manufacturing electronic components, a pellicle is sometimes used to protect a photomask from dust. The pellicle has a frame on which a pellicle film is arranged and a mask adhesive layer arranged on the frame, and is attached to the photomask via the mask adhesive layer.

[0003] On the other hand, when the mask adhesive layer is exposed to stray light during exposure, it is likely to react with the surface of the photomask, and as a result, the adhesion to the photomask is likely to increase. In this case, even if the pellicle is peeled off from the photomask, the adhesive layer for the mask may remain on the photomask, which is called "glue residue". In recent years, with the shortening of the wavelength of the exposure light, the frequency of replacing the photomask has also increased, and under such circumstances, a pellicle that is easy to reduce the adhesive residue is desired.

[0004] Here, a pellicle has been proposed with the aim of reducing adhesive residue (see Patent Document 1). Patent Document 1 proposes controlling the content of carboxylic acid-containing monomer units in the pressure-sensitive adhesive layer for masks to 0.9% by mass or less relative to 100% by mass of the (meth)acrylic acid alkyl ester copolymer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2017-90719 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, there has been a demand for further reduction in the amount of residual adhesive rather than the reduction achieved by the technology described in Patent Document 1. Further reduction in the amount of residual adhesive is expected to further improve the efficiency of photomask replacement work. In addition, because the deterioration behavior of a pellicle differs between heating and light irradiation, there was a background to the expectation that an evaluation of adhesive residue as described in Patent Document 1 would be conducted.

[0007] In addition, under the circumstances where the pattern formed by the lithography process is required to have higher and higher resolution, distortion of the photomask, i.e., "mask distortion", has become a problem. From the viewpoint of preventing the above-mentioned adhesive residue, it is often advantageous to reduce the flexibility of the mask adhesive layer, but it is considered that a mask adhesive layer with reduced flexibility is more likely to cause mask distortion. The mask adhesive layer attached to the photomask is said to be one of the causes of mask distortion, and further efficiency of the mask replacement work is expected to be improved by reducing the mask distortion caused by the mask adhesive layer.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a pellicle that can further improve the efficiency of the photomask replacement work. Another object of the present invention is to provide an exposure master and exposure apparatus using the above pellicle, as well as a method for producing a pellicle and a method for testing an adhesive layer for a mask. [Means for solving the problem]

[0009] An example of an embodiment according to the present invention is as follows. [1] A pellicle having a frame on which a pellicle film is arranged and a mask adhesive layer arranged on the frame, A pellicle in which, when a portion of the adhesive layer attached to a quartz mask is irradiated with light from a xenon (Xe) excimer lamp from the back surface of the mask for 2 minutes and the pellicle is then peeled off, the remaining rate of the adhesive layer (remaining area of ​​the adhesive layer on the mask / area of ​​the attached portion of the adhesive layer) is 0.001 to 5.0%. [2] 2. The pellicle according to item 1, wherein when the attached portion is irradiated with Xe excimer lamp light from the back surface of the mask for 2 minutes and the pellicle is then peeled off, the remaining rate is 5.0% or less. [3] 3. The pellicle according to item 1 or 2, wherein the residual rate is 2.0% or less. [4] The pressure-sensitive adhesive layer is stretched in the longitudinal direction at an elongation of 20%, and then the tension is released. After 3 minutes, the residual stress value per unit cross-sectional area is greater than 0 and less than 10 mN / mm 2 A pellicle according to any one of items 1 to 3 below. [5] The pressure-sensitive adhesive layer is A (meth)acrylic copolymer, A curing agent having a crosslink density ensuring unit and a flexibility imparting unit; 5. The pellicle according to any one of items 1 to 4, comprising a reaction product of: [6] The (meth)acrylic copolymer contains a hydroxyl group-containing monomer, Item 6. The pellicle according to item 5, wherein the proportion of the hydroxyl group-containing monomer relative to the total amount of the (meth)acrylic copolymer is 4.0 mass % or less. [7] The crosslink density ensuring unit contains three or more isocyanate groups, 6. The pellicle according to item 5, wherein the flexibility-imparting unit comprises an aliphatic isocyanate compound containing an isocyanate group at the end of an alkyl chain having 4 or more carbon atoms. [8] 7. The pellicle according to item 5 or 6, wherein 95% by mass or more of the curing agent is an aliphatic isocyanate compound. [9] 9. The pellicle according to any one of items 5 to 8, wherein less than 5% by mass of the curing agent is an aromatic isocyanate compound.

[10] 10. The pellicle according to any one of items 5 to 9, wherein the ratio of the curing agent to the total amount of the (meth)acrylic copolymer is 0.20 to 3.00% by mass.

[11] 11. An exposure master comprising: a quartz mask; and the pellicle according to any one of items 1 to 10 attached to the mask.

[12] A light source that emits xenon (Xe) excimer lamp light; Item 12. An exposure master according to item 11, which is irradiated with light from a xenon (Xe) excimer lamp; An exposure apparatus comprising:

[13] A method for manufacturing a pellicle having a frame on which a pellicle film is arranged and a mask pressure-sensitive adhesive layer arranged on the frame, comprising: A method for producing a pellicle, in which when a portion of the adhesive layer attached to a quartz mask is irradiated with light from a xenon (Xe) excimer lamp from the back side of the mask for 2 minutes and then the pellicle is peeled off, the remaining rate of the adhesive layer (remaining area of ​​the adhesive layer on the mask / area of ​​the attached portion of the adhesive layer) is 0.001 to 5.0%.

[14] A pellicle having a frame on which a pellicle film is arranged and an adhesive layer for a mask arranged on the frame is used, A method for testing an adhesive layer for a mask, in which a value based on the remaining rate of the adhesive layer (remaining area of ​​the adhesive layer on a quartz mask / area of ​​the portion of the adhesive layer attached to the mask) is compared with a predetermined threshold value.

