WO2011016148A1 - モールド固定用粘着シートおよびモールド固定用粘着テープ、並びに微細構造の製造方法 - Google Patents
モールド固定用粘着シートおよびモールド固定用粘着テープ、並びに微細構造の製造方法 Download PDFInfo
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- WO2011016148A1 WO2011016148A1 PCT/JP2009/068384 JP2009068384W WO2011016148A1 WO 2011016148 A1 WO2011016148 A1 WO 2011016148A1 JP 2009068384 W JP2009068384 W JP 2009068384W WO 2011016148 A1 WO2011016148 A1 WO 2011016148A1
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- mold
- pressure
- sensitive adhesive
- adhesive sheet
- melting point
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/30—Mounting, exchanging or centering
- B29C33/305—Mounting of moulds or mould support plates
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- 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
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
- B29C2059/023—Microembossing
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to an adhesive sheet and an adhesive tape for fixing a mold used in imprint lithography, and a method for manufacturing a fine structure.
- imprint lithography a film made of a curable resin composition is formed on the surface of a substrate, the surface of the film is pressed with a mold to transfer a fine pattern of the mold, and the film to which the fine pattern has been transferred is cured to form a fine film.
- a pattern is formed on the substrate surface (see, for example, Non-Patent Document 1).
- the mold is usually used in a state of being fixed to the pedestal with a jig such as a vacuum chuck or a mechanical chuck.
- pressure-sensitive adhesive sheets and pressure-sensitive adhesive tapes composed of general acrylic pressure-sensitive adhesives have the following problems. That is, when, for example, a UV curable resin composition is employed as the curable resin composition, the mold is usually peeled off from the cured film after UV is irradiated to cure the film. However, since the mold is difficult to peel when the film is cured, a relatively large load is applied to the pressure-sensitive adhesive sheet and pressure-sensitive adhesive tape during the vertical peeling.
- a general pressure-sensitive adhesive sheet and pressure-sensitive adhesive tape are not sufficiently fixed to the mold, and the mold falls off the pressure-sensitive adhesive sheet and pressure-sensitive adhesive tape when subjected to the load. Moreover, since a general adhesive sheet and an adhesive tape cannot be used repeatedly, it is not economical.
- An object of the present invention is to provide a mold fixing pressure-sensitive adhesive sheet, a mold fixing pressure-sensitive adhesive tape, and a method for producing a fine structure, which can fix a mold with a high fixing force while ensuring its surface smoothness. .
- the pressure-sensitive adhesive sheet for mold fixation of the present invention contains a side chain crystalline polymer as a main component.
- the side chain crystalline polymer is crystallized at a temperature lower than the melting point, exhibits fluidity at a temperature higher than the melting point, and has a storage elastic modulus G ′ of 1 ⁇ 10 2 to 1 ⁇ 10 5 Pa at the melting point + 10 ° C. It is.
- the mold fixing pressure-sensitive adhesive tape of the present invention is provided with pressure-sensitive adhesive layers on both surfaces of a base film, and at least the mold-side pressure-sensitive adhesive layer is made of the mold fixing pressure-sensitive adhesive sheet.
- the microstructure manufacturing method of the present invention uses the mold fixing pressure-sensitive adhesive sheet and includes the following steps (i) to (iv).
- (I) The process of interposing the said adhesive sheet between a mold and a base.
- (Ii) A step of setting the temperature of the pressure-sensitive adhesive sheet to a temperature lower than the melting point after the temperature of the side-chain crystalline polymer is higher than the melting point, and fixing the mold to the base via the pressure-sensitive adhesive sheet.
- (Iv) A step of curing the film on which the fine pattern is transferred to obtain a fine structure.
- the “sheet” in the present invention is not limited to a sheet shape, and is a concept including a sheet shape or a film shape as long as the effects of the present invention are not impaired.
