WO2017200103A1 - 離型フィルム - Google Patents
離型フィルム Download PDFInfo
- Publication number
- WO2017200103A1 WO2017200103A1 PCT/JP2017/018931 JP2017018931W WO2017200103A1 WO 2017200103 A1 WO2017200103 A1 WO 2017200103A1 JP 2017018931 W JP2017018931 W JP 2017018931W WO 2017200103 A1 WO2017200103 A1 WO 2017200103A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- adhesive
- polymer
- group
- sensitive adhesive
- Prior art date
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- 239000012790 adhesive layer Substances 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000004065 semiconductor Substances 0.000 claims description 19
- 238000007789 sealing Methods 0.000 claims description 10
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- 239000013464 silicone adhesive Substances 0.000 claims description 8
- 239000003522 acrylic cement Substances 0.000 claims description 7
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- -1 methacryloyl group Chemical group 0.000 description 91
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 44
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- 244000043261 Hevea brasiliensis Species 0.000 description 28
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- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 6
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
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- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- SZNCKQHFYDCMLZ-UHFFFAOYSA-L zinc;propan-2-yloxymethanedithioate Chemical compound [Zn+2].CC(C)OC([S-])=S.CC(C)OC([S-])=S SZNCKQHFYDCMLZ-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
-
- 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
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/552—Protection against radiation, e.g. light or electromagnetic waves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/212—Electromagnetic interference shielding
-
- 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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the “peeling force between the adhesive layer and the electromagnetic wave shielding sheet” is a value (N / 50 mm) measured under conditions of a peeling angle of 180 ° and a peeling speed of 0.3 m / min in an atmosphere of 170 ° C. It is.
- the peeling force can be measured, for example, using a Tensilon universal material testing machine (manufactured by A & D Co., Ltd.).
- the thickness of the adhesive layer 40 is preferably 1 ⁇ m to 20 ⁇ m, and more preferably 2 ⁇ m to 12 ⁇ m. If the thickness of the pressure-sensitive adhesive layer 40 is 1 ⁇ m or more, the electromagnetic wave shielding sheet 30 tends to be favorably transferred from the pressure-sensitive adhesive layer 40 to the adherend, and if it is 20 ⁇ m or smaller, the electromagnetic wave shielding sheet 30 is in the sealing step. Tends to be difficult to peel from the adhesive layer 40.
- the content of alkenyl groups in the first polydimethylsiloxane is preferably 0.01% to 10%, and preferably 0.1% to 5%. It is more preferable.
- the alkenyl group is preferably present at least at both ends of the molecular chain, and more preferably present at both ends and the side chain.
- the polymerization degree (number of siloxane bonds) of the first polydimethylsiloxane is preferably 200 to 5,000, and more preferably 500 to 3,000.
- the weight average molecular weight of the first polydimethylsiloxane is preferably 20,000 to 1,300,000, and more preferably 300,000 to 1,200,000.
- the tackifying resin preferably has a softening point (softening temperature) of 80 ° C. or higher (preferably 100 ° C. or higher). By using such a tackifying resin, a higher-performance (for example, highly adhesive) pressure-sensitive adhesive tends to be obtained.
- the upper limit in particular of the softening point of tackifying resin is not restrict
- the softening point of the tackifying resin referred to here is a value measured by a softening point test method (ring ball method) defined in either JIS K 5902: 2006 and JIS K 2207: 2006.
- the method for applying the rubber adhesive on the substrate is not particularly limited.
- a method of directly forming a pressure-sensitive adhesive layer on a base material by applying a pressure-sensitive adhesive composition in which a rubber-based pressure-sensitive adhesive component is dissolved or dispersed in a suitable medium to the base material and then drying A known method such as a method of transferring a pressure-sensitive adhesive layer formed on a surface having a surface to a substrate can be appropriately employed.
- the pressure-sensitive adhesive composition can be prepared, for example, by mixing a polymer component, typically a tackifier, other components used as necessary, and the medium by a conventional method.
- the vulcanization accelerator contained in the rubber-based pressure-sensitive adhesive may be one type alone or two or more types.
- dithiocarbamic acids and thiurams may be used in combination.
- the amount of the vulcanization accelerator used can be, for example, 0.1 to 10 parts by mass (preferably 0.5 to 5 parts by mass) with respect to 100 parts by mass of the polymer component.
- Bifunctional or higher isocyanate compounds include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2,4-tolylene diisocyanate , 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and other aromatic diisocyanates; trimethylolpropane / tolylene diisocyanate trimer adduct (trade name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / Hexamethylene diisocyanate trimer adduct (trade name Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethylene diisocyanate Isocyanurate body (Nippon
- the rubber-based adhesive may contain additives as necessary.
- additives include softeners, flame retardants, antistatic agents, light stabilizers (radical scavengers, ultraviolet absorbers, etc.), antioxidants, and the like.