[15] A pellicle having a frame on which a pellicle film is arranged and a mask adhesive layer arranged on the frame, A xenon (Xe) excimer lamp was irradiated from the back surface of the quartz mask to the portion where the adhesive layer was attached, with an integrated radiation dose of 6.0 J / cm. 2and then peeling off the pellicle, the remaining rate of the adhesive layer (remaining area of ​​the adhesive layer on the mask / area of ​​the attached portion of the adhesive layer) is 0.001 to 5.0%. Effect of the Invention

[0010] According to the present invention, it is possible to provide a pellicle that can achieve both reduction in adhesive residue and reduction in mask distortion caused by the adhesive layer for the mask, thereby further improving the efficiency of photomask replacement work. Also, according to the present invention, it is possible to provide an exposure master and an exposure device, a method for producing a pellicle, and a method for testing an adhesive layer for a mask, all of which use the pellicle. [Brief description of the drawings]

[0011] [Figure 1] FIG. 2 is a diagram showing an example of the arrangement of an exposure apparatus and an exposure master according to the present embodiment. [Diagram 2] FIG. 2 is a diagram showing an example of the configuration of a pellicle according to the embodiment; [Diagram 3] 4 is a micrograph for explaining adhesive residue in the examples and comparative examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described. In this embodiment, a numerical range described using "~" includes the numerical values ​​described before and after "~" within the range. In this embodiment, an upper limit value or a lower limit value described in a certain numerical range in a stepwise described numerical range can be replaced with an upper limit value or a lower limit value of a numerical range in another stepwise described numerical range. In this embodiment, an upper limit value or a lower limit value described in a certain numerical range can also be replaced with a value described in the examples. In this embodiment, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes, as long as the function of the process is achieved. The scale, shape, and length of each part in the drawings may be exaggerated for further clarity.

[0013] [Exposure equipment and exposure master] 1 is a schematic diagram showing an example of the configuration of an exposure apparatus 1 and an original plate 2 according to this embodiment. As shown in the figure, the exposure apparatus 1 includes a light source 3 that emits light and an original plate 2 that is irradiated with the light. Among these, the original plate 2 includes a photomask 4 and a pellicle 5 that is attached to the photomask 4.

[0014] The light emitted from the light source 3 is Xe excimer lamp light, and the photomask 4 is made of quartz. Hereinafter, a photomask containing quartz may be referred to as a quartz mask.

[0015] Pellicle 5 is attached to photomask 4 so as to cover a circuit pattern (not shown) formed on photomask 4. Pellicle 5 functions as a dust-proof cover for photomask 4. In exposure apparatus 1, light (indicated by an arrow in FIG. 1) emitted from light source 3 passes through the circuit pattern of photomask 4, and further passes through the pellicle film of pellicle 5 to be guided to a photoresist (not shown) on stage 6.

[0016] Since the exposure device 1 and the exposure master 2 are equipped with the pellicle 5 according to this embodiment, it is possible to achieve both a reduction in adhesive residue and a reduction in mask distortion caused by the mask adhesive layer, thereby making it possible to further improve the efficiency of the photomask 4 replacement work.

[0017] [Pellicle] [Schematic configuration] 2(a) and (b) are diagrams showing an example of the configuration of a pellicle 5 according to this embodiment. As shown in the figures, the pellicle 5 has a frame 12 on which a pellicle film 11 is arranged, and an adhesive layer for a mask (hereinafter, may be simply referred to as an "adhesive layer") 13 arranged on the frame 12. In the pellicle 5, when a portion S1 where the adhesive layer 13 is attached to the photomask 4 is irradiated with Xe excimer lamp light from the back surface of the photomask 4 for 2 minutes and the pellicle 5 is then peeled off, the remaining rate of the adhesive layer 13 is 0.001 to 5.0%.

[0018] According to the above-mentioned configuration, it is possible to simultaneously reduce adhesive residue and mask distortion caused by the adhesive layer 13, and further improve the efficiency of the replacement work of the photomask 4.

[0019] [Frame] The frame 12 is a member for supporting the pellicle film 11. The frame 12 has a pair of sides 12A and a pair of sides 12B. Side 12A may be a long side, and side 12B may be a short side. These long sides 12A and short sides 12B form a rectangular outer shape, and a rectangular opening Op is formed inside the outer shape.

[0020] Both the long side 12A and the short side 12B are substantially rectangular parallelepiped shaped. Each of the long side 12A and the short side 12B has four faces (one face 12a, another face 12b opposite to the one face 12a, an inner peripheral face 12c, and an outer peripheral face 12d opposite to the inner peripheral face 12c). The one face 12a has an area where the pellicle film 11 is attached, and the other face 12b has an area where the adhesive layer 13 is formed.

[0021] The length of the long side 12A is, for example, 50 mm or more, 80 mm or more, or 100 mm or more, and 200 mm or less, 180 mm or less, or 160 mm or less. The length of the short side 12B is 30 mm or more, 50 mm or more, or 80 mm or more, and 180 mm or less, 160 mm or less, or 140 mm or less. The above length of the long side 12A and / or the short side 12B makes it easy to prevent the pellicle film 11 from bending, and also makes it easy to surround the circuit pattern formed on the photomask 4.

[0022] However, the configuration of the frame 12 (length, width, thickness, shape, etc.) can be changed as desired depending on the configuration of the pellicle film 11, the size of the circuit pattern formed on the photomask 4, etc. The frame 12 may be configured as an integral unit, or may be configured to be separable.

[0023] Frame 12 is aluminum; Aluminum alloys (e.g. 5000 series, 6000 series, 7000 series, etc.); Steel; stainless steel; Magnesium alloys; Ceramics such as silicon carbide (SiC), aluminum nitride (AlN), and aluminum oxide (Al2O3); Ceramic-metal composites (e.g. Al-SiC, Al-AlN, Al-Al2O3, etc.); Engineering plastics, such as polyethylene (PE), polyamide (PA), polycarbonate (PC), polyether ether ketone (PEEK), etc.; Fiber composite materials, such as glass fiber reinforced plastics (GFRP), carbon fiber reinforced plastics (CFRP), etc.; or Combinations of these; The insulating layer 11 can be made of known materials such as aluminum, copper, nickel, nickel alloy, and the like.

[0024] The inner peripheral surface 12c of the frame 12 may have an adhesive component for capturing foreign matter, if necessary. The adhesive component here may be: Acrylic, vinyl acetate, silicone, and rubber adhesives; Silicone-based and fluorine-based greases; etc.

[0025] [Pellicle membrane] The pellicle film 11 is a thin film having transparency. The pellicle film 11 covers the opening Op. The pellicle film 11 is attached to one surface 12a of the frame 12 via a pellicle film adhesive (not shown) in a state where a certain amount of tension is applied to the pellicle film 11 so that the film does not bend excessively due to the weight of the film itself.

