Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
  • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
  • G03F1/64—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof characterised by the frames, e.g. structure or material, including bonding means therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
  • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
  • C09J183/04—Polysiloxanes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present disclosure relates to a pellicle used as a dust repellent for a lithography mask in a lithography process such as a semiconductor device such as an LSI or a superLSI or a liquid crystal display panel, and a manufacturing method thereof.
• Pellicle is used for the purpose of preventing foreign matter from adhering to the mask by mounting it on a lithography mask in the lithography process of semiconductor devices such as LSIs and superLSIs and liquid crystal display panels.
• the pellicle usually has a pellicle frame, a transparent pellicle film stretched on the upper end surface thereof, and an adhesive layer provided on the lower end surface for attaching the pellicle to the mask.
• a distorted pellicle is attached to a mask, the mask is distorted and the exposure position is displaced. Therefore, a pellicle without distortion is required. Therefore, the pressure-sensitive adhesive layer of the pellicle is required to have flatness and stress relaxation property.
• the wavelength of exposure light has been shortened with the miniaturization of mask patterns.
• Examples of short wavelength light include excimer light such as KrF excimer laser and ArF excimer laser. Since such a short wavelength has high energy, the components of the pressure-sensitive adhesive are easily decomposed during exposure, and the decomposition of the pressure-sensitive adhesive component may cause problems such as peeling of the pellicle from the mask in the exposure process.
• Patent Document 2 discloses a pellicle having a pressure-sensitive adhesive layer having a thickness of 400 ⁇ m or more, which contains a thermal radical polymerization initiator.
• the thickness of the pressure-sensitive adhesive layer is increased to 400 ⁇ m or more, but when the thickness is increased in this way, the flatness of the pressure-sensitive adhesive layer tends to deteriorate. Therefore, the pellicle is easily distorted, and when the pellicle is attached, the mask is often distorted.
• Many of the conventional pellicle pressure-sensitive adhesive layers are formed of a resin composition containing one kind of curing agent.
• a thick coating film was formed from such a resin composition, it was difficult to cure the cured coating film to an appropriate hardness capable of flattening.
• the coating film is completely cured and cannot be crushed in the flattening process, or the coating film is soft due to insufficient curing and is crushed more than necessary in the flattening process and protrudes from the frame. There was a case that it ended up. Therefore, it is difficult to produce a pellicle having a pressure-sensitive adhesive layer having good flatness with good reproducibility, and even when flattening is possible, the thickness of the pressure-sensitive adhesive layer varies.
• the present disclosure relates to the following pellicle: [1] A pellicle having a pellicle frame, a pellicle film stretched on one end surface of the pellicle frame, and an adhesive layer provided on the other end surface of the pellicle frame, and the pressure-sensitive adhesive layer is cured. A pellicle containing a cured product of a resin composition containing a sex polymer (A), a curing agent (B1), and a curing agent (B2) different from the curing agent (B1). [2] The pellicle according to [1], wherein the curing agent (B1) and the curing agent (B2) are radical polymerization initiators.
• the thermal radical polymerization initiator is a peroxide-based radical polymerization initiator or an azo-based radical polymerization initiator.
• the curable polymer (A) is selected from the group consisting of a (meth) acrylic acid ester copolymer (A-1), an organopolysiloxane (A-2) and a polyurethane polyol (A-3).
• the multiple bond equivalent of the (meth) acrylic acid ester copolymer is 156 g / mol or more and 100,000 g / mol or less.
• the curable polymer (A) has a weight average molecular weight of 10,000 or more and 1 million or less.
• the resin composition further contains a cross-linking agent (C).
• the cross-linking agent (C) is a compound having a polyfunctional carbon-carbon multiple bond.
• the present disclosure relates to the following pellicle manufacturing method.
• a method for producing a pellicle which comprises a step of applying a photocuring treatment, a thermosetting treatment, and a flattening treatment to provide an adhesive layer.
• a pellicle having an adhesive layer having good flatness it is possible to provide a pellicle having an adhesive layer having good flatness and a method for producing the pellicle.
• the pressure-sensitive adhesive layer of the pellicle contains a cured product of a resin composition containing a curable polymer and at least two curing agents having different curing conditions. It was found that the flatness was good. The reason is not clear, but it is presumed as follows.
• the type and amount of the curing agent to be used are adjusted, and further, there are a plurality of steps according to the curing agent.
• the curing step of it is possible to adjust the degree of curing of the coating film containing the resin composition.
• the pressure-sensitive adhesive layer can be flattened without being excessively crushed, and further, it becomes easy to make the thickness of the pressure-sensitive adhesive layer uniform.
• the pellicle of the present disclosure has a pellicle frame, a pellicle film stretched on one end surface of the pellicle frame, and an adhesive layer provided on the other end surface of the pellicle frame.
• Pellicle frame The pellicle frame may be one that is usually used as a pellicle frame.
• pellicle frame materials include aluminum alloys, stainless steel, polyethylene, black anodized aluminum and the like. Among these, aluminum alloys and black alumite-treated aluminum are preferable because of their light weight.
• the pellicle membrane is fixed to one opening of the pellicle frame.
• the pellicle membrane may be one that is usually used as a pellicle membrane.