- the urethane-based adhesive means an adhesive having a urethane polymer as a base polymer.
- the urethane polymer include a polymer obtained by reacting a polyol and a polyisocyanate compound, and a terminal isocyanate group-containing urethane prepolymer (hereinafter referred to as “terminal NCO”) obtained by reacting a polyol with an excess amount of a polyisocyanate compound. (Referred to as "prepolymer”).
- Polyol is a polyether obtained by addition polymerization of propylene oxide or propylene oxide and alkylene oxide such as ethylene oxide to polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, etc.
- the polyol may be rosin diol.
- Rosin diol is a diol having two rosin skeletons and two hydroxyl groups in the molecule.
- the rosin diol include a rosin ester obtained by reacting rosin and a polyhydric alcohol, a reaction product of rosin and bisphenol A diglycidyl ether, and the like. These rosin diols can be produced by a conventionally known method.
- those having a polyoxyalkylene skeleton are preferable from the viewpoint of compatibility with the NCO-terminated prepolymer.
- Examples of commercially available rosin diols having a polyoxyalkylene skeleton include Pine Crystal D-6011, KE-615-3, and D-6250 (all of which are Arakawa Chemical Industries, Ltd.).
- polyfunctional polyols can be produced by a conventionally known method, and are also available as commercial products.
- examples of commercially available polyfunctional polyols include EL-410NE (Asahi Glass Co., Ltd.), POLYPL 4525 (Perstorp Specialty Chemicals AB), and the like.
- the polyfunctional polyol is preferably used in combination with other polyols.
- polypropylene glycol is preferable, and a combination of polypropylene glycol and rosin diol is more preferable.
- the amount of the polyfunctional polyol used is such that the number of hydroxyl groups in the polyfunctional polyol is 60, the number of hydroxyl groups in the entire polyol, from the viewpoint of the flexibility of the cured product (adhesive). %, Preferably in an amount of 5% to 20%.
- the polyisocyanate compound is not particularly limited, and may be any one belonging to aromatic, aliphatic or alicyclic. Specifically, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,4-phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, Examples thereof include naphthylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, crude TDI, polymethylene / polyphenyl isocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate, and hydrogenated xylylene diisocyanate.
- TDI tolylene diisocyanate
- MDI diphenylmethane diisocyanate
- IPDI isophor
- polyfunctional polyisocyanates include Coronate HX (alicyclic polyisocyanate, Nippon Polyurethane Industry Co., Ltd.), Takenate D-170N (alicyclic polyisocyanate, Takeda Pharmaceutical Co., Ltd.), Sumidur N-3500 (Fat Group polyisocyanate, Sumika Bayer Urethane Co., Ltd.), Sumidur N-3200 (aliphatic polyisocyanate, Sumika Bayer Urethane Co., Ltd.), Duranate 24A-100 and Duranate E-405-80T (Asahi Kasei Chemicals Corporation) Can be mentioned.
- the polyfunctional polyisocyanate compound is preferably used in combination with other polyisocyanate compounds.
- IPDI is preferable.
- the amount of the polyfunctional polyisocyanate compound used is such that the number of NCO groups in the polyfunctional polyisocyanate compound is the entire polyisocyanate compound from the viewpoint of properties after the reaction.
- the amount is preferably 60% or less of the number of NCO groups, and more preferably 5% to 20%.
- the terminal NCO prepolymer can be obtained by reacting a polyol, an excess amount of a polyisocyanate compound, and a monool as necessary. In this case, the adhesive strength (peel strength) after curing of the adhesive is more excellent.
- the monool When the monool is a polymer, its number average molecular weight may be, for example, 100 to 10,000, and is preferably 500 to 10,000 from the viewpoint of versatility and handling.
- Examples of the commercially available monool polymer include PML-S1004F (Asahi Glass Co., Ltd.).
- the amount used is preferably 5% by mass to 50% by mass with respect to the total amount of the polyol from the viewpoint of performance after curing, and is 5% by mass to 30% by mass. It is more preferable.
- the urethane-based pressure-sensitive adhesive contains a tackifier
- the content thereof is preferably 10% by mass to 60% by mass with respect to the total amount of the pressure-sensitive adhesive composition from the viewpoint of the balance between physical properties after curing and performance. More preferably, it is from 50% by mass to 50% by mass.
- the urethane-based pressure-sensitive adhesive may contain a reactive monofunctional compound as necessary. By including the reactive monofunctional compound, the adhesive strength (peel strength) after curing of the adhesive is more excellent.
- Urethane adhesive may contain additives as necessary.