- the mold is fixed to the pedestal with an adhesive sheet or an adhesive tape, there is no need to process the pedestal as in the prior art, and therefore the cost can be reduced, while ensuring the surface smoothness of the mold. Can be fixed to the pedestal.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape according to the present invention reversibly causes a crystalline state and a fluid state corresponding to a temperature change, and the storage elastic modulus G ′ in the fluid state has a specific value. It contains a chain crystalline polymer as a main component. Since this side-chain crystalline polymer exhibits high fluidity in a fluid state, the pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape containing the side-chain crystalline polymer as a main component has fine irregularities and voids present on the surface of the mold or pedestal. In the process of getting into the crystal well and changing from the fluid state to the crystal state, a so-called anchor effect is expressed and a high fixing force can be obtained.
- the mold can be prevented from falling off. Furthermore, since the said adhesive sheet or adhesive tape utilizes the phase change of a side chain crystalline polymer, it can be used repeatedly.
- (A)-(d) is process drawing which shows one Embodiment which manufactures a microstructure using the adhesive sheet for mold fixation of this invention.
- the pressure-sensitive adhesive sheet for mold fixation of the present invention contains a side chain crystalline polymer as a main component.
- the side-chain crystalline polymer is crystallized at a temperature lower than the melting point, and exhibits a fluidity by phase transition at a temperature higher than the melting point. That is, the side chain crystalline polymer reversibly causes a crystalline state and a fluid state in response to a temperature change.
- the side chain crystalline polymer has a storage elastic modulus G ′ at the melting point + 10 ° C. of 1 ⁇ 10 2 to 1 ⁇ 10 5 Pa, preferably 2 ⁇ 10 2 to 9 ⁇ 10 4 Pa.
- the side chain crystalline polymer in the fluidized state exhibits high fluidity
- the pressure-sensitive adhesive sheet containing the side chain crystalline polymer as a main component also exhibits high fluidity.
- the pressure-sensitive adhesive sheet enters into the fine irregularities and voids existing on the surface of the mold or pedestal without any gaps.
- the anchor effect is exhibited by crystallization of the side chain crystalline polymer, so that a high fixing force can be obtained.
- the storage elastic modulus G ′ at the melting point + 10 ° C. is smaller than 1 ⁇ 10 2 Pa, the cohesive force of the pressure-sensitive adhesive sheet is lowered, and the fixing force is also lowered accordingly.
- the storage elastic modulus G ′ is larger than 1 ⁇ 10 5 Pa, the fluidity of the side chain crystalline polymer is lowered, so that the anchor effect is hardly obtained and the fixing force is lowered.
- the side chain crystalline polymer preferably has a storage elastic modulus G ′ of 1 ⁇ 10 5 to 1 ⁇ 10 9 Pa at the melting point of ⁇ 10 ° C., preferably 1 ⁇ 10 6 to 1 ⁇ 10 8 Pa. More preferred. Thereby, the elasticity required to develop the anchor effect can be ensured. Further, since the side chain crystalline polymer in the crystalline state has appropriate elasticity, the pressure-sensitive adhesive sheet functions as a cushioning material. Therefore, it becomes possible to follow the warp of the substrate, minute projections, etc., and transfer defects can be prevented.
- the storage elastic modulus G ′ is a value obtained by measuring with a dynamic viscoelasticity measuring device as described in a synthesis example described later.
- the melting point of the side-chain crystalline polymer means a temperature at which a specific portion of the polymer originally aligned in an ordered arrangement becomes disordered by a certain equilibrium process
- a differential thermal scanning calorimeter ( DSC) is a value obtained by measurement under measurement conditions of 10 ° C./min.
- the melting point is preferably 30 to 70 ° C, more preferably 30 to 60 ° C. If the melting point is too low, when the ambient temperature changes during mold fixing and the temperature rises, the ambient temperature easily exceeds the melting point, and the side chain crystalline polymer exhibits fluidity, thereby fixing force. May decrease and the mold may fall off the adhesive tape. On the other hand, if the melting point is too high, a large amount of heat energy is required to bring the side chain crystalline polymer into a fluid state, which is economically disadvantageous.