[0026] The pellicle film 11 can be formed of nitrocellulose, a cellulose derivative, a fluoropolymer, etc. The thickness of the pellicle film 11 is, for example, 10 μm or less from the viewpoints of the transmittance of light emitted from the light source, the light resistance to such light, the self-supporting property of the pellicle film 11 itself, etc. The thickness is preferably 5 μm or less, and more preferably 1 μm or less.

[0027] [Protective film] Pellicle 5 may include a protective film 14 (liner) laminated on adhesive layer 13. Protective film 14 protects adhesive layer 13 during storage or transportation of pellicle 5, and is peeled off from adhesive layer 13 when pellicle 5 is attached to photomask 4.

[0028] The protective film 14 can be made of a resin such as polyester and has a thickness of, for example, 30 to 200 μm. The protective film 14 may have a silicone layer or a fluorine layer on the surface in contact with the pressure-sensitive adhesive layer 13 in order to improve peelability.

[0029] [Adhesive layer for mask] <Outline configuration> The adhesive layer 13 is a member for attaching the frame 12 to the photomask 4. The adhesive layer 13 can be disposed on the other surface 12b of the frame 12.

[0030] In the case of pellicle 5, when a portion S1 where adhesive layer 13 is attached to photomask 4 is irradiated with Xe excimer lamp light from the back surface of photomask 4 for 2 minutes and then pellicle 5 is peeled off, the remaining rate of adhesive layer 13 is 0.001 to 5.0%. The remaining rate is calculated by the following formula: Residual rate=(remaining area of ​​adhesive layer 13 on photomask 4) / (area of ​​attached portion S1 of adhesive layer 13) It is calculated by: For example, if the adhesive layer 13 remains in an area that is approximately 10% of the area of ​​the attached portion S1 of the adhesive layer 13, the remaining rate is expected to be approximately 10%, and at least 5.0%.

[0031] When the residual rate of the adhesive layer 13 is 5.0% or less, the operation of removing the adhesive layer 13 remaining on the photomask 4 can be shortened and / or simplified, thereby reducing the effort required for the removal operation. When the residual rate is sufficiently small, the removal operation itself can be omitted. From the above, further efficiency improvements in the replacement operation of the photomask 4 are expected. From the same viewpoint, the residual rate is preferably 2.0% or less, 1.5% or less, or 1.0% or less.

[0032] On the other hand, when the residual rate of the adhesive layer 13 is less than 0.001%, the flexibility of the mask adhesive layer is very low, i.e., the mask adhesive layer is often hard, and in this case, mask distortion is likely to occur. Therefore, when the residual rate of the adhesive layer 13 is 0.001% or more, the mask distortion caused by the adhesive layer 13 can be reduced, which makes it easier to reuse the photomask 4, and therefore further efficiency in replacing the photomask 4 is expected.

[0033] 2, the "area of ​​the affixed portion of the adhesive layer for the mask" corresponds to the area of ​​a portion S1 where the adhesive layer 13 is affixed to the photomask 4 when the adhesive layer 13 is affixed to the photomask 4. The area of ​​the portion S1 may correspond to the area of ​​the contact portion between the photomask 4 and the adhesive layer 13. When the adhesive layer 13 is disposed over the entire surface of the other surface 12b of the frame 12, the area of ​​the portion S1 may also correspond to the area of ​​the entire surface of the other surface 12b.

[0034] The "back side of the photomask" corresponds to the side of the photomask 4 opposite to the side to which the adhesive layer 13 is attached in FIG. 2. Using the exposure device 1 as shown in FIG. 1, Xe excimer lamp light is irradiated for 2 minutes under normal conditions and operations conforming to the actual lithography process. Then, the pellicle 5 is peeled off from the photomask 4 under normal conditions and operations conforming to the actual lithography process. The above realizes "irradiation of the back side of the photomask with Xe excimer lamp light for 2 minutes and then peeling off the pellicle." The peeling can be performed by using a known tensile tester to pull up the pellicle 5 perpendicular to the photomask 4 at a speed of 1 to 10 mm / min.

[0035] The "remaining area of ​​the mask adhesive layer on the photomask" corresponds to the area of ​​the adhesive layer 13 remaining on the photomask 4 after the peeling. The remaining area is also understood as the so-called "adhesive residue area." This remaining area can be roughly calculated by visual inspection, for example, or can be calculated in more detail by image analysis of the photomask 4.

[0036] The irradiation time of the Xe excimer lamp light is 2 minutes. The longer the irradiation time of the Xe excimer lamp light, the easier it is to harden the adhesive layer 13, and therefore the easier it is to reduce adhesive residue. In the pellicle 5 according to this embodiment, even if the irradiation time of the Xe excimer lamp light is selected to be as short as 2 minutes, the adhesive layer 13 can achieve both reduction in adhesive residue and reduction in mask distortion caused by the adhesive layer 13.

[0037] The adhesive layer 13 is stretched in the longitudinal direction at an elongation of 20% and then the tension is released. After 3 minutes, the residual stress value per unit cross-sectional area is greater than 0 and less than 10.0 mN / mm 2 The residual stress value is preferably more than 0, more preferably 1.0 mN / mm 2 The adhesive layer 13 having a residual stress value of more than 10.0 mN / mm is less likely to undergo cohesive failure, and therefore, adhesive residue is more likely to be reduced. 2The adhesive layer 13 having a residual stress value of 10.0 mN / mm or less is unlikely to have a strong adhesive force with the photomask 4, and therefore, adhesive residue is more likely to be reduced. 2 The adhesive layer 13 having a compressive strength of 8.0 mN / mm or less is likely to suitably reduce mask distortion caused by the adhesive layer 13. 2 Less than or equal to 6.0 mN / mm 2 Less than 5.0 mN / mm 2 If it is equal to or less than this, it is easier to suitably reduce the mask distortion. Here, the "elongation of 20%" is defined by the following formula: Elongation 20% = {(length of the adhesive layer for the mask after tension - length of the adhesive layer for the mask before tension) / length of the adhesive layer for the mask before tension} x 100 is revealed by.