- Additives include urethane catalysts, plasticizers (acrylic ester plasticizers, phthalic diesters, epoxidized hexahydrophthalic diesters, alkylene dicarboxylic diesters, alkylbenzenes, etc.), fillers (heavy calcium carbonate) , Fatty acid-treated calcium carbonate, fumed silica, precipitated silica, carbon black, talc, titanium oxide, balloons, beads, etc.), antioxidants (hindered phenols, etc.), flame retardants, thixotropic agents (colloidal silica, Organic bentonite, fatty acid amide, polyamide wax, hydrogenated castor oil, etc.), UV absorbers (benzotriazoles, hindered amines, etc.), anti-aging agents (hindered phenols, mercaptans, sulfides, dithiocarboxylates, thiourea) Thiophosphin
- the method for producing the urethane pressure-sensitive adhesive is not particularly limited. For example, you may produce as a one-pack type urethane adhesive by mixing the polymer component contained in a urethane type adhesive, and the other component contained as needed.
- the urethane-based adhesive may be a solventless adhesive that does not substantially contain a solvent. When the urethane-based pressure-sensitive adhesive does not substantially contain a solvent, environmental pollution due to generation of odor, volatile organic compound (VOC), or the like can be suppressed when the pressure-sensitive adhesive is cured by heat.
- a treatment for improving the adhesion between the substrate and the adhesive layer may be applied to the surface of the substrate on which the adhesive layer is provided.
- the treatment method include surface treatment such as corona treatment and plasma treatment, and application of a primer (primer).
- a back treatment agent for adjusting the unwinding property from the roll of the adhesive film may be provided on the back surface of the substrate (the surface opposite to the adhesive layer side).
- the back surface treatment agent include simple substances such as silicone resins, fluorine-containing resins, polyvinyl alcohol, and alkyl groups, modified products, and mixtures.
- an antistatic agent is applied to the back surface of the substrate or the surface on which the adhesive layer is provided in order to suppress the generation of static electricity when the adhesive film is unwound or peeled off from the adherend. May be.
- Antistatic agents include quaternary ammonium salts, pyridium salts, cationic antistatic agents having cationic groups such as primary to tertiary amino groups, anions such as sulfonate groups, sulfate ester bases, phosphate ester bases, etc.
- Example 1 100 parts by mass of adhesive A, 0.5 parts by mass of catalyst, and 275 parts by mass of a solvent (a mixture of toluene and methyl isobutyl ketone, mass ratio of 1: 1) are mixed and stirred with a disper to form an adhesive layer forming composition A product was prepared.
- This pressure-sensitive adhesive layer-forming composition was applied to the entire surface of one side of a base material (PET film having a thickness of 50 ⁇ m) so that the thickness of the pressure-sensitive adhesive layer was 3 ⁇ m, and heated at 120 ° C. for 1 minute. To form a support.
- a base material PET film having a thickness of 50 ⁇ m
- Example 1 and Comparative Example 1 in which an electromagnetic wave shielding sheet was formed by a laminating method, the produced release film was put in an atmosphere at 170 ° C., and after a predetermined time passed, The peeling force (N / 50 mm) was measured with a Tensilon universal material testing machine (manufactured by A & D Co., Ltd.) under a peeling angle of 180 ° and a peeling speed of 0.3 m / min. The results are shown in Table 1. In Example 2 and Example 3 in which the electromagnetic wave shielding sheet was formed by the ion plating method, the produced release film was cut into a predetermined size and placed on a 170 ° C.
- the transfer property of the electromagnetic wave shielding sheet is “Yes” when the electromagnetic wave shielding sheet can be peeled from the support without causing wrinkles, creases, tears, etc., or the electromagnetic wave shielding sheet has wrinkles, breaks, tears, or the like, or When it was not able to peel from a support body, it evaluated as “impossible”. The results are shown in Table 1.
- the release sheet of the example in which the peeling force between the adhesive layer and the electromagnetic wave shielding sheet is 0.10 N / 50 mm to 2.00 N / 50 mm has good transferability of the electromagnetic wave shielding sheet.
- Met the peeling force between the adhesive layer and the electromagnetic wave shielding sheet is less than 0.10 N / 50 mm, the peeled electromagnetic wave shielding sheet is wrinkled, and the transferability of the electromagnetic wave shielding sheet is an example. It was inferior.