• Examples of the material of the pellicle film include nitrocellulose, ethyl cellulose, cellulose acetate, cellulose propionate, pullulan compound, amorphous fluoropolymer, silicone-modified polyvinyl alcohol and the like. Among these, an amorphous fluorine-based polymer having sufficient resistance to excimer light is preferable.
• the adhesive layer contains a cured product of a resin composition containing a curable polymer (A), a curing agent (B1), and a curing agent (B2) different from the curing agent (B1).
• the curable polymer (A) is a polymer that is cured by applying light or heat in the presence of a curing agent (B1) or a curing agent (B2).
• the curable polymer (A) is a functional group having a reactivity with the curing agent (B1) and a functional group having a reactivity with the curing agent (B2) (these may be the same functional group, or they may be the same functional group. It suffices to have a different functional group depending on the curing agent) in the molecule, for example, a polymer having a carboxy group, a hydroxyalkyl group or a group containing a carbon-carbon multiple bond in the molecule. Can be done.
• the type of the curable polymer (A) is not limited, and any curable polymer may be used.
• the curable polymer (A) include a (meth) acrylic acid ester copolymer (A-1), an organopolysiloxane (A-2) and a polyurethane polyol (A-3).
• the (meth) acrylic acid ester copolymer (A-1) is preferable because it has high heat resistance and light resistance and is not easily decomposed.
• the curable polymer (A) preferably has a group containing a carbon-carbon multiple bond from the viewpoint of being cured by a photoinitiator or a heat initiator.
• the carbon-carbon multiple bond-containing group is not particularly limited as long as it is a group containing a carbon-carbon double bond and / or a carbon-carbon triple bond.
• the polymerizable carbon-carbon multiple bond means an ethylenic as well as an alkyne carbon-carbon multiple bond.
• the carbon-carbon double bond-containing group is not particularly limited as long as it is a group containing a carbon-carbon double bond.
• Examples thereof include functional groups ((meth) acryloyl group, vinyl group, allyl group, styryl group, etc.) obtained by polymerizing polyethylene glycol # 600 diacrylate, isoprene, diallyl ether, and divinylbenzene.
• the carbon-carbon triple bond-containing group is not particularly limited as long as it is a group containing a carbon-carbon triple bond.
• a functional group obtained by polymerizing hexane-1,5-diine, diethynylbenzene or diethylene glycol bis (2-propynyl) ether can be mentioned.
• a (meth) acryloyl group which is a carbon-carbon double bond-containing group, is preferable from the viewpoint of being more excellent in radical stability and reactivity and having a sufficiently large decrease in adhesive strength after heating.
• the curable polymer (A) may have a multiple bond-containing group in either the side chain or the terminal, but it improves the reactivity of the polymerizable carbon-carbon multiple bond and is after heating or UV curing. It is preferable to have it in the side chain from the viewpoint of increasing the decrease in adhesive strength sufficiently.
• the curable polymer (A) in which a multiple bond-containing group is introduced into the side chain for example, a precursor polymer having a hydroxy group or an epoxy group in the side chain is prepared, and the hydroxy group or carboxy group of the precursor polymer is used.
• a precursor polymer having a hydroxy group or an epoxy group in the side chain is prepared, and the hydroxy group or carboxy group of the precursor polymer is used.
• it can also be obtained by a method of reacting an isocyanate compound or an epoxy compound having a multiple bond.
• the range of the multiple bond equivalent which represents the content of the multiple bond-containing group in the curable polymer (A), is preferably 156 g / mol or more and 100,000 g / mol or less, and 500 g / mol or more and 50,000 g / mol or less. More preferably, it is more preferably 1000 g / mol or more and 20,000 g / mol or less.
• the multiple bond equivalent is the solid content mass (g) of the curable polymer (A) with respect to the total number of moles (mol) of the multiple bonds (that is, double bonds and triple bonds) of the curable polymer (A). Yes, it can be expressed by the following formula.
• Multiple bond equivalent (g / mol) mass of solid content (g) in the curable polymer (A) / number of moles of multiple bonds of the curable polymer (A).
• the solid content mass of the curable polymer (A) here is the average molecular weight (Mw) of the curable polymer (A).
• the number of moles of the multiple bond of the curable polymer (A) is the number of moles of the compound having a polymerizable multiple bond group located in the side chain.
• the weight average molecular weight (Mw) of the curable polymer (A) is the polystyrene-equivalent weight average molecular weight by GPC. The measuring method will be described later.
• the number of moles of multiple bonds of the curable polymer (A) can be calculated from the integrated value of 1 1 H-NMR.
• a solution prepared by adding an arbitrary amount (for example, 0.1 mmol) of a standard reagent (such as styrene) to the curable polymer (A) is prepared, and the solution is diluted with a deuterated solvent (for example, CDCl 3).
• a deuterated solvent for example, CDCl 3
• 1 H-NMR is measured on the prepared sample solution to obtain a spectrum. With respect to the obtained spectrum, the number of moles of multiple bonds can be obtained from the integrated value of the peak derived from the standard reagent and the integrated value of the peak derived from the multiple bond contained in the curable polymer (A).
• the weight average molecular weight of the curable polymer (A) is preferably 10,000 or more and 1 million or less, and more preferably 30,000 or more and 100,000 or less. When it is within the above range, the cohesive force and the adhesive force of the pressure-sensitive adhesive layer become moderately large, and adhesive residue is unlikely to remain, which is preferable.
• the weight average molecular weight is the polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC).