[0038] The thickness of the adhesive layer 13 may be, for example, 0.15 to 3.0 mm, and can be appropriately selected depending on the field and / or use of the final product realized through the lithography process. When lithography is performed to obtain a semiconductor device, the thickness of the adhesive layer 13 suitable for the photomask used in the lithography is, for example, 0.15 mm or more, 0.20 mm or more, or 0.25 mm or more, and 1.0 mm or less, 0.8 mm or less, or 0.7 mm or less. When lithography is performed to obtain a liquid crystal device, the thickness of the adhesive layer 13 suitable for the photomask used in the lithography is, for example, 0.80 mm or more, 1.0 mm or more, or 1.2 mm or more, and 3.0 mm or less, 2.5 mm or less, or 2.0 mm or less.

[0039] The flatness of the adhesive layer 13 in the cross-sectional direction may be 1 μm or more, or 2 μm or more, and may be 20 μm or less, 15 μm or less, or 13 μm or less. If the flatness of the adhesive layer 13 in the cross-sectional direction is 1 μm or more, even if air bubbles are entrapped when the pellicle 5 is attached to the photomask 4, it is easy to preferably secure an escape route for the air bubbles. Furthermore, if the flatness of the adhesive layer 13 in the cross-sectional direction is 20 μm or less, the load when the pellicle 5 is attached to the photomask 4 is easily applied uniformly to the adhesive layer 13 and, in turn, to the photomask 4. Therefore, when the flatness of the adhesive layer 13 in the cross-sectional direction is within the above range, mask distortion is easily reduced.

[0040] The "cross-sectional direction of the adhesive layer for a mask" corresponds to the thickness direction of the frame 12. The flatness of the adhesive layer 13 in the cross-sectional direction can be derived by the following method. Each cross-section of the adhesive layer 13 disposed on the frame 12 is checked for any number of points (for example, 10 points, 12 points, 15 points, or 20 points). For each cross-section, the difference between the maximum thickness and the minimum thickness (height difference) is obtained. Then, the average value of the height differences obtained for the number of points is calculated. This average value corresponds to the flatness.

[0041] The thickness of the pressure-sensitive adhesive layer 13, and therefore the flatness, can be measured using a laser displacement meter. For a pellicle 5 with a protective film 14, the flatness may be measured after peeling off the protective film 14, or, if the flatness is not affected by the protective film 14, the flatness may be measured with the protective film 14 attached.

[0042] The pressure-sensitive adhesive layer 13 is, for example, Component (A): a base material having a specific functional group, (B) component: a curing agent having reactivity with a specific functional group; It can include structures derived from each of the above. In other words, the pressure-sensitive adhesive layer 13 can be composed of a reaction product of the above-mentioned component (A) and component (B). Depending on the type and / or ratio of each of the above-mentioned component (A) and component (B), various physical properties of the pressure-sensitive adhesive layer 13 can be controlled, and thus the above-mentioned residual rate can be controlled.

[0043] The pressure-sensitive adhesive layer 13 contains, for example, an acrylic copolymer. The physical properties of the acrylic copolymer can be easily controlled, and the raw materials thereof can be easily procured.

[0044] The proportion of component (A) relative to the total amount of pressure-sensitive adhesive layer 13 is preferably 98.0 mass% or more, or 99.0 mass% or more, and preferably 99.9 mass% or less, or 99.8 mass% or less. When the proportion of component (A) is within the above range, good adhesion of pressure-sensitive adhesive layer 13 to photomask 4, appropriate releasability of pressure-sensitive adhesive layer 13 from photomask 4, etc. are easily achieved.

[0045] <(A) Component: Main ingredient> The component (A) includes, for example, a (meth)acrylic copolymer, that is, a (meth)acrylic acid ester copolymer. In one embodiment, the (meth)acrylic acid ester copolymer is a copolymer of a (meth)acrylic acid ester and a monomer having a specific functional group. Among them, a copolymer obtained by using a mixture containing 80 to 99 mass % of a (meth)acrylic acid ester and 1 to 20 mass % of a monomer having a specific functional group is preferable from the viewpoint of exhibiting an appropriate adhesive strength to the photomask 4.

[0046] The weight average molecular weight of component (A) is, for example, 700,000 to 2,500,000, in which case it is easy to control the cohesive strength of pressure-sensitive adhesive layer 13 and / or the adhesive strength of pressure-sensitive adhesive layer 13 to photomask 4 to an appropriate level, and thus it is easy to reduce adhesive residue. From the same viewpoint as above, the weight average molecular weight of component (A) is 900,000 or more, or 1,050,000 or more, and 2,000,000 or less, or 1,500,000 or less.

[0047] The weight average molecular weight of component (A) tends to be large, for example, when the monomer concentration is high, the amount of polymerization initiator is small, or the polymerization temperature is low when the monomer raw material is polymerized. In general, the larger the weight average molecular weight, the larger the cohesive force tends to be, and the larger the cohesive force, the larger the residual stress value tends to be.

[0048] The component (A) can be produced by utilizing a known polymerization method. Examples of such polymerization methods include radical polymerization, ionic polymerization, living polymerization, living radical polymerization, etc. In the polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, etc. may be appropriately selected and used.

[0049] ((Meth)acrylic acid ester) The (meth)acrylic acid ester has, for example, an alkyl group having 1 to 14 carbon atoms, and the alkyl group may be linear or branched. However, from the viewpoint of reducing adhesive residue and good adhesion to the photomask 4, the alkyl group preferably has 4 to 8 carbon atoms and is linear. One type of (meth)acrylic acid ester may be used alone, or two or more types may be used in combination. The (meth)acrylic acid ester means one that does not have a specific functional group described later.

[0050] Examples of the (meth)acrylic acid ester having a linear alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate.

[0051] Examples of the (meth)acrylic acid ester having a branched alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, isopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and isononyl (meth)acrylate.

[0052] (Monomers with specific functional groups) The monomer having a specific functional group is copolymerizable with the (meth)acrylic acid ester. Here, the "specific functional group" refers to a functional group having reactivity with the (B) component, such as a carboxyl group (-COOH) and / or a hydroxyl group (-OH). The monomer having a specific functional group may be used alone or in combination of two or more kinds.

[0053] The monomer having a specific functional group is Carboxyl group-containing monomers such as (meth)acrylic acid, itaconic acid, maleic acid, and crotonic acid; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate; etc.

[0054] The quartz photomask 4 has hydroxyl groups on its surface. When a reaction occurs between the hydroxyl groups in the photomask 4 and the carboxyl groups contained in the carboxyl group-containing monomer in the adhesive layer 13, the photomask 4 and the adhesive layer 13 tend to bond strongly, and in this case, adhesive residue tends to occur. Therefore, the proportion of the carboxyl group-containing monomer relative to the total amount of the component (A) is preferably 0.9 mass% or less, 0.5 mass% or less, or 0.3 mass% or less.