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- Toxicology (AREA)
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- Laminated Bodies (AREA)
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Abstract
Description
<1>基材及び前記基材上に配置される粘着層を含む支持体と、前記支持体の前記粘着層上に配置される電磁波遮蔽シートと、を含み、前記粘着層と前記電磁波遮蔽シートの間の剥離力が0.10N/50mm~2.00N/50mmである、離型フィルム。
<2>前記電磁波遮蔽シートの厚みは0.01μm~50μmである、<1>に記載の離型フィルム。
<3>前記粘着層の厚みは1μm~20μmである、<1>又は<2>に記載の離型フィルム。
<4>前記粘着層はシリコーン系粘着剤及びアクリル系粘着剤からなる群より選択される少なくとも1種を含む、<1>~<3>のいずれか1項に記載の離型フィルム。
<5>半導体素子を封止する封止材に前記電磁波遮蔽シートを転写する工程を含む半導体装置の製造のための、請求項1~請求項4のいずれか1項に記載の離型フィルム。
本明細書において「~」を用いて示された数値範囲には、「~」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において組成物中の各成分の含有率又は含有量は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本明細書において組成物中の各成分の粒子径は、組成物中に各成分に該当する粒子が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
本明細書において「層」又は「膜」との語には、当該層又は膜が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
本明細書において「積層」との語は、層を積み重ねることを示し、二以上の層が結合されていてもよく、二以上の層が着脱可能であってもよい。
本明細書において「(メタ)アクリロイル基」はアクリロイル基及びメタクリロイル基の少なくとも一方を意味し、「(メタ)アクリル」はアクリル及びメタクリルの少なくとも一方を意味し、「(メタ)アクリレート」はアクリレート及びメタクリレートの少なくとも一方を意味する。
粘着層は、電磁波遮蔽シートとの間の剥離力が上記の範囲内となるものであれば、特に制限されない。例えば、シリコーン系粘着剤、アクリル系粘着剤、ゴム系粘着剤、ウレタン系粘着剤等の粘着剤を含む層が挙げられる。粘着層に含まれる粘着剤は、1種単独であっても2種以上であってもよい。
本発明において粘着層に含まれる粘着剤は、部分的又は完全に反応していても、未反応であってもよい。また、熱等により硬化した状態であっても、硬化していない状態であってもよい。
本明細書においてシリコーン系粘着剤は、シリコーンポリマーをベースポリマー(ポリマー成分のうちの主成分、すなわちポリマー成分全体の50質量%以上を占める成分)とする粘着剤を意味する。
シリコーン系粘着剤は、剥離力を比較的低くすることができ電磁波遮蔽シートが粘着層から剥離しやすい、電磁波遮蔽シートへの糊残り(粘着剤の残存)を抑制できる、等の観点から有利である。シリコーン系粘着剤としては、付加反応型シリコーン系粘着剤、過酸化物硬化型シリコーン系粘着剤、縮合型シリコーン系粘着剤等が挙げられる。硬化反応に過酸化物を使用せず、分解物が発生しないという観点からは、付加反応型シリコーン系粘着剤が好ましい。
付加反応型シリコーン系粘着剤とは、1分子中に少なくとも2個のアルケニル基(ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基等の1価の炭化水素基が挙げられ、中でもビニル基が特に好ましい。)を有する第1のポリジメチルシロキサンと1分子中に少なくとも2個のヒドロシリル基を有する第2のポリジメチルシロキサンとを含む付加反応型シリコーン樹脂と、シリコーンレジンとを含有するシリコーン系粘着剤である。
第1のポリジメチルシロキサンの重量平均分子量は、20,000~1,300,000であることが好ましく、300,000~1,200,000であることがより好ましい。
シリコーンレジンとしては、例えば、一官能シロキサン単位[(CH3)3SiO1/2]であるM単位と、四官能シロキサン単位[SiO4/2]であるQ単位とから構成されるMQレジンが挙げられる。MQレジンにおいてM単位とQ単位のモル比(M単位/Q単位)は、0.6~1.7であることが好ましい。