• the lower limit of the molecular weight distribution of the curable polymer (A), that is, the ratio of Mw (Mw / Mn) to the polystyrene-equivalent number average molecular weight (Mn) by GPC is usually 1, preferably 1.1.
• As the upper limit of the above ratio 5 is preferable, 3 is more preferable, 2 is more preferable, and 1.7 is particularly preferable.
• the molecular weight distribution is in the above range, the degree of cross-linking can be controlled, the control of functional groups which are considered to be bad for the adhesive residue is improved, and the adhesive residue is reduced.
• GPC column For example, two "TSKgel Multipore HXL-M" from Tosoh Corporation, Column temperature: 40 ° C Elution solvent: Tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0 mL / min Sample concentration: 0.05% by mass Sample injection volume: 100 ⁇ L Detector: Differential refractometer Standard material: Monodisperse polystyrene
• the (meth) acrylic acid ester copolymer (A-1) is a reactivity between a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms and a curing agent (B) described later. It is preferable that the monomer unit contains a reactive monomer having a functional group having.
• (meth) acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms include butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and decyl (meth) acrylate.
• (Meta) acrylic acid ester of linear aliphatic alcohols such as dodecyl (meth) acrylic acid, lauryl (meth) acrylic acid, isobutyl (meth) acrylic acid, isoamyl (meth) acrylic acid, 2- (meth) acrylic acid Ethylhexyl, isooctyl (meth) acrylate, isononyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate and the like can be mentioned. These may be used alone or in combination of two or more.
• Examples of the reactive monomer having a functional group having reactivity with a curing agent include carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, and crotonic acid, and 2-hydroxyethyl (meth) acrylic acid.
• a hydroxyl group-containing monomer such as 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and a carbon-carbon multiple bond-containing group described later can be introduced.
• Monomers eg, polyfunctional monomers
• These monomers may be used alone or in combination of two or more.
• hydroxyl group having a hydroxyalkyl group having 2 to 4 carbon atoms such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
• Carboxyl group-containing monomers such as meta) acrylate and (meth) acrylic acid are preferred.
• (meth) acrylic acid is preferable from the viewpoint of reducing adhesive residue.
• the (meth) acrylic acid ester copolymer (A-1) contains a structural unit derived from the (meth) acrylic acid ester (hereinafter, also referred to as “structural unit (I)”) and a carbon-carbon multiple bond-containing group. It is preferably a polymer having a side chain containing it. Further, the (meth) acrylic acid ester copolymer (A-1) may further have a structural unit containing a hydroxy group (hereinafter, also referred to as “structural unit (II)”) in addition to the structural unit (I). preferable. Further, it may further have other structural units other than the structural units (I) to (II).
• the carbon-carbon multiple bond-containing group may be contained in the structural unit (II) or other structural unit.
• structural unit (II) or other structural unit.
• carbon-carbon multiple bond-containing groups and each structural unit will be described.
• the structural unit (I) is a structural unit derived from the (meth) acrylic acid ester.
• the structural unit (I) has a structure represented by -CH 2- CH (COOCH 3)-.
• the structural unit (I) is preferably a structural unit derived from a (meth) acrylic acid alkyl ester containing an alkyl group having 4 or more and 10 or less carbon atoms.
• alkyl group having 4 or more and 10 or less carbon atoms include an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group and an n-decyl group. Of these, n-butyl group and 2-ethylhexyl group are preferable.
• the structural unit (I) is preferably a compound in which the desorbed product derived from the structural unit (I) has a boiling point of 150 ° C. or lower.
• the desorbed product is butanol having a boiling point of 117 ° C.
• the outgas can be easily removed. Examples of the structural unit (I) that produces a desorbed product having a boiling point of 150 ° C.
• esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate.
• esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate.
• examples thereof include (meth) acrylic acid esters having a group having 5 or less carbon atoms.
• the lower limit of the content ratio of the structural unit (I) is the (meth) acrylic acid ester copolymer (A-1).
• 5% by mass is preferable, 10% by mass is more preferable, 30% by mass is further preferable, and 40% by mass is particularly preferable.
• the upper limit of the content ratio is preferably 95% by mass, more preferably 80% by mass, further preferably 70% by mass, and 60% by mass with respect to the total mass of the (meth) acrylic acid ester copolymer (A-1). Is particularly preferable.
• the strength of the pressure-sensitive adhesive layer can be further increased, and as a result, the adhesive strength can be further increased.
• the adhesive strength can be designed from weak adhesive to strong adhesive, and the adhesive residue can be sufficiently reduced.
• the structural unit (II) is a structural unit containing a hydroxy group.
• the adhesive strength is further improved.
• Examples of the hydroxy group include an alcoholic hydroxy group. Among these, an alcoholic hydroxy group is preferable from the viewpoint of reducing the adhesive residue.
• Examples of the monomer giving the structural unit (II) include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; hydroxyphenyl (meth) acrylate and hydroxynaphthyl.
• Examples thereof include hydroxyaryl (meth) acrylates such as (meth) acrylates.
• hydroxyalkyl (meth) acrylate is preferable, hydroxyalkyl acrylate is more preferable, and hydroxyethyl acrylate is further preferable.
• the lower limit of the content ratio of the structural unit (II) is the (meth) acrylic acid ester copolymer (A-1).