[0055] When the number of crosslinks formed by the reaction between the hydroxyl groups contained in the hydroxyl-containing monomer and the component (B) in the unit polymer length of the pressure-sensitive adhesive layer 13 increases, the flexibility of the polymer is impaired, and the residual stress tends to increase. In addition, if the number of hydroxyl groups contained in the hydroxyl group-containing monomer in component (A) increases, the number of hydroxyl groups remaining after the reaction with component (B) increases, and the remaining hydroxyl groups are more likely to be naturally oxidized or oxidized in an exposure environment, which makes it easier for carboxyl groups to be generated. In this case, adhesive residue is more likely to occur as described above.

[0056] Therefore, the ratio of the hydroxyl group-containing monomer to the total amount of component (A) depends on the compatibility with component (B), but from the viewpoint of residual stress, for example, it is preferably 10 mass% or less, more preferably 4.0 mass% or less, and even more preferably 2.0 mass% or less. The lower limit of the ratio of the hydroxyl group-containing monomer is not particularly limited, but from the same viewpoint, it is preferably more than 0 mass%, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more.

[0057] The photomask 4 may have a chrome-deposited film formed on its surface. In this case, the light emitted from the light source is blocked by the chrome-deposited film. This prevents the reaction between the photomask 4 and the adhesive layer 13 from being caused by such light. On the other hand, by controlling the ratio of the carboxyl group-containing monomer to the total amount of component (A) as described above, it is easy to effectively reduce adhesive residue even for photomasks 4 that do not have a chrome-deposited film.

[0058] <Component (B): Hardener> The component (B) has reactivity with the specific functional group in the component (A) above. The component (B) is preferably an isocyanate compound and / or an epoxy compound, and among these, an isocyanate compound is more preferred.

[0059] The ratio of component (B) to the total amount of component (A) is preferably 0.20 to 3.00% by mass. This makes it easier to simultaneously reduce adhesive residue and mask distortion caused by the pressure-sensitive adhesive layer 13. From the same viewpoint, it is more preferably 0.25% by mass or more, 0.30% by mass or more, or 0.40% by mass (e.g., 0.400% by mass or more), and more preferably 2.00% by mass or less, 1.20% by mass or less, or 1.00% by mass or less.

[0060] The pressure-sensitive adhesive layer 13 has various properties, but in one embodiment, attention can be paid to its crosslink density and flexibility. It is preferable to focus on the crosslink density and flexibility and realize a configuration in the pressure-sensitive adhesive layer 13 that is advantageous in terms of each property. For example, it is preferable that the component (B) has a crosslink density ensuring unit and a flexibility imparting unit. This makes it easy to achieve both a reduction in adhesive residue and a reduction in mask distortion caused by the pressure-sensitive adhesive layer 13 in the pressure-sensitive adhesive layer 13.

[0061] The "crosslink density ensuring unit" in component (B) is a structural unit for ensuring the crosslink density in pressure-sensitive adhesive layer 13. When component (B) has a crosslink density ensuring unit, a structure derived from such a unit is introduced into pressure-sensitive adhesive layer 13, and as a result, the crosslink density in pressure-sensitive adhesive layer 13 is ensured to a degree suitable in light of the effects of the present invention.

[0062] The crosslinking density ensuring unit is preferably a plurality of isocyanate groups and / or a plurality of epoxy groups, and among these, a plurality of isocyanate groups is preferred. A compound having a plurality of isocyanate groups in one molecule is called, for example, a polyfunctional isocyanate compound. For example, a polyfunctional isocyanate compound may be a compound having three or more (for example, three, four, five, six, seven, or eight) isocyanate groups in one molecule.

[0063] The "flexibility-imparting units" in component (B) are structural units for imparting flexibility to pressure-sensitive adhesive layer 13. When component (B) has a flexibility-imparting unit, a structure derived from such a unit is introduced into pressure-sensitive adhesive layer 13, and as a result, flexibility is imparted to pressure-sensitive adhesive layer 13 to a degree suitable in light of the effects of the present invention.

[0064] The flexibility-imparting unit is preferably an isocyanate group located at the end of an alkyl chain having 4 or more carbon atoms, and among these, an isocyanate group located at the end of an alkyl chain having 5 to 7 carbon atoms (5, 6, or 7 carbon atoms) is preferred. The alkyl chain here may be linear, branched, or cyclic.

[0065] By ensuring a crosslink density in the adhesive layer 13 and / or imparting flexibility to the adhesive layer 13 to a suitable degree in light of the effects of the present invention, tearing of the adhesive layer 13 when peeling the pellicle 5 from the photomask 4 can be suitably prevented, and the adhesive layer 13 does not become too hard so as to cause mask distortion. This makes it easy to simultaneously reduce adhesive residue and reduce mask distortion caused by the adhesive layer 13, and thus makes it easy to further improve the efficiency of the work of replacing the photomask 4.

[0066] In one embodiment, the (B) component preferably contains an aliphatic isocyanate compound. This makes it easier to reduce adhesive residue. From the same viewpoint, it is preferable that 95% by mass or more of the (B) component is an aliphatic isocyanate compound, in other words, it is preferable that less than 5% by mass of the (B) component is an aromatic isocyanate compound. In the (B) component, 97% by mass or more may be an aliphatic isocyanate compound (less than 3% by mass is an aromatic isocyanate compound), 99% by mass or more may be an aliphatic isocyanate compound (less than 1% by mass is an aromatic isocyanate compound), or 100% by mass may be an aliphatic isocyanate compound. In addition, the term "aliphatic isocyanate compound" refers to an isocyanate compound that does not have an aromatic ring in its molecule, or that has an aromatic ring in its molecule and in which the isocyanate group is separated from the aromatic ring by at least two atoms, and the term "aromatic isocyanate compound" refers to an isocyanate compound in which the isocyanate group is directly bonded to the aromatic ring, or in which the isocyanate group is bonded to the aromatic ring via one carbon atom.