- the storage elastic modulus G ′ and the melting point can be arbitrarily set by changing the composition and molecular weight of the side chain crystalline polymer.
- the composition of the side chain crystalline polymer is, for example, 20 to 100 parts by weight of a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms and (meth) acrylate 0 having an alkyl group having 1 to 6 carbon atoms. Examples thereof include a polymer obtained by polymerizing ⁇ 70 parts by weight and 0 to 10 parts by weight of a polar monomer.
- Examples of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms include 16 to 16 carbon atoms such as cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, and behenyl (meth) acrylate.
- Examples of the (meth) acrylate having 22 linear alkyl groups include (meth) acrylate having an alkyl group having 1 to 6 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) Acrylate, hexyl (meth) acrylate and the like.
- Examples of the polar monomer include carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; 2 -Hydroxyethyl (meth) acrylate, 2 Hydroxypropyl (meth) acrylate, 2-hydroxyhexyl (meth) ethylenically unsaturated monomer having a hydroxyl group such as acrylate and the like, which may be used alone or in combination.
- carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid
- 2 -Hydroxyethyl (meth) acrylate 2 Hydroxypropyl (meth) acrylate
- (meth) acrylate having a linear alkyl group having 16 or more carbon atoms has a great influence on the storage elastic modulus G ′ and the melting point.
- the storage elastic modulus G ′ and the melting point tend to be the specific values described above.
- a polymer etc. are mentioned.
- the storage elastic modulus G ′ and the melting point tend to be the specific values described above.
- Specific examples include copolymers obtained by polymerizing 40 to 50 parts by weight of behenyl acrylate, 45 to 55 parts by weight of butyl acrylate, and 0 to 10 parts by weight of acrylic acid.
- the polymerization method is not particularly limited, and for example, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method and the like can be employed.
- a solution polymerization method a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method and the like can be employed.
- the monomer exemplified above can be mixed with a solvent as necessary, and the monomer can be polymerized by stirring at about 40 to 90 ° C. for about 2 to 10 hours.
- the weight average molecular weight of the side chain crystalline polymer is preferably 5,000 or more, and more preferably 5,000 to 900,000. If the weight average molecular weight is too small or too large, the storage elastic modulus G ′ and the melting point may deviate from the specific values described above. Further, if the weight average molecular weight is too small, the cohesive force may be reduced and the fixing force may be reduced. If the weight average molecular weight is too large, the side chain crystallinity may be obtained even if the pressure-sensitive adhesive sheet is heated to a temperature equal to or higher than the melting point. There is a possibility that the polymer is difficult to exhibit fluidity.
- the weight average molecular weight is a value obtained by measuring a side chain crystalline polymer by gel permeation chromatography (GPC) and converting the obtained measurement value to polystyrene.
- the thickness of the pressure-sensitive adhesive sheet is preferably 15 to 400 ⁇ m, more preferably 120 to 150 ⁇ m. If the thickness of the pressure-sensitive adhesive sheet is too thin, the fixing force may be reduced, and it is difficult to function as a cushioning material, which is not preferable. Moreover, since it will become difficult to prepare an adhesive sheet with uniform thickness when the thickness of the adhesive sheet is too large, it is not preferable.
- a release-treated film that is, a release film
- the release film include a film surface made of polyethylene terephthalate or the like and a release agent such as silicone applied thereto.
- a coating solution obtained by adding a side chain crystalline polymer to a solvent is applied onto the release film and dried to obtain a pressure-sensitive adhesive sheet.
- a release film may be disposed.
- Various additives such as a crosslinking agent, a tackifier, a plasticizer, an anti-aging agent, and an ultraviolet absorber can be added to the coating solution.
- the application can be generally performed by a knife coater, a roll coater, a calendar coater, a comma coater or the like. Further, depending on the coating thickness and the viscosity of the coating solution, a gravure coater, a rod coater or the like can be used.
- the pressure-sensitive adhesive sheet can be formed into a sheet shape by, for example, extrusion molding or calendering.