過酸化物硬化型シリコーン系粘着剤は、一般に、オルガノポリシロキサンを過酸化物により硬化(架橋)させてシリコーン系ポリマーを生成させる粘着剤である。また、縮合型シリコーン系粘着剤は、一般に、末端にシラノール基又はアルコキシシリル基等の加水分解性シリル基を有するポリオルガノシロキサン間の脱水又は脱アルコール反応によりシリコーン系ポリマーを生成させる粘着剤である。
本明細書においてアクリル系粘着剤とは、アクリル系ポリマーをベースポリマーとする粘着剤を意味する。アクリル系ポリマーとは、1分子中に少なくとも1つの(メタ)アクリロイル基を有するモノマー(以下、これを「アクリル系モノマー」ということがある。)を主たる構成単量体成分(アクリル系ポリマーを構成するモノマーの総量のうち50質量%以上を占める成分)とするポリマーを指す。アクリル系粘着剤は、透明性、耐候性、耐熱性、耐溶剤性等の点で有利である。
CH2=C(R1)COOR2 (1)
リン酸基含有モノマーとしては、2-ヒドロキシエチルアクリロイルホスフェート等が挙げられる。
シアノ基含有モノマーとしては、アクリロニトリル、メタクリロニトリル等が挙げられる。
ビニルエステル類としては、酢酸ビニル、プロピオン酸ビニル、ラウリン酸ビニル等が挙げられる。
芳香族ビニル化合物としては、スチレン、置換スチレン(クロロスチレン、クロロメチルスチレン、α-メチルスチレン等)などが挙げられる。
酸無水物基含有モノマーとしては、無水マレイン酸、無水イタコン酸、上記カルボキシ基含有モノマーの酸無水物等が挙げられる。
アミド基含有モノマーとしては、アクリルアミド、メタクリルアミド、ジエチルアクリルアミド、N-ビニルピロリドン、N,N-ジメチルアクリルアミド、N,N-ジメチルメタクリルアミド、N,N-ジエチルアクリルアミド、N,N-ジエチルメタクリルアミド、N,N’-メチレンビスアクリルアミド、N,N-ジメチルアミノプロピルアクリルアミド、N,N-ジメチルアミノプロピルメタクリルアミド、ジアセトンアクリルアミド等が挙げられる。
アミノ基含有モノマーとしては、アミノエチル(メタ)アクリレート、N,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジメチルアミノプロピル(メタ)アクリレート等が挙げられる。
イミド基含有モノマーとしては、シクロへキシルマレイミド、イソプロピルマレイミド、N-シクロへキシルマレイミド、イタコンイミド等が挙げられる。
エポキシ基含有モノマーとしては、グリシジル(メタ)アクリレート、メチルグリシジル(メタ)アクリレート、アリルグリシジルエーテル等が挙げられる。
ビニルエーテル類としては、メチルビニルエーテル、エチルビニルエーテル、イソブチルビニルエーテル等が挙げられる。
n-ブチルアクリレートのホモポリマー:-55℃
エチルアクリレートのホモポリマー:-22℃
メチルアクリレートのホモポリマー:8℃
メチルメタクリレートのホモポリマー:105℃
シクロヘキシルメタクリレートのホモポリマー:66℃
酢酸ビニルのホモポリマー:32℃
スチレンのホモポリマー:100℃
アクリル酸のホモポリマー:106℃
メタクリル酸のホモポリマー:130℃
温度計、撹拌機、窒素導入管及び還流冷却管を備えた反応器に、モノマー100質量部、アゾビスイソブチロニトリル0.2質量部、及び重合溶媒として酢酸エチル200質量部を投入し、窒素ガスを流通させながら室温(25℃)で1時間撹拌する。このようにして重合系内の酸素を除去した後、63℃に昇温して10時間反応させる。次いで、室温(25℃)まで冷却し、固形分濃度が33質量%のホモポリマー溶液を得る。次いで、このホモポリマー溶液を剥離ライナー上に流延塗布し、乾燥して厚み約2mmの試験サンプル(シート状のホモポリマー)を作製する。この試験サンプルを直径7.9mmの円盤状に打ち抜き、パラレルプレートで挟み込み、粘弾性試験機(ARES、レオメトリックス社)を用いて周波数1Hzのせん断歪みを与えながら、温度領域-70℃~150℃、5℃/分の昇温速度でせん断モードにより粘弾性を測定し、tanδのピークトップ温度をホモポリマーのTgとする。
ロジン誘導体としては、未変性ロジン又は変性ロジンをアルコール類によりエステル化したもの(ロジンエステル);未変性ロジン又は変性ロジンを不飽和脂肪酸で変性したもの(不飽和脂肪酸変性ロジン);ロジンエステルを不飽和脂肪酸で変性したもの(不飽和脂肪酸変性ロジンエステル);未変性ロジン、変性ロジン、不飽和脂肪酸変性ロジン又は不飽和脂肪酸変性ロジンエステルにおけるカルボキシ基を還元処理したもの(ロジンアルコール);未変性ロジン、変性ロジン及び上述したロジン誘導体(特に、ロジンエステル)の金属塩;未変性ロジン、変性ロジン及び上述したロジン誘導体にフェノールを酸触媒で付加させ熱重合することにより得られるロジンフェノール樹脂;などが挙げられる。
脂肪族系炭化水素樹脂としては、炭素数が4~5程度のオレフィン及びジエンから選択される1種又は2種以上の脂肪族炭化水素の重合体等が挙げられる。オレフィンとしては、1-ブテン、イソブチレン、1-ペンテン等が挙げられる。ジエンとしては、ブタジエン、1,3-ペンタジエン、イソプレン等が挙げられる。