• the upper limit of the content ratio is preferably 30% by mass, more preferably 25% by mass, further preferably 15% by mass, and 10% by mass with respect to the total mass of the (meth) acrylic acid ester copolymer (A-1). Is particularly preferable.
• Organopolysiloxane (A-2) As the organopolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, fluoropolysiloxane, tetramethyltetraphenylpolysiloxane, methylhydrogenpolysiloxane and the like can be used. These have reactivity with a functional group having reactivity with a curing agent (B1) and reactivity with a curing agent (B2) by epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, epoxy polyether modification and the like. It is preferable that functional groups (these may be the same functional group or different functional groups depending on the curing agent) are introduced into the molecule. Among these, an acrylic modified product of dimethylpolysiloxane is preferably used.
• the polyurethane polyol is obtained by at least reacting the polyisocyanate with the polyol component.
• the polyurethane polyol is a functional group having reactivity with the curing agent (B1) and a functional group having reactivity with the curing agent (B2) (these may be the same functional group, or depending on the curing agent). It is preferable that a different functional group) is introduced into the molecule.
• polyisocyanate examples include aromatic polyisocyanates, aromatic aliphatic polyisocyanates, and aliphatic polyisocyanates (including alicyclic polyisocyanates).
• aromatic polyisocyanate examples include 4,4'-, 2,4'-or 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or a mixture thereof.
• MDI 4,4'-, 2,4'-or 2,2'-diphenylmethane diisocyanate or a mixture thereof
• TODI 4,4'-toluene diisocyanate
• NDI 1,5-naphthalenediocyanate
• m- or p-phenylenediocyanate or a mixture thereof 4,4'-diphenyl diisocyanate
• 4,4'-diphenyl ether examples thereof include aromatic diisocyanates such as diisocyanates.
• aromatic aliphatic polyisocyanate examples include 1,3- or 1,4-xylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylene diisocyanate or a mixture thereof (TMXDI), and the like.
• aromatic aliphatic diisocyanates such as ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene.
• aliphatic polyisocyanate examples include hexamethylene diisocyanate (HDI), trimethylene diisocyanate, tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,2-, 2,3- or 1,3-butylenediocyanate, 2 , 4,4- or 2,2,4-trimethylhexamethylene diisocyanate and other aliphatic diisocyanates.
• HDI hexamethylene diisocyanate
• trimethylene diisocyanate trimethylene diisocyanate
• tetramethylene diisocyanate 1,5-pentamethylene diisocyanate
• 1,2-, 2,3- or 1,3-butylenediocyanate 2,4- or 2,2,4-trimethylhexamethylene diisocyanate
• other aliphatic diisocyanates examples include hexamethylene diisocyanate (HDI), trimethylene diisocyanate, tetramethylene diisocyanate, 1,5-p
• an aliphatic polyisocyanate can be further mentioned.
• alicyclic polyisocyanate examples include 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'-or 2,2'-dicyclohexyl.
• Methandiisocyanate or a mixture thereof H12MDI
• 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof hydrogenated xylylene diisocyanate
• H6XDI hydroxylylene diisocyanate
• NBDI bis (isocyanatomethyl) norbornan
• 1 3-Cyclopentene diisocyanate, 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate and other alicyclic diisocyanates.
• the above-mentioned modified polyisocyanate can be used, and as such a modified form, for example, a multimer (for example, a dimer, a trimer, a heptamer) of the above-mentioned polyisocyanate can be used.
• a multimer for example, a dimer, a trimer, a heptamer
• a biuret-modified product produced by the reaction of the above-mentioned polyisocyanate or multimer with water, an allophanate-modified product produced by the reaction of monool or a polyhydric alcohol (described later),
• examples thereof include an oxadiazine trimer modified product produced by reaction with carbon dioxide gas, and a polyol modified product produced by reaction with a low molecular weight polyol (described later).
• These polyisocyanates can be used alone or in combination of two or more.
• polyol component examples include polyether polyols, polyester polyols, polycarbonate polyols, and the like.
• polyether polyol examples include polyoxyalkylene polyol and polytetramethylene ether glycol.
• the polyoxyalkylene polyol is, for example, an addition polymer of alkylene oxide using a low molecular weight polyol or a low molecular weight polyamine as an initiator.
• alkylene oxide examples include propylene oxide, ethylene oxide, butylene oxide, styrene oxide and the like.
• these alkylene oxides can be used alone or in combination of two or more.
• propylene oxide and ethylene oxide are preferable.
• the types of the curing agent (B1) and the curing agent (B2) used in the resin composition are not particularly limited as long as the curable polymer (A) to be used can be cured.
• the curing agent (B1) and the curing agent (B2) may have different curing conditions, and the curing agent (B1) and the curing agent (B2) can be arbitrarily determined.
• the curing agent having the largest amount of the pressure-sensitive adhesive is the curing agent (B1)
• the curing agent having the smaller amount is the curing agent (B2).
• At least two types of a curing agent (B1) and a curing agent (B2) may be used, and other curing agents may be contained.
• Examples of the curing agent (B1) and the curing agent (B2) include a radical polymerization initiator. Further, as the radical polymerization initiator, a photoradical polymerization initiator and a thermal radical polymerization initiator can be used.
• the thermal radical polymerization initiator is a compound that generates radicals by heat, that is, a compound that absorbs heat energy and decomposes to generate radical species.