[0067] The component (B) is Having an isocyanurate skeleton; Having a reaction product of a diisocyanate and a polyol such as a diol or triol; etc. are preferred, in particular, Having an isocyanate skeleton in which an isocyanate group is attached to the nitrogen (N) atom in the isocyanurate skeleton via an alkyl chain; It has an isocyanate skeleton in which an isocyanate group is attached via an alkyl chain to a urethane bond containing an oxygen (O) atom derived from a polyol such as a diol or triol; This allows the crosslink density ensuring unit and the flexibility imparting unit to be introduced into the pressure-sensitive adhesive layer 13 relatively easily.

[0068] In summary, component (B) is: By including three or more isocyanate groups, it is possible to impart sufficient crosslink density to the pressure-sensitive adhesive layer 13, and the cohesive force is improved, making it easier to reduce adhesive residue. Furthermore, by including an isocyanate group at the end of an alkyl chain having 4 or more carbon atoms, the adhesive layer 13 can be given flexibility, and the residual stress can be kept low when the cohesive force is improved by the effect of the curing agent. This makes it easier to achieve both a reduction in adhesive residue and a reduction in mask distortion, and further improves the efficiency of the replacement work of the photomask 4. By not including aromatic isocyanate, it is possible to prevent the residual stress value from increasing excessively when the cohesive strength of the adhesive layer 13 is improved by the effect of the curing agent. This makes it easier to achieve both a reduction in adhesive residue and a reduction in mask distortion, and further makes it easier to further improve the efficiency of the replacement work of the photomask 4.

[0069] Examples of the component (B) include an aromatic isocyanate compound, an alicyclic isocyanate compound, and an aliphatic isocyanate compound.

[0070] Examples of aromatic isocyanate compounds include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), reaction products of the above diisocyanates with trimethylolpropane, isocyanurates made from the above diisocyanates, etc. Examples of products of aromatic isocyanate compounds include Coronate L (manufactured by Toso Corporation) and Desmodur L75 (manufactured by Covestro).

[0071] Examples of alicyclic isocyanate compounds include isophorone diisocyanate (IPDI), 1,4-bis(isocyanatomethyl)cyclohexane (hereinafter sometimes abbreviated as "hydrogenated XDI"), reaction products of the above diisocyanates with trimethylolpropane, isocyanurates made from the above diisocyanates as raw materials, etc. Examples of products of alicyclic isocyanate compounds include Desmodur Z4470 (manufactured by Covestro) and VESTANAT T1890E (manufactured by Evonik).

[0072] Examples of the aliphatic isocyanate compound include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (hereinafter sometimes abbreviated as "HDI"), 1,9-diisocyanatononane, 1,12-diisocyanatododecane, etc. Among them, as the aliphatic diisocyanate, HDI is particularly preferred because it is easily available industrially and has excellent weather resistance and flexibility of the coating film.

[0073] Examples of compounds having three or more isocyanate groups include reaction products of the above diisocyanates with polyols such as diols and triols, and isocyanurates and biuret products made from the above diisocyanates as raw materials.

[0074] Among the above, aliphatic isocyanate compounds are preferred, and among them, those containing three or more isocyanate groups are preferred in order to ensure crosslink density, and among those containing three or more isocyanate groups, in order to keep residual stress low, Isocyanurate bodies; Reaction products of diisocyanates with polyols such as diols and triols; It is more preferable to include etc. Examples of products of the aliphatic isocyanate compound include Desmodur N3300, N3600 (manufactured by Covestro), Coronate HX (manufactured by Toso Corporation), Duranate TPA-100, TKA-100, MFA-75B, MHG-80B, and E402-80B (manufactured by Asahi Kasei Corporation). The above-described (B) component may be used alone or in combination of two or more types.

[0075] <Other ingredients> The pressure-sensitive adhesive layer 13 may contain known additives, such as fillers, pigments, diluents, antioxidants, UV stabilizers, etc. The additives may be used alone or in combination of two or more.

[0076] [Manufacturing method of pellicle] The manufacturing method according to this embodiment includes the steps of: This is a method for producing a pellicle 5 in which, when a portion S1 of the adhesive layer 13 on the photomask 4 is irradiated with Xe excimer lamp light from the back surface of the photomask 4 for 2 minutes and then the pellicle 5 is peeled off, the remaining rate of the adhesive layer 13 is 0.001 to 5.0%.

[0077] Such a manufacturing method may, for example, include the following steps: First step: a step of obtaining a precursor composition for the pressure-sensitive adhesive layer 13. Second step: applying the resulting precursor composition to the frame 12 . The third step: a step of drying the applied precursor composition to obtain the adhesive layer 13.

[0078] In the first step, the component (A) and the component (B) are mixed to obtain a precursor composition for the pressure-sensitive adhesive layer 13. The component (A) and / or the component (B) may be mixed as is, or may be mixed after diluting with a predetermined solvent. The precursor composition may further contain a solvent from the viewpoint of controlling the coatability onto the frame 12 and / or the viewpoint of controlling the thickness of the resulting pressure-sensitive adhesive layer 13. Examples of such solvents include, but are not limited to, acetone, ethyl acetate, butyl acetate, toluene, etc.

[0079] As described above, the various physical properties of the pressure-sensitive adhesive layer 13 can be controlled by the type and / or ratio of each of the (A) component and the (B) component, and thus the residual rate can be controlled.

[0080] In the second step, the obtained precursor composition is applied to the frame 12. In one embodiment, in the second step, the precursor composition is applied to the other surface 12b of the frame 12. A method using a dispenser is preferable as the application method. In this case, the viscosity of the precursor composition may be 1 P·s or more, or 2 P·s or more, and may be 5 P·s or less, 4 P·s or less, or 3 P·s or less. The viscosity here is measured, for example, at 25° C. using a B-type viscometer.

[0081] In the third step, the applied precursor composition is dried to obtain the pressure-sensitive adhesive layer 13. This third step may further include the following steps. Third (1) step: Drying step. Third (2) process: Molding process.

[0082] In the third (1) step, the applied precursor composition is dried to reduce the amount of solvent in the precursor composition. In the third (1) step, the dried precursor composition may be heated to a moldable degree. The heating time may be, for example, 50 to 10,000 seconds, and the heating temperature may be, for example, 50 to 200° C. Heat drying may be performed multiple times with different heating times or different temperatures.

[0083] In the third step (2), the precursor composition is molded to a predetermined thickness and / or width. In the third step (2), the molded precursor composition may be further heated so as to further promote the curing reaction between the (A) component and the (B) component.