本明細書においてゴム系粘着剤は、ゴム系ポリマーをベースポリマーとする粘着剤を意味する。ゴム系ポリマーは特に制限されず、天然ゴム系ポリマー(変性天然ゴム系ポリマーを含む)であっても合成ゴム系ポリマーであってもよい。合成ゴム系ポリマーとしては、ABA型又はAB型のブロック共重合体(Aは熱可塑性ブロックを示し、Bはラバーブロックを示す。スチレン-イソプレン-スチレン共重合体(SIS)、スチレン-ブタジエン-スチレン共重合体(SBS)等が挙げられる)が挙げられる。ゴム系ポリマーは、天然ゴム系ポリマーと合成ゴム系ポリマーの組み合わせであってもよい。
変性天然ゴム系ポリマーとしては、天然ゴム系ポリマーにグラフトさせるモノマーのうち50質量%以上がアクリル系モノマーであるもの(アクリル変性天然ゴム系ポリマー)が好ましい。
他の一態様では、天然ゴム系ポリマーにメタクリル酸メチル(MMA)がグラフトしてなるアクリル変性天然ゴム系ポリマー(NR-MMAグラフト共重合体)が好ましい。かかるグラフト共重合体は、常法により製造することができ、市販品としても入手できる。NR-MMAグラフト共重合体におけるMMAのグラフト率(天然ゴムに結合したMMAの質量/グラフト化に使用した天然ゴムの質量×100(%)により表され、通常はNR-MMAグラフト共重合体の製造に用いた天然ゴムとMMAとの質量比から算出される値と同等である)は、例えば1%~120%とすることができ、好ましくは5%~100%であり、より好ましくは10%~90%、さらに好ましくは30%~80%である。グラフト化率は、好ましくは50%~90%であり、より好ましくは60%~80%である。グラフト化率が1%以上であると、粘着力が高くなりすぎるのが抑制され、グラフト化率が120%以下であると、SUS板等の被着体に対する粘着力が低くなりすぎるのが抑制される。NR-MMAグラフト共重合体の製造に用いるMMAは、その一部(例えば、天然ゴムにグラフトさせるモノマー全体の5質量%以下、典型的には3質量%以下)が他のモノマーに置き換えられていてもよい。
本明細書においてウレタン系粘着剤は、ウレタンポリマーをベースポリマーとする粘着剤を意味する。ウレタンポリマーとしては、ポリオールとポリイソシアネート化合物を反応させて得られるポリマーが挙げられ、ポリオールと、過剰量のポリイソシアネート化合物とを反応させて得られる末端イソシアネート基含有ウレタンプレポリマー(以下、「末端NCOプレポリマー」と称する)が好ましい。末端NCOプレポリマーは、各種のポリオールと、過剰量のポリイソシアネート化合物とを、例えば、OHとNCOの当量比(OHの数/NCOの数)が1/1.2~3.5となるように反応させることにより合成することができる。反応は、必要により適当な反応触媒(ジブチル錫ジラウレート等の有機錫系触媒、オクチル酸ビスマス等のビスマス系触媒、1,4-ジアザ[2.2.2]ビシクロオクタン等の三級アミン系触媒など)の存在下で、例えば、20℃~90℃(好ましくは60℃~90℃)で1時間~7時間の条件で行うことができる。
発泡抑制、作業性、硬化性及び物性の安定性の観点からは、とりわけ、後述する特定の硬化触媒と組み合わせた際にこれらの特性の優れたバランスが得られる観点から、ポリオールは、プロピレンオキサイドの付加物としてのポリオキシアルキレンポリオールであるか、プロピレンオキサイドとエチレンオキサイドの付加物としてのポリオキシアルキレンポリオールであることが好ましい。実用性の観点からは、プロピレンオキサイドの付加物としてのポリオキシアルキレンポリオール(即ちポリプロピレンポリオール)がより好ましく、ポリプロピレングリコールがさらに好ましい。
ロジンジオールとしては、ロジンと多価アルコールとを反応させて得られるロジンエステル、ロジンとビスフェノールAジグリシジルエーテル等との反応物などが挙げられる。これらのロジンジオールは、従来から既知の方法によって製造できる。
ロジンジオールのなかでも、NCO末端プレポリマーとの相溶性の観点からは、ポリオキシアルキレン骨格を有するものが好ましい。ポリオキシアルキレン骨格を有するロジンジオールの市販品としては、パインクリスタルD-6011、KE-615-3、D-6250(いずれも荒川化学工業株式会社)等が挙げられる。
多官能ポリイソシアネートの市販品としては、コロネートHX(脂環族ポリイソシアネート、日本ポリウレタン工業株式会社)、タケネートD-170N(脂環族ポリイソシアネート、武田薬品株式会社)、スミジュールN-3500(脂肪族ポリイソシアネート、住化バイエルウレタン株式会社)、スミジュールN-3200(脂肪族ポリイソシアネート、住化バイエルウレタン株式会社)、デュラネート24A-100及びデュラネートE-405-80T(旭化成ケミカルズ株式会社)等が挙げられる。