• the photoradical polymerization initiator refers to a compound that generates radicals when irradiated with light, that is, a compound that absorbs light energy and decomposes to generate radical species.
• the curing agents (B1) and (B2) are radical polymerization initiators, the multiple bonds contained in the curable polymer (A) can be obtained by using a combination of starting agents that generate radicals. It is preferable because the polymerization reaction occurs quickly, the degree of polymerization is increased, and curing can be easily achieved.
• radical polymerization initiators when radical polymerization initiators are used as the curing agents (B1) and (B2), at least two different types of photoradical polymerization initiators and at least two different types of thermal radical polymerization initiators can also be used. However, a thermal radical polymerization initiator and a photoradical polymerization initiator can also be used in combination. In order to flatten the pressure-sensitive adhesive layer and make the thickness uniform, it is preferable to use the thermal radical polymerization initiator as the curing agent (B1) and the photoradical polymerization initiator as the curing agent (B2).
• thermal radical polymerization initiator used as the curing agent (B1) a peroxide-based radical polymerization initiator or an azo-based radical polymerization initiator is preferable.
• peroxide-based radical polymerization initiator examples include the following compounds and commercially available products.
• Ketone peroxides such as Perhexa H, peroxyketals such as Perhexa TMH, hydroperoxides such as Perbutyl H-69, Park Mill D, Perbutyl C, Perbutyl D, Perbutyl O, etc., which are commercially available from NOF CORPORATION.
• Dialkyl peroxides diacyl peroxides such as NOF BW, peroxyesters such as perbutyl Z and perbutyl L, and peroxydicarbonates such as parloyl TCP.
• Trigonox 36-C75 Laurox, Parkadox L-W75, Parkadox CH-50L, Trigonox TMBH, Kayakumen H, Kayabutyl H-70, Parkadox BC-FF, Kayahexa AD, Parkadox 14 manufactured by Kayaku Akzo.
• the peroxide-based radical polymerization initiator may be used alone or in combination of two or more.
• azo radical polymerization initiator examples include compounds having an azo group, such as an azonitrile compound, an azo ester compound, an azoamide compound, an azoamidine compound, an azoimidazoline compound, and a high molecular weight azo compound.
• Examples of the polymer azo compound include trade names VPE-0201, VPE-0401, VPE-0601, VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.
• the azo radical polymerization initiator may be used alone or in combination of two or more.
• the 10-hour half-life temperature of the radical polymerization initiator is preferably 50 ° C. to 150 ° C., more preferably 60 ° C. to 140 ° C., and even more preferably 70 ° C. to 130 ° C.
• the 10-hour half-life temperature is within the above range, there are few curing defects, so that adhesive residue can be suppressed.
• the value of the 10-hour half-life temperature of the radical polymerization initiator can also be obtained from the literature, and the manufacturer's catalog or the like can be referred to.
• the catalog value (http://www.nov.co.jp/upload_public/sogo/B0100.pdf) of NOF CORPORATION can be referred to.
• photoradical polymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 1- [4- (2-hydroxyethoxy). ) -Phenyl] -2-Hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -1-butanone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-1- ⁇ 4- [4- (2) -Hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propane, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)
• the above compounds are available as commercial products, and are OMNIRAD1000, 248, 481, 4817, 4MBZ-flakes, 500, 659, 73, 784, 81, BDK, MBS, and MBS.
• the amount ratio of the curing agent (B1) to the curing agent (B2) has no technical demerit because the amount of the curing agent (B1) is large, and from the viewpoint of cost, the curing agent (B1) / curing agent (B2) Is preferably 100 or less, more preferably 30 or less, very preferably 10 or less, and particularly preferably 5 or less.
• the curing agent (B1) / curing agent (B2) is preferably 1 or more, and 3 or more, because the degree of curing that facilitates flattening during flattening processing can be easily set and the processing time can be shortened. More preferably, it is more preferably 5 or more, and particularly preferably 10 or more.
• the amount ratio of the thermal radical polymerization initiator: the photoradical polymerization initiator is also the same as above. ..
• Thermal radical polymerization initiator When the photoradical polymerization initiator is within the above range, curing by the photoradical polymerization initiator proceeds easily first, and a certain amount of hard adhesive layer is formed. After that, curing by the thermal radical polymerization initiator proceeds, and it becomes possible to form a pressure-sensitive adhesive layer with little variation in the height of the adhesive while maintaining flatness.
• the blending amount of the curing agent (that is, the total of the curing agent (B1) and the curing agent (B2)) in the resin composition is, for example, 0.01 to 10% by mass with respect to 100 parts by mass of the curable polymer (A). Can be a department.
• the blending amount of the curing agent (that is, the total of the curing agent (B1) and the curing agent (B2)) in the resin composition is preferably 0.01% by mass or more. It is more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more.
• the blending amount of the curing agent (that is, the total of the curing agent (B1) and the curing agent (B2)) in the resin composition is preferably 10 parts by mass or less. It is more preferably 5 parts by mass or less, and particularly preferably 1 part by mass or less.
• the resin composition according to the present disclosure may further contain a cross-linking agent (C).
• the cross-linking agent (C) is a component capable of forming a cross-linked structure in the curable polymer (A) by heating.
• a pressure-sensitive adhesive layer having a cross-linked structure can be formed.