- the pressure-sensitive adhesive tape for mold fixation of the present invention (hereinafter sometimes referred to as “pressure-sensitive adhesive tape”) is provided with pressure-sensitive adhesive layers on both surfaces of a base film, and at least the pressure-sensitive adhesive layer on the mold side is the above-described book. It consists of the adhesive sheet for mold fixation of invention. Thereby, the effect similar to an above-described adhesive sheet is acquired, and since the base film is included, the rigidity is higher than an adhesive sheet and the handleability is excellent.
- the base film examples include synthetic resins such as polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyimide, polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene polypropylene copolymer, and polyvinyl chloride. A film is mentioned.
- the base film may be composed of a single layer or a multilayer, and the thickness is usually about 25 to 250 ⁇ m.
- the surface of the base film can be subjected to surface treatment such as corona discharge treatment, plasma treatment, blast treatment, chemical etching treatment, and primer treatment in order to improve the adhesion to the pressure-sensitive adhesive layer.
- a coating solution obtained by adding the above-mentioned side chain crystalline polymer to a solvent may be applied to one side of the base film and dried.
- the thickness of the pressure-sensitive adhesive layer is preferably 5 to 60 ⁇ m, more preferably 10 to 60 ⁇ m, and even more preferably 10 to 40 ⁇ m.
- the pressure-sensitive adhesive layer on the other surface is not particularly limited, and may be composed of the above-described pressure-sensitive adhesive sheet for mold fixation of the present invention, for example, similarly to the pressure-sensitive adhesive layer on one side.
- the side chain crystalline polymer of the pressure-sensitive adhesive layer on one side and the side chain crystalline polymer of the pressure-sensitive adhesive layer on the other side may have the same composition or different compositions.
- a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive can be used as the pressure-sensitive adhesive layer on the other surface.
- the pressure-sensitive adhesive is an adhesive polymer, and examples thereof include natural rubber adhesives, synthetic rubber adhesives, styrene / butadiene latex base adhesives, and acrylic adhesives.
- the thickness of the pressure-sensitive adhesive layer on one side and the thickness of the pressure-sensitive adhesive layer on the other side may be the same or different from each other.
- the above-described pressure-sensitive adhesive sheet 1 for mold fixation of the present invention is interposed between a mold 10 and a base 15.
- the material constituting the mold 10 include silicon, silicone, (SiO 2 ) glass, nickel, and polyethylene terephthalate.
- a predetermined fine pattern 11 is formed on the surface 10 a of the mold 10.
- the fine pattern 11 is preferably a nano to micrometer scale.
- a suitable thickness of the mold 10 is about 10 to 2,000 ⁇ m.
- the thickness of the mold 10 means a thickness at which the distance between the front surface 10a and the back surface 10b is the largest.
- the pedestal 15 stably supports the mold 10 and its thickness is preferably, for example, 1 to 2 mm.
- the mold 10 After interposing the adhesive sheet 1 between the mold 10 and the pedestal 15, the mold 10 is fixed to the pedestal 15 via the adhesive sheet 1.
- the temperature of the pressure-sensitive adhesive sheet 1 is set to a temperature equal to or higher than the melting point of the side-chain crystalline polymer, preferably equal to or higher than the melting point + 10 ° C., and then the temperature lower than the melting point, preferably equal to or lower than the melting point ⁇ 10 ° C. To do.
- the side chain crystalline polymer changes phase from a fluid state to a crystalline state, thereby exhibiting an anchor effect for the reason described above, and thus high fixation while ensuring surface smoothness.
- the mold 10 can be fixed to the base 15 with force.
- the temperature of the pressure-sensitive adhesive sheet 1 can be adjusted by adjusting the ambient temperature and the temperature of the pedestal 15 using temperature adjusting means such as gas, a fan, and a heater.
- a film 21 is formed on the surface of the substrate 20 as shown in FIG.