ポリエステルモノオールとしては、例えば、既知のポリエステルポリオールの末端水酸基のアルキル化変性物、モノヒドロキシ化合物を開始剤として環状ラクトン化合物を開環付加共重合反応又はエステル化反応させて得られるラクトン系ポリエステルモノオール、多価アルコールと、飽和脂肪酸又は(メタ)アクリル酸、桂皮酸若しくは炭素数10以上の高級不飽和脂肪酸であるオレイン酸、リノール酸、リノレン酸等のエチレン性不飽和二重結合を有するカルボン酸と、から得られるエステルモノオールなどが挙げられる。
ポリエーテル・エステルモノオールとしては、脂肪酸エステルモノオールに前記(モノ)アルキレンオキサイドを付加重合させた、ポリオキシアルキレン脂肪酸エステルモノオール等が挙げられる。
高級飽和モノオールとしては、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール等の炭素数10以上の直鎖状で一価の高級飽和アルコールなどが挙げられる。
エチレン性不飽和二重結合を有するモノオールとしては、オレイルアルコール、リノレイルアルコール、リノレニルアルコール等の炭素数10以上の直鎖状で一価の高級不飽和アルコール、アリルアルコールなどが挙げられる。
なかでも、汎用及び安全性の観点から、ポリオキシアルキレン系モノオールが好ましくポリオキシプロピレンアルキルエーテルがより好ましい。
モノオールは、ポリマーであってもよい。モノオールがポリマーである場合、その数平均分子量は、例えば100~10,000であってよく、汎用性及びハンドリングの観点からは500~10,000であることが好ましい。
ポリマーであるモノオールの市販品としては、PML-S1004F(旭硝子株式会社)等が挙げられる。
ポリマーであるモノオールを使用する場合、その使用量は、硬化後の性能の観点から、ポリオール全量に対して5質量%~50質量%であることが好ましく、5質量%~30質量%であることがより好ましい。
粘着層は、フィラーを含んでもよい。粘着層がフィラーを含むことにより、粘着層の外表面(基材側とは逆の面)を粗化する等の効果が得られる。
フィラーの材質は特に制限されず、樹脂等の有機物質であっても、金属、金属酸化物等の無機物質であっても、有機物質と無機物質の組み合わせであってもよい。また、粘着層に含まれるフィラーは1種単独であっても2種以上であってもよい。
基材の材質は、特に制限されない。金型への追従性の観点からは、樹脂が好ましい。樹脂としては、ポリエチレンテレフタラート(PET)等のポリエステル、ポリイミド、ポリアミド、ポリエステルエーテル、ポリアミドイミド、フッ素含有樹脂などが挙げられる。樹脂を用いる場合は、封止工程中の加熱温度に対して充分な耐熱性を有するものであることが好ましい。
粘着剤A100質量部と、触媒0.5質量部と、溶剤(トルエンとメチルイソブチルケトンの混合物、質量比1:1)275質量部とを配合し、ディスパーで撹拌して、粘着層形成用組成物を調製した。この粘着層形成用組成物を、基材(厚みが50μmのPETフィルム)の一方の面の全面に、粘着層の厚みが3μmとなるように塗布し、120℃で1分間加熱して粘着層を形成して、支持体を作製した。次いで、長さが232mm、幅が67mm、厚みが9μmの銅箔(「F2-WS」、古河電気工業株式会社)を、図2に示すように支持体の粘着層にラミネート法で貼り合わせて電磁波遮蔽シートを形成し、所定の形状に打ち抜いて離型フィルムを作製した。
粘着剤B100質量部と、架橋剤A10質量部と、溶剤(トルエンとメチルエチルケトンの混合物、質量比8:2)227質量部とを配合し、ディスパーで撹拌して、粘着層形成用組成物を調製した。この粘着層形成用組成物を、基材(厚みが38μmのPETフィルム)の一方の面の全面に、粘着層の厚みが3μmとなるように塗布し、100℃で1分間加熱して粘着層を形成し、支持体を作製した。次いで、粘着層の全面に、イオンプレーティング法にてアルミニウム層を厚みが1μmとなるように形成して電磁波遮蔽シートを形成し、所定の形状に打ち抜いて離型フィルムを作製した。
粘着剤C100質量部と、架橋剤B17.4質量部と、フィラー10質量部と、溶剤(トルエンとメチルエチルケトンの混合物、質量比8:2)87質量部とを配合し、ディスパーで撹拌して、粘着層形成用組成物を調製した。この粘着層形成用組成物を用いたこと以外は実施例2と同様にして、離型フィルムを作製した。
実施例2と同様にして調製した粘着層形成用組成物を用いて、実施例2と同様にして基材上に粘着層を形成して支持体を作製した。次いで、粘着層の上に実施例1と同様にして電磁波遮蔽シートを形成し、離型フィルムを作製した。
(粘着剤)
・粘着剤A:付加反応型シリコーン系粘着剤、商品名「LTC755」、固形分30質量%、東レ・ダウコーニング株式会社
・粘着剤B:アクリル系粘着剤、商品名「S-43」、固形分24質量%、総研化学株式会社、ブチルアクリレート(BA)と4-ヒドロキシブチルアクリレート(4HBA)の混合モノマーで構成
・粘着剤C:アクリル系粘着剤、商品名「FS-1208」、固形分45質量%、ライオン・スペシャル・ケミカルズ株式会社、メタクリル酸エステルの複数種の混合モノマーで構成
(触媒)
・白金触媒(商品名「NC-25」、東レ・ダウコーニング株式会社)