[0084] The manufacturing method according to this embodiment may further include the following steps. Fourth step: a step of laminating a protective film 14 on the adhesive layer 13.

[0085] In the fourth step, a protective film 14 is laminated on the adhesive layer 13. In the fourth step, after the protective film 14 is laminated, the state may be maintained at room temperature (20±3° C.) for several days. This may stabilize the adhesive strength.

[0086] In the manufacturing method of this embodiment, the pellicle membrane 11 may be attached to the frame 12 before the first step, between the first and second steps, between the second and third steps, between the third and fourth steps, or after the fourth step.

[0087] [Test method for adhesive layer for masks] The test method according to this embodiment includes the following steps: This is a method for testing a mask adhesive layer, which compares a value based on the remaining rate of the mask adhesive layer (remaining area of ​​the mask adhesive layer on the quartz mask / area of ​​the adhesive layer attached to the quartz mask) with a predetermined threshold value. This method makes it possible to evaluate the efficiency of the replacement work of the quartz mask.

[0088] In the above test method, the value of the remaining rate itself may be compared with a threshold value, or a value correlated with the remaining rate may be compared with a threshold value. The threshold value may be appropriately determined, and when the value of the remaining rate itself is compared with a threshold value, the threshold value is, for example, 0.001% and / or 5.0%. By setting the remaining rate to 0.001 to 5.0%, it is expected that the efficiency of the mask replacement work will be further improved.

[0089] In the above test method, the part of the quartz mask where the adhesive layer for the mask is attached may or may not be irradiated with Xe excimer lamp light from the back side of the mask. When irradiating with Xe excimer lamp light, the irradiation time is, for example, 30 seconds to 5 minutes, or 30 seconds to 2 minutes, and in one embodiment, 2 minutes. By performing the above test under the assumption of a normal environment and normal operation in accordance with an actual lithography process, it is easy to evaluate the efficiency of the mask replacement work in the actual lithography process.

[0090] The present embodiment has been described above, but the present embodiment is not limited to the above aspects and can be modified in various ways within the scope of the present invention. EXAMPLES

[0091] Next, the present embodiment will be described more specifically with reference to examples and comparative examples.

[0092] Example 1 <Preparation of Pressure-Sensitive Adhesive Composition> First, ethyl acetate (30 parts by mass) and the raw materials (raw materials for component (A)) shown in the table were charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube, and reacted for 8 hours at reflux temperature under a nitrogen atmosphere. After the reaction was completed, butyl acetate (33 parts by mass) was added to obtain a solution of a (meth)acrylic acid ester copolymer (component (A)) with a non-volatile content concentration of 37% by mass. The raw materials (component (B)) shown in the table were added to 100 parts by mass of the obtained solution, and the mixture was stirred and mixed to obtain a pressure-sensitive adhesive composition.

[0093] <Fabrication of a pellicle> The adhesive composition prepared as described above was applied to the other surface of an aluminum alloy frame (outer diameter 115 mm x 149 mm, inner diameter 111 mm x 145 mm, height 3.0 mm) with a pellicle film attached to one surface, using a dispenser. The applied adhesive composition was heated in two stages (first stage: 115°C, 11 minutes; second stage: 150°C, 5 minutes) to obtain an adhesive layer for a mask (thickness 0.30 mm). Thereafter, a 100 μm thick polyester protective film having a silicone layer formed thereon was laminated onto the pressure-sensitive adhesive layer for masking, and the film was cured at 100° C. for 12 hours. As described above, the pellicle of Example 1 was produced.

[0094] [Other Examples] and [Comparative Examples] The raw materials for component (A) and component (B) were changed as shown in the table, and a pellicle was produced in the same manner as in Example 1. The adhesive composition of Comparative Example 2 had poor coatability, and a pellicle could not be produced, so the efficiency of the photomask replacement work was not evaluated.

[0095] [Micrograph of glue residue] 3(a) and (b) are micrographs of adhesive residue, where Fig. 3(a) corresponds to the results of the example, and Fig. 3(b) corresponds to the results of the comparative example.

[0096] <Residual stress> One side of the pellicle with the protective film was cut, and the protective film was peeled off so that the adhesive layer for the mask would not deform, and then the adhesive layer for the mask was gradually peeled off from the frame. When peeling was difficult, a siccarol was attached to the adhesive layer for the mask, and the adhesive layer for the mask was gradually peeled off. The direction of the adhesive layer for the mask along the length direction of the pellicle corresponds to the longitudinal direction of the adhesive layer for the mask, and the direction of the adhesive layer for the mask along the width direction of the pellicle corresponds to the transverse direction of the adhesive layer for the mask. The adhesive layer for the peeled adhesive layer for the mask was pulled in the longitudinal direction until the elongation of the adhesive layer for the mask was 20%. After the pulling, the pulling was released, and the residual stress value per unit cross-sectional area was obtained after 3 minutes had passed. The above pulling and residual stress values ​​were derived according to the following device and conditions. Device name: Autograph (SHIMAZU EZ-S, manufactured by Shimadzu Corporation) Load cell: 1N (clip-type chuck) Chuck Distance: 10mm Crosshead speed: 5mm / min

[0097] The pellicles of the examples and comparative examples were evaluated according to the following criteria. A: Residual stress value is greater than 0 and 5.0 mN / mm 2 below B: Residual stress value is 5.0mN / mm 2 Exceeds 10.0mN / mm 2 below C: Residual stress value is 10.0mN / mm 2 Exceed

[0098] <Glue residue> The pellicles of the examples and comparative examples (pellicles with protective films, after the protective films were removed) were attached to a photomask (6025 size, made of quartz) by applying a load (5 kgf, 60 seconds) using a simplified mounter. This resulted in an exposure master plate having a photomask and a pellicle attached to the photomask.