- the material constituting the substrate 20 include silicon, (SiO 2 ) glass, and the like, polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyimide, polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, Examples include synthetic resins such as ethylene polypropylene copolymer and polyvinyl chloride.
- the thickness of the substrate 20 is preferably 50 to 300 ⁇ m, and more preferably 100 to 150 ⁇ m.
- the substrate 20 preferably has flexibility.
- the coating 21 is made of a UV curable resin composition.
- the UV curable resin composition is cured by being irradiated with UV (ultraviolet rays), and various known ones can be adopted.
- the coating film 21 may be formed by adding a UV curable resin composition to a predetermined solvent to obtain a coating solution, coating the coating solution on the surface of the substrate 20, and drying the coating solution.
- the application can be performed, for example, by spin coating, slit coating, spray coating, roller coating, or the like.
- the thickness of the uncured film 21 is preferably 0.01 to 1000 ⁇ m, and more preferably 0.01 to 500 ⁇ m.
- the mold 10 After forming the film 21 on the surface of the substrate 20, the mold 10 is disposed above the film 21. This arrangement is performed so that the fine pattern 11 of the mold 10 faces the coating 21. Next, the mold 10 is moved together with the base 15 in the direction of arrow A, and the surface of the coating 21 is pressurized with the mold 10 as shown in FIG. Thereby, the fine pattern 11 of the mold 10 is transferred to the coating 21.
- the pressure is about 0.1 to 100 MPa, and the pressurizing time is about 5 to 300 seconds.
- Curing of the film 21 to which the fine pattern 11 has been transferred is performed by irradiating the film 21 in a state where the surface of the film 21 is pressed with the mold 10, that is, in the state shown in FIG.
- the UV irradiation direction is not particularly limited as long as the coating 21 can be irradiated with UV. That is, when the substrate 20 has UV transparency, the coating 21 may be irradiated with UV from the back side of the substrate 20. Moreover, the adhesive sheet 1 usually has UV transparency. Therefore, if both the pedestal 15 and the mold 10 are made of a material having UV transparency, the coating film 21 can be irradiated with UV from the back side of the pedestal 15 through the pedestal 15, the adhesive sheet 1 and the mold 10. .
- the mold 10 is moved together with the pedestal 15 in the direction of arrow B, and the mold 10 is peeled from the cured coating 22.
- This peeling is usually performed by vertical peeling in order to suppress damage to the cured coating 22.
- a relatively large load is applied to the pressure-sensitive adhesive sheet 1. Since the pressure-sensitive adhesive sheet 1 fixes the mold 10 with a high fixing force for the reason described above, the mold 10 can be prevented from falling off even when the load is applied.
- the thickness of the cured coating 22 is preferably 0.01 to 1000 ⁇ m, and more preferably 0.01 to 500 ⁇ m.
- the residual film 26 is removed by, for example, oxygen reactive ion etching, and the surface of the substrate 20 is exposed from between the adjacent cured films 22, 22, and then etched using the cured film 22 as a mask. Processing can be performed, or aluminum or the like can be lifted off and used for wiring or the like. Moreover, what is necessary is just to repeat an above-described process, when manufacturing of the new fine structure 25 is continued.
- the mold 10 when the mold 10 is damaged or when another fine structure having a different fine pattern is manufactured, it is necessary to remove the mold 10 from the base 15 and replace it with another mold. In this case, what is necessary is just to heat the adhesive sheet 1 to the temperature more than melting
- the pressure-sensitive adhesive sheet 1 can be used repeatedly many times by performing the same operation as described above.
- the UV curable resin composition is described as an example of the curable resin composition.
- a thermoplastic resin composition such as polymethyl methacrylate (PMMA) is used. Things can also be used.
- PMMA polymethyl methacrylate
- Table 1 shows the copolymers of Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2.
- the said weight average molecular weight is a value which measured the copolymer by GPC and converted the obtained measured value into polystyrene.
- fusing point is the value measured on 10 degree-C / min measurement conditions using DSC.