• the cross-linking agent (C) is preferably a compound having a polyfunctional carbon-carbon multiple bond, and a polyfunctional (meth) acrylate is particularly preferable.
• the polyfunctional (meth) acrylate is not particularly limited as long as it has 2 or more and 10 or less (meth) acryloyl groups, but it is preferable that the number of (meth) acryloyl groups is 2 or more and 6 or less.
• polyfunctional (meth) acrylate used as the cross-linking agent (C) include the following compounds. Alkyl di (meth) acrylate, hydroxyl group-containing alkyl di (meth) acrylate, polyalkylene glycol di (meth) acrylate, dioxandi (meth) acrylate, tricyclodecanoldi (meth) acrylate, full orange (meth) acrylate, alkoxylation.
• Preferred examples of the polyfunctional acrylate compound are polyethylene glycol # 400 diacrylate (NK ester A-400 (molecular weight 508)) and polyethylene glycol # 600 diacrylate (NK ester A-600 (molecular weight 742)) manufactured by Shin-Nakamura Chemical Co., Ltd. )), A-DOD-N, A-BPE-10, A-GLY-9E, A-9300, A-9300-1CL, AD-TMP-L.
• the cross-linking agent (C) is more preferably a bifunctional or higher functional (meth) acrylate curing agent containing 2 or more and 10 or less acrylate groups in one molecule.
• Specific examples of such a compound include glycerolpropyl-added tri (meth) acrylate, ditrimethyloltetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate.
• the content of the carbon-carbon multiple bond contained in the cross-linking agent (C) is not particularly limited, but the multiple bond equivalent thereof is preferably 60 g / mol or more and 1000 g / mol or less, and more preferably 80 g / mol or more and 900 g / mol or less. , 100 g / mol or more and 700 g / mol or less is more preferable, and 200 g / mol or more and 400 g / mol or more is further preferable.
• the multiple bond equivalent can be determined by the method described above in relation to the curable polymer (A).
• the blending amount of the cross-linking agent (C) is preferably 0 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the curable polymer (A).
• the resin composition according to the present disclosure may contain other optional components in addition to the above components.
• Optional components include, for example, antioxidants, antioxidants, UV absorbers, light stabilizers, defoamers, leveling agents, antistatic agents, surfactants, storage stabilizers, thermal polymerization inhibitors, plasticizers, etc. Examples thereof include a wettability improving agent, an adhesion imparting agent, an antistatic agent (tacky fire), and an organic solvent.
• These optional components may be one kind, but two or more kinds may be added.
• Such an optional component may be added in an amount that does not impair the effects of the present disclosure.
• the blending amount thereof is 0 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total mass of the resin composition. Is.
• the method for producing the cured product for forming the pressure-sensitive adhesive layer of the pellicle is not particularly limited, and the cured product can be produced by a method known as a method for producing the cured product for forming the pressure-sensitive adhesive layer.
• a method for producing the cured product for forming the pressure-sensitive adhesive layer For example, by mixing the above-mentioned curable polymer (A), the curing agents (B1) and (B2), and optionally the cross-linking agent (C), the organic solvent and other components in the above-mentioned blending amounts.
• the cured product can be obtained by obtaining a resin composition and curing the solution of the pressure-sensitive adhesive.
• the above-mentioned cured product can be obtained by curing the resin composition according to the present disclosure.
• the curing method and the like refer to the following pellicle manufacturing method.
• the pellicle of the present disclosure can be produced by a method including the following steps. Step 1) of applying a pellicle film on one end surface of the pellicle frame, Step 2) of applying the resin composition containing at least the curable polymer (A), the curing agent (B1) and the curing agent (B2) to the other end surface of the pellicle frame. A step 3) in which the applied resin composition is subjected to a curing treatment of the curing agent (B1), a curing treatment of the curing agent (B2), and a flattening treatment to provide a pressure-sensitive adhesive layer (3).
• the pellicle of the present disclosure has been conventionally used except that in step 2), a pressure-sensitive adhesive layer is provided using a resin composition containing at least two kinds as a curing agent, and in step 3), a two-step curing step is performed. It can be manufactured in the same manner as the pellicle of. When three or more types of curing agents that cure under different conditions are used, it is possible to carry out three or more stages of curing steps under conditions suitable for curing by each curing agent.
• Step 1) in the method for manufacturing a pellicle may be carried out before step 2) or after step 3). However, step 3) must be carried out after step 2).
• the resin composition used in step 2) is a curable polymer (A), a curing agent (B1) which is a thermal radical polymerization initiator, and photoradical polymerization initiation. It contains a curing agent (B2), which is an agent, and is subjected to a photocuring treatment, a thermosetting treatment, and a flattening treatment in step 3).
• the curing treatment may be a known method, for example, a photocuring treatment, a thermosetting treatment, a radiation effect treatment, or the like.
• a pellicle film is stretched on one opening of the pellicle frame.
• the pellicle film can be applied by a usual method.
• a commonly used adhesive may be applied to one end face of the pellicle frame to form an adhesive layer, and the pellicle film may be fixed on the adhesive layer.
• the adhesive may be a known one, and may be, for example, a cellulose derivative, a chlorinated polypropylene, a polyamide-based adhesive, a fluororesin-based adhesive, an acrylic-based adhesive, an epoxy resin, a polyimide-based adhesive, or the like.