[0099] The part of the photomask where the adhesive layer for mask is attached is irradiated with Xe excimer lamp light from the back side of the photomask for 2 minutes, and then the pellicle is peeled off from the photomask. The peeling is performed by using a known tensile tester and pulling up the photomask vertically at a speed of 5 mm / min. The photomask is observed visually and with a microscope, and the remaining area of ​​the adhesive layer for mask on the photomask, and therefore the remaining rate of the adhesive layer for mask, are calculated. The pellicles of the examples and comparative examples are evaluated according to the following criteria. A: Residual rate is 0.001-2.0% B: Residual rate is more than 2.0 and 5.0% or less C: Residual rate exceeds 5.0% The irradiation conditions for the Xe excimer lamp light are as follows: Light source: Xe Illuminance: 50mW / cm 2 Accumulated radiation: 6.0J / cm 2

[0100] <Efficiency of photomask replacement work> As described above, by reducing the amount of adhesive residue, the removal work of the mask adhesive layer remaining on the photomask can be shortened and / or simplified. Also, as described above, by keeping the residual stress within the reference value, the mask distortion caused by the mask adhesive layer can be easily reduced, which makes it easier to reuse the photomask. Therefore, the pellicles of the examples and comparative examples were evaluated according to the following criteria. A: "Adhesive residue" was rated A and "Residual stress" was rated A B: "Adhesive residue" is rated A or B, and "Residual stress" is rated B or C. C: "Glue residue" is rated C

[0101] [Table 1] BuA: butyl acrylate HEA: Hydroxyethyl acrylate Duranate TPA-100 (manufactured by Asahi Kasei Corporation) Duranate E402-80B (manufactured by Asahi Kasei Corporation) Duranate MHG-80B (manufactured by Asahi Kasei Corporation) Coronate L (manufactured by Toso Co., Ltd.)

[0102] As can be seen from the table, the pellicle of the embodiment was evaluated as passing for both "glue residue" and "residual stress." Therefore, by using the pellicle of the embodiment, it is expected that the efficiency of the photomask replacement work will be further improved. [Industrial Applicability]

[0103] The present invention can be suitably applied to lithography processes for obtaining electronic components such as integrated circuits (ICs), large scale integrated circuits (LSIs), liquid crystal displays (LCDs), etc. The present invention can be suitably applied to the fields of pellicles, exposure masters, and exposure apparatuses, as well as methods for producing pellicles, and methods for testing pressure-sensitive adhesive layers for masks. [Explanation of symbols]

[0104] 1: Exposure equipment 2: Exposure master 3:Light source 4: Photomask (quartz mask) 5: Pellicle 6: Stage 11: Pellicle membrane 12: Frame 12A: Side (long side) 12B: Side (short side) 12a: One side 12b: Other side 12c: Inner surface 12d: Outer surface 13: Adhesive layer (adhesive layer for mask) 14: Protective film Op: Opening

Claims

1. A pellicle having a frame on which a pellicle film is arranged and a mask adhesive layer arranged on the frame, a residual rate of the adhesive layer (remaining area of ​​the adhesive layer on the mask / area of ​​the adhesive layer attached portion) of 0.001 to 5.0% when a xenon (Xe) excimer lamp light is irradiated from the back surface of the quartz mask for 2 minutes and the pellicle is then peeled off; The pressure-sensitive adhesive layer is A (meth)acrylic copolymer, A curing agent having a crosslink density ensuring unit and a flexibility imparting unit; comprising the reaction product of The crosslink density ensuring unit contains three or more isocyanate groups, A pellicle, wherein the flexibility-imparting unit comprises an aliphatic isocyanate compound containing an isocyanate group at the end of an alkyl chain having 4 or more carbon atoms.

2. 2. The pellicle of claim 1, wherein when the attached portion is irradiated with Xe excimer lamp light from the back surface of the mask for two minutes and the pellicle is then peeled off, the remaining rate is 5.0% or less.

3. The pellicle according to claim 1 or 2, wherein the residual rate is 2.0% or less.

4. The pressure-sensitive adhesive layer is stretched in the longitudinal direction at an elongation of 20% and then the tension is released. After 3 minutes, the residual stress value per unit cross-sectional area is greater than 0 and less than 10 mN / mm ２ The pellicle according to claim 1 or 2, wherein:

5. The (meth)acrylic copolymer contains a hydroxyl group-containing monomer, The pellicle according to claim 1 , wherein the ratio of the hydroxyl group-containing monomer to the total amount of the (meth)acrylic copolymer is 4.0 mass % or less.

6. The pellicle according to claim 1 , wherein 95% by mass or more of the curing agent is an aliphatic isocyanate compound.

7. The pellicle of claim 1 , wherein less than 5% by weight of the curing agent is an aromatic isocyanate compound.

8. The pellicle according to claim 1, wherein the ratio of the curing agent to the total amount of the (meth)acrylic copolymer is 0.20 to 3.00 mass %.

9. An exposure master comprising: a quartz mask; and the pellicle according to claim 1 or 2 attached to the mask.

10. A light source that emits xenon (Xe) excimer lamp light; The exposure master according to claim 9 , which is irradiated with light from a xenon (Xe) excimer lamp; An exposure apparatus comprising:

11. A method for manufacturing a pellicle having a frame on which a pellicle membrane is arranged and a mask pressure-sensitive adhesive layer arranged on the frame, comprising: a residual rate of the adhesive layer (remaining area of ​​the adhesive layer on the mask / area of ​​the adhesive layer attached portion) of 0.001 to 5.0% when a xenon (Xe) excimer lamp light is irradiated from the back surface of the quartz mask for 2 minutes and the pellicle is then peeled off; The pressure-sensitive adhesive layer is A (meth)acrylic copolymer, A curing agent having a crosslink density ensuring unit and a flexibility imparting unit; comprising the reaction product of The crosslink density ensuring unit contains three or more isocyanate groups, The method for producing a pellicle, wherein the flexibility-imparting unit comprises an aliphatic isocyanate compound containing an isocyanate group at the end of an alkyl chain having 4 or more carbon atoms.

12. A pellicle having a frame on which a pellicle film is arranged and a mask adhesive layer arranged on the frame, A xenon (Xe) excimer lamp was irradiated from the rear surface of the quartz mask to the portion of the adhesive layer attached thereto with an integrated radiation dose of 6.0 J / cm. ２ and then peeling off the pellicle, the remaining rate of the pressure-sensitive adhesive layer (remaining area of ​​the pressure-sensitive adhesive layer on the mask / area of ​​the attached portion of the pressure-sensitive adhesive layer) is 0.001 to 5.0%, The pressure-sensitive adhesive layer is A (meth)acrylic copolymer, A curing agent having a crosslink density ensuring unit and a flexibility imparting unit; comprising the reaction product of The crosslink density ensuring unit contains three or more isocyanate groups, A pellicle, wherein the flexibility-imparting unit comprises an aliphatic isocyanate compound containing an isocyanate group at the end of an alkyl chain having 4 or more carbon atoms.

Images