- the storage elastic modulus G ′ is measured by using a dynamic viscoelasticity measuring device “DMS 6100” manufactured by Seiko Instruments Inc. in a heating process of 10 Hz, 5 ° C./min, and ⁇ 100 to 400 ° C. The storage elastic modulus G ′ at a melting point ⁇ 10 ° C. is measured.
- each copolymer solution obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2 was adjusted to have a solid content of 30% using ethyl acetate to obtain each copolymer solution.
- an adhesive solution obtained by adding 0.5 part of an isocyanate-based crosslinking agent in terms of solid content to 100 parts of each copolymer solution was applied to one side of a 100 ⁇ m thick polyethylene terephthalate film (PET film).
- PET film polyethylene terephthalate film
- the adhesive tape was fixed on an acrylic resin base plate.
- the other surface of the PET film opposite to the one surface on which the pressure-sensitive adhesive layer is formed is bonded onto the base plate using an acrylic adhesive ("AS5020" manufactured by Yushi Kogyo Co., Ltd.). Performed by fixing. Thereby, the said adhesive layer was made into the state which faced the upper direction with respect to the said baseplate.
- a regular cube made of stainless steel (SUS) having a side of 10 mm was brought into close contact with the pressure-sensitive adhesive layer under the following conditions and pressurized with 2 kg for 5 seconds, and then the regular cube was adhered to the regular cube at a speed of 300 mm / min. Vertical peeling from the agent layer. The vertical peel strength at this time was measured with a load cell. (60 ° C) The regular cube was tightly pressed against the pressure-sensitive adhesive layer at an atmospheric temperature of 60 ° C., and then vertically peeled.
- SUS stainless steel
- Examples 1 to 3 exhibit a higher fixing force than Comparative Examples 1 and 2 in the vertical peel strength of 60 ⁇ 23 ° C. Further, the results of the vertical peel strength at 60 ° C. show that Examples 1 to 3 can be removed relatively easily by heating to a temperature higher than the melting point.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