• step 2 a resin composition containing the curable polymer (A), the curing agent (B1) and the curing agent (B2) is applied to the other end surface of the pellicle frame.
• the resin composition can be produced by a method known as a method for producing an adhesive.
• a method for producing an adhesive For example, the above-mentioned curable polymer (A), the curing agent (B1) and the curing agent (B2), and optionally the cross-linking agent (C), the organic solvent and other components are mixed in the above-mentioned blending amounts.
• the above resin composition can be obtained.
• the resin composition can be applied to the pellicle frame as it is, or it may be further added with other components to prepare a coating solution.
• the coating solution may further contain an organic solvent together with the resin composition.
• the solvent include the following compounds. Aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and 2-methyl-5-hexanone; ester solvents such as ethyl acetate and butyl acetate; Halogen solvent; Glycol ether solvents such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono n-propyl ether and propylene glycol; glycol ether carboxylate solvents such as propylene glycol monomethyl ether acetate.
• the organic solvent may be one kind, but two or more kinds may be mixed and used.
• the boiling point of the organic solvent (that is, the boiling point of the solvent used in the case of one kind) (that is, the boiling point of the mixture in the case of two or more kinds) is preferably 150 ° C. or less. Since the thermal decomposition start temperature of the (meth) acrylic acid ester copolymer used as an example of the curable polymer (A) is around 150 ° C., if the boiling point of the organic solvent used is 150 ° C. or lower, (meth) ) It is possible to remove the organic solvent without heating to around 150 ° C. where the acrylic acid ester copolymer can be decomposed.
• the amount of the organic solvent to be blended is not particularly limited, but is usually 0 parts by mass or more and 90 parts by mass or less, more preferably 0 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the entire coating solution. preferable.
• the above resin composition or coating solution can be applied by using any coating means, for example, a spray coating method, a dipping coating method, a brush coating method, a spatula coating method, a roller coating method, a casting coating method, etc. Can be done by.
• a spray coating method for example, after dropping a droplet on the surface of a pellicle frame, the droplet can be stretched by a jig and applied to a uniform thickness.
• the thickness of the coating film formed here is not particularly limited, but is usually 0.2 mm or more and 0.8 mm or less.
• Step 3) The coating film formed by applying the resin composition to the pellicle frame is subjected to a curing treatment of the curing agent (B1), a curing treatment of the curing agent (B2), and a flattening treatment to obtain a pressure-sensitive adhesive.
• a curing treatment of the curing agent (B1) is a thermal radical polymerization initiator
• the curing agent (B2) is a photoradical polymerization initiator
• the photocuring treatment, the thermosetting treatment, and the flattening treatment are performed.
• the above resin composition after application can also be dried before carrying out the treatment for curing.
• As the heating conditions it can be carried out at a temperature of 40 ° C. to 110 ° C. for 5 minutes to 60 minutes.
• a photocuring treatment, a thermosetting treatment, and a flattening treatment are performed on the dried coating film.
• the order in which the photo-curing treatment, the thermosetting treatment, and the flattening treatment are performed is not particularly limited, and the photo-curing treatment may be performed after the photo-curing treatment, or the photo-curing treatment may be performed after the heat-curing treatment. It is desirable to first pre-cure the coating by photo-curing and then completely cure the coating by thermosetting. Further, the flattening treatment can be carried out at the same time as the photocuring treatment and / or the thermosetting treatment.
• the photocuring treatment be carried out under conditions that satisfy the curing conditions of the photoradical polymerization initiator contained as the curing agent (B2).
• the wavelength used for the photohardening treatment is preferably 254 nm to 365 nm, and the treatment time is preferably 10 minutes to 30 minutes. In such a photocuring treatment, since a certain amount of light irradiation is possible, it is easy to make the cured portion of the coating film constant.
• thermosetting treatment be carried out under conditions that satisfy the curing conditions of the thermal radical polymerization initiator contained as the curing agent (B1).
• the temperature used for the thermosetting treatment is preferably 40 ° C. to 170 ° C., and the treatment time is preferably 10 minutes to 2880 minutes.
• thermosetting treatment By performing the photocuring treatment under heating, the thermosetting treatment can be performed at the same time as the photocuring treatment. For example, the thermosetting treatment can be continued by starting the photocuring treatment under heating and continuously heating the photocuring treatment even after the photocuring treatment is completed.
• the flattening treatment is a treatment for adjusting the thickness of the pressure-sensitive adhesive layer containing the cured product and increasing the flatness thereof.
• the pellicle can be flattened by sandwiching a pellicle frame (or pellicle) provided with a coating film of an adhesive solution on a surface plate having a high degree of flatness, processing by putting it in a mold, or by its own weight alone.
• the flattening treatment can be carried out at the same time as the above-mentioned photocuring treatment and / or thermosetting treatment. For example, by heating the coating film while pressing a flat glass plate against the coating film, heat is generated. It is also possible to perform the curing treatment and the flattening treatment at the same time.
• a protective film can be attached to the adhesive provided on the pellicle frame.
• a polyester film or a polyethylene film that has been subjected to a mold release treatment with silicone or fluorine can be used.
• the pressure-sensitive adhesive layer obtained after the flattening step usually has a flatness of 20 ⁇ m to 1 ⁇ m, preferably 10 ⁇ m to 1 ⁇ m.