(架橋剤)
・架橋剤A:商品名「コロネートHL」、固形分75質量%、東ソー株式会社、トリメチロールプロパン/ヘキサメチレンジイソシアネート3量体付加物の75%酢酸エチル溶液、1分子中のイソシアネート基数:3個
・架橋剤B:商品名「デュラネートE405-80T」、固形分80質量%、旭化成ケミカルズ株式会社、ポリイソシアネート系架橋剤(ヘキサメチレンジイソシアネート架橋剤(HMDI))、1分子中のイソシアネート基数:2個
・フィラー:架橋アクリル中分散粒子、商品名「MZ-10HN」、体積平均粒子径10μm、総研化学株式会社
作製した離型フィルムを用いて、以下の評価試験を行った。
電磁波遮蔽シートをラミネート法により形成した実施例1及び比較例1では、作製した離型フィルムを170℃雰囲気下に投入し、所定の時間経過後、テンシロン万能材料試験機(株式会社エー・アンド・デイ製)にて剥離角度180°、剥離速度0.3m/分の剥離条件で剥離力(N/50mm)を測定した。結果を表1に示す。
電磁波遮蔽シートをイオンプレーティング法により形成した実施例2及び実施例3では、作製した離型フィルムを所定の大きさにカットし、170℃のホットプレート上に粘着層が上になるように置き、封止材(商品名「CEL-9750」、日立化成株式会社)を粘着層の上に所定量散布し、厚みが100μmのPETフィルムを載せた。次いで、PETフィルムの上に4kgの重りを載せて、封止材が硬化するまで3分間放置した。その後、離型フィルムを50mm幅にカットし、170℃雰囲気下に投入した。1分経過後、テンシロン万能材料試験機(株式会社エー・アンド・デイ製)にて、剥離角度180°、剥離速度0.3m/分の剥離条件で剥離力を測定した。結果を表1に示す。
実施例1及び比較例1で作製した離型フィルムを所定の大きさにカットし、170℃のホットプレート上に粘着層が上になるように置き、封止材(商品名「CEL-9750」、日立化成株式会社)を粘着層の上に所定量散布し、厚みが100μmのPETフィルムを載せた。次いで、PETフィルムの上に4kgの重りを載せて、封止材が硬化するまで3分間放置した。その後、支持体(基材及び粘着層)から電磁波遮蔽シートを剥離して、電磁波遮蔽シートの転写性を目視にて確認した。
実施例2及び実施例3では、粘着層-電磁波遮蔽シート間剥離力の評価と同じく封止材が硬化した状態で、支持体(基材及び粘着層)から電磁波遮蔽シートを剥離して、電磁波遮蔽シートの転写性を目視にて確認した。
Claims (5)
- 基材及び前記基材上に配置される粘着層を含む支持体と、前記支持体の前記粘着層上に配置される電磁波遮蔽シートと、を含み、前記粘着層と前記電磁波遮蔽シートの間の剥離力が0.10N/50mm~2.00N/50mmである、離型フィルム。
- 前記電磁波遮蔽シートの厚みは0.01μm~50μmである、請求項1に記載の離型フィルム。
- 前記粘着層の厚みは1μm~20μmである、請求項1又は請求項2に記載の離型フィルム。
- 前記粘着層はシリコーン系粘着剤及びアクリル系粘着剤からなる群より選択される少なくとも1種を含む、請求項1~請求項3のいずれか1項に記載の離型フィルム。
- 半導体素子を封止する封止材に前記電磁波遮蔽シートを転写する工程を含む半導体装置の製造のための、請求項1~請求項4のいずれか1項に記載の離型フィルム。
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WO2019235556A1 (ja) * | 2018-06-08 | 2019-12-12 | 倉敷紡績株式会社 | 離型フィルムおよび離型フィルム製造方法 |
JPWO2019168008A1 (ja) * | 2018-02-27 | 2021-02-12 | 三菱ケミカル株式会社 | ポリエステルフィルム |
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- 2017-05-19 JP JP2018518395A patent/JP6863375B2/ja active Active
- 2017-05-19 CN CN201780031010.3A patent/CN109153239B/zh active Active
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KR20190010593A (ko) | 2019-01-30 |
CN109153239B (zh) | 2021-05-04 |
CN109153239A (zh) | 2019-01-04 |
JPWO2017200103A1 (ja) | 2019-04-18 |
TW201808629A (zh) | 2018-03-16 |
JP6863375B2 (ja) | 2021-04-21 |
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