しかしながら、一般的なアクリル系粘着剤で構成された粘着シートや粘着テープには、以下の問題がある。すなわち、前記硬化性樹脂組成物として、例えばUV硬化性樹脂組成物を採用した場合には、通常、UVを照射して皮膜を硬化させた後にモールドを硬化被膜から垂直剥離する。ところが、皮膜を硬化させるとモールドを剥離し難くなるので、前記垂直剥離の際には、前記粘着シートや粘着テープに比較的大きな負荷がかかる。一般的な粘着シートおよび粘着テープは、モールドに対する固定力が十分ではなく、前記負荷を受けるとモールドが粘着シートや粘着テープから脱落してしまう。また、一般的な粘着シートおよび粘着テープは、繰り返し使用することができないので、経済的ではない。
(i)前記粘着シートをモールドと台座との間に介在させる工程。
(ii)前記粘着シートの温度を、前記側鎖結晶性ポリマーの融点以上の温度にした後に前記融点未満の温度にし、該粘着シートを介して前記モールドを台座に固定する工程。
(iii)固定されたモールドで、硬化性樹脂組成物からなる皮膜の表面を加圧し、モールドの微細パターンを転写する工程。
(iv)微細パターンが転写された皮膜を硬化させて微細構造を得る工程。
本発明のモールド固定用粘着シート(以下、「粘着シート」と言うことがある。)は、側鎖結晶性ポリマーを主成分として含有する。該側鎖結晶性ポリマーは、融点未満の温度で結晶化し、かつ融点以上の温度で相転移して流動性を示す。すなわち、前記側鎖結晶性ポリマーは、温度変化に対応して結晶状態と流動状態とを可逆的に起こす。
本発明のモールド固定用粘着テープ(以下、「粘着テープ」と言うことがある。)は、基材フィルムの両面に粘着剤層を設けてなり、少なくともモールド側の粘着剤層が、前記した本発明のモールド固定用粘着シートからなる。これにより、前記した粘着シートと同様の効果が得られ、かつ基材フィルムを含む分、粘着シートよりも剛性が高く、取り扱い性に優れるという効果が得られる。
次に、本発明の微細構造の製造方法にかかる一実施形態について、モールドの固定に前記した本発明のモールド固定用粘着シートを用い、硬化性樹脂組成物にUV硬化性樹脂組成物を用いた場合を例に挙げ、図1を参照して詳細に説明する。
まず、ベヘニルアクリレートを45部、ブチルアクリレートを50部、アクリル酸を5部、重合開始剤としてパーブチルND(日油社製)を0.5部、および連鎖移動剤としてN-ドデシルメルカプタン(日本油脂)を6部の割合で混合し、80℃で4時間撹拌し、これらのモノマーを重合させた。得られた共重合体の重量平均分子量は7,000、融点は37℃であった。また、前記融点+10℃における貯蔵弾性率G’は3×102Pa、融点-10℃における貯蔵弾性率G’は5×106Paであった。
まず、ベヘニルアクリレートを45部、ブチルアクリレートを50部、アクリル酸を5部および重合開始剤としてパーブチルND(日油社製)を0.5部の割合で混合し、55℃で4時間撹拌した。ついで、80℃へ昇温した後、重合開始剤としてパーへキシルPV(日油社製)を0.5部添加して2時間撹拌し、これらのモノマーを重合させた。得られた共重合体の重量平均分子量は67万、融点は46℃であった。また、前記融点+10℃における貯蔵弾性率G’は7×103Pa、融点-10℃における貯蔵弾性率G’は1×106Paであった。
まず、ベヘニルアクリレートを15部、ステアリルアクリレートを30部、メチルアクリレートを50部、アクリル酸を5部および重合開始剤としてパーブチルND(日油社製)を0.5部の割合で混合し、55℃で4時間撹拌した。ついで、80℃へ昇温した後、重合開始剤としてパーへキシルPV(日油社製)を0.5部添加して2時間撹拌し、これらのモノマーを重合させた。得られた共重合体の重量平均分子量は65万、融点は41℃であった。また、前記融点+10℃における貯蔵弾性率G’は8×104Pa、融点-10℃における貯蔵弾性率G’は2×107Paであった。
まず、ベヘニルアクリレートを20部、ステアリルアクリレートを25部、メチルアクリレートを50部、アクリル酸を5部、重合開始剤としてパーブチルND(日油社製)を0.5部、および連鎖移動剤としてN-ドデシルメルカプタン(日本油脂)を6部の割合で混合し、80℃で4時間撹拌し、これらのモノマーを重合させた。得られた共重合体の重量平均分子量は7,000、融点は40℃であった。また、前記融点+10℃における貯蔵弾性率G’は5×101Pa、融点-10℃における貯蔵弾性率G’は5×107Paであった。