• the flatness is the height difference (difference between the highest point and the lowest point from the reference point) obtained by measuring the height of the pressure-sensitive adhesive layer every 0.3 mm over the entire circumference.
• the flatness is defined as the flatness as a result of measurement by a flatness measuring machine (manufactured by Corning Tropel Co., Ltd., device name "FlatMaster") of the Fizeau type oblique incident interference measurement method.
• the Fizeau-type oblique oblique interference measurement shall be performed under the following conditions. Wavelength: 635 nm, fringe sensitivity: 8.28 ⁇ m
• the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is generally 0.2 mm or more and 0.8 mm or less. Further, it is preferably 0.1 mm or more from the viewpoint of enabling uniform attachment to the mask. Since the metal frame of the pellicle is hard and hard to be deformed, it is considered that if the adhesive layer is made thicker, the metal frame can be made thinner and the flatness of the pellicle as a whole is improved.
• volatile components can be removed.
• the volatile components can be removed by heating and drying the pellicle at 150 ° C. for 4 hours or 120 ° C. for 20 hours under conditions where the pressure-sensitive adhesive layer and the pellicle film do not deteriorate.
• the pellicle thus obtained is mounted on the mask via the pressure-sensitive adhesive layer. As a result, it is possible to prevent foreign matter from adhering to the mask. Foreign matter adhering to the mask causes poor resolution on the wafer when the exposure light is focused on it. Therefore, the pellicle is mounted so as to cover the exposed area of the mask.
• a mask is a glass substrate or the like on which a patterned light-shielding film is arranged.
• the light-shielding film can be a metal film such as Cr or MoSi.
• the exposure light is incident from a part other than the light-shielding film of the mask and passes through the pellicle film.
• the exposure light is usually incident substantially parallel to the normal of the pellicle film, but may be incident diagonally to the normal of the pellicle film.
• the exposure light used for lithography such as the process of forming a circuit pattern drawn on a semiconductor element is short such as i-line (wavelength 365 nm) of a mercury lamp, KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm). It can be excimer light of wavelength or the like.
• the pressure-sensitive adhesive layer of the pellicle contains at least two types of curing agents to improve the flatness of the pressure-sensitive adhesive layer, resulting in less distortion of the mask with the pellicle and exposure. Positional deviation is also reduced.
• Curable polymer (A) RA-341 "Art Cure RA-341" manufactured by Negami Kogyo Co., Ltd. (Multiple bond equivalent: 13000 g / mol, Weight average molecular weight: 80000)
• RA-341 solid content concentration: 100%
• a thermal radical was added to 100 parts by mass of RA-341 as a curing agent (B1).
• a polymerization initiator peroxide-based radical polymerization initiator, solid content concentration: 25%
• 0.01 part by mass of a photoradical polymerization initiator as a curing agent (B2)
• the resin composition 1 was applied to the end face of an anodized aluminum pellicle frame (outer dimensions: 149 mm ⁇ 122 mm, frame height: 5.8 mm, frame width: 2 mm) at a coating temperature of 60 ° C. using a dispenser. Was applied with. This was heated and dried (60 ° C., 30 minutes) to obtain a coating film. The obtained coating film was subjected to a photocuring treatment by adjusting the irradiation amount so that the dose amount was 410 mJ / cm 2. Then, a PET separator was attached to the light-cured coating film.
• Example 2 to 3 Except for changing the amount of each component so that the solid content concentration ratio of the curable polymer (A): curing agent (B1): curing agent (B2) of the resin composition becomes the value shown in Table 1.
• a resin composition was prepared in the same manner as in Example 1 to obtain resin compositions 2 and 3, respectively. Using the obtained resin composition, an adhesive layer was formed on the end face of the pellicle frame in the same manner as in Example 1 to obtain a pellicle.
• the resin composition 1 was applied to the end face of an anodized aluminum pellicle frame (outer dimensions: 149 mm ⁇ 122 mm, frame height: 5.8 mm, frame width: 2 mm) at a coating temperature of 60 ° C. using a dispenser. Was applied with. This was heated and dried (60 ° C., 30 minutes) to obtain a coating film. A PET separator was attached to the obtained coating film. In order to obtain an adhesive layer with a separator, a heat hardening treatment (120 ° C./30 minutes) was carried out while pressing a flat glass plate from above the separator.
• the flatness was measured by tropel measurement. Using the pellicle produced in Examples and Comparative Examples as a test piece (outer dimensions: 149 mm ⁇ 122 mm, frame height H: 5.8 mm, frame width W: 2 mm), a Fizeau-type oblique incident interference measurement type flatness measuring machine (flatness measuring machine) It was placed in a device named "FlatMaster” manufactured by Corning Tropel Co., Ltd., and the height difference was measured under the conditions of wavelength: 635 nm and stripe sensitivity: 8.28 ⁇ m. The flatness was measured every 0.3 mm in height over the entire circumference of the pressure-sensitive adhesive layer, and was used as the height difference (difference between the highest point and the lowest point from the reference point) obtained from the measurement.
• the flatness was as good as 10 ⁇ m or less.
• a pellicle having an adhesive layer with good flatness and a method for producing the pellicle with good reproducibility are disclosed.
• the distortion of the mask is reduced, and the deviation of the exposure position is less likely to occur.
• the method for producing a pellicle of the present disclosure it is possible to produce a pellicle having an adhesive layer having good flatness with a high yield.

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