まず、ベヘニルメタクリレートを65部、ブチルメタクリレートを30部、メタクリル酸を5部および重合開始剤としてパーブチルND(日油社製)を0.5部の割合で混合し、55℃で4時間撹拌した。ついで、80℃へ昇温した後、重合開始剤としてパーへキシルPV(日油社製)を0.5部添加して2時間撹拌し、これらのモノマーを重合させた。得られた共重合体の重量平均分子量は25万、融点は35℃であった。また、前記融点+10℃における貯蔵弾性率G’は5×105Pa、融点-10℃における貯蔵弾性率G’は9×105Paであった。
<粘着テープの作製>
まず、前記合成例1~3および比較合成例1,2で得られた各共重合体を、酢酸エチルを用いて固形分が30%になるよう調整して各共重合体溶液を得た。ついで、前記各共重合体溶液100部に対して固形分換算でイソシアネート系架橋剤を0.5部添加して得た粘着剤溶液を、厚さ100μmのポリエチレンテレフタレートフィルム(PETフィルム)の片面に塗布して乾燥させ、厚さ40μmの粘着剤層が形成された粘着テープをそれぞれ作製した。
上記で得た各粘着テープについて、垂直剥離強度を評価した。評価方法を以下に示すとともに、その結果を表2に示す。
まず、前記粘着テープをアクリル樹脂製の台板上に固定した。この固定は、PETフィルムの前記粘着剤層が形成された片面と反対側の他面を、アクリル系接着剤(一方社油脂工業株式会社製の「AS5020」)を用いて前記台板上に接着固定することにより行った。これにより、前記粘着剤層が、前記台板に対して上方を向く状態にした。
(60℃)
60℃の雰囲気温度で前記正立方体を前記粘着剤層に密着加圧した後、垂直剥離した。
(60℃→23℃)
60℃の雰囲気温度で前記正立方体を前記粘着剤層に密着加圧した後、雰囲気温度を23℃に低下させ、この雰囲気温度で20分間静置した後、垂直剥離した。
Claims (11)
- 側鎖結晶性ポリマーを主成分として含有するモールド固定用粘着シートであって、
前記側鎖結晶性ポリマーは、
融点未満の温度で結晶化し、かつ前記融点以上の温度で流動性を示すとともに、
前記融点+10℃における貯蔵弾性率G’が1×102~1×105Paであることを特徴とするモールド固定用粘着シート。 - 前記側鎖結晶性ポリマーは、前記融点-10℃における貯蔵弾性率G’が1×105~1×109Paである請求項1記載のモールド固定用粘着シート。
- 前記側鎖結晶性ポリマーの融点が30~70℃である請求項1または2記載のモールド固定用粘着シート。
- 前記側鎖結晶性ポリマーが、炭素数16以上の直鎖状アルキル基を有する(メタ)アクリレート20~100重量部と、炭素数1~6のアルキル基を有する(メタ)アクリレート0~70重量部と、極性モノマー0~10重量部と、を重合させて得られる重合体である請求項1~3のいずれかに記載のモールド固定用粘着シート。
- 前記側鎖結晶性ポリマーが、ベヘニルアクリレート5~15重量部と、ステアリルアクリレート30~40重量部と、メチルアクリレート45~55重量部と、アクリル酸0~10重量部と、を重合させて得られる共重合体である請求項1~4のいずれかに記載のモールド固定用粘着シート。
- 前記側鎖結晶性ポリマーが、ベヘニルアクリレート40~50重量部と、ブチルアクリレート45~55重量部と、アクリル酸0~10重量部と、を重合させて得られる共重合体である請求項1~4のいずれかに記載のモールド固定用粘着シート。
- 基材フィルムの両面に粘着剤層を設けてなり、少なくともモールド側の粘着剤層が、請求項1~6のいずれかに記載のモールド固定用粘着シートからなることを特徴とするモールド固定用粘着テープ。
- 請求項1~6のいずれかに記載のモールド固定用粘着シートを用いて微細構造を製造する方法であって、
前記粘着シートをモールドと台座との間に介在させる工程と、
前記粘着シートの温度を、前記側鎖結晶性ポリマーの融点以上の温度にした後に前記融点未満の温度にし、該粘着シートを介して前記モールドを台座に固定する工程と、
固定されたモールドで、硬化性樹脂組成物からなる皮膜の表面を加圧し、モールドの微細パターンを転写する工程と、
微細パターンが転写された皮膜を硬化させて微細構造を得る工程と、
を含むことを特徴とする微細構造の製造方法。 - 前記粘着シートの温度を、前記側鎖結晶性ポリマーの融点+10℃以上の温度にした後に前記融点-10℃以下の温度にし、該粘着シートを介して前記モールドを台座に固定する請求項8記載の微細構造の製造方法。
- 前記硬化性樹脂組成物がUV硬化性樹脂組成物からなり、該UV硬化性樹脂組成物からなる皮膜表面をモールドで加圧して前記微細パターンを転写し、UVを照射して皮膜を硬化させた後、該硬化被膜からモールドを垂直剥離する請求項8または9記載の微細構造の製造方法。
- 前記モールドの微細パターンがナノないしマイクロメートルスケールである請求項8~10のいずれかに記載の微細構造の製造方法。
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