KR20160121434A - Temperature sensitive adhesive sheet for dicing ceramic electronic component and method for manufacturing ceramic electronic component - Google Patents
Temperature sensitive adhesive sheet for dicing ceramic electronic component and method for manufacturing ceramic electronic component Download PDFInfo
- Publication number
- KR20160121434A KR20160121434A KR1020160043260A KR20160043260A KR20160121434A KR 20160121434 A KR20160121434 A KR 20160121434A KR 1020160043260 A KR1020160043260 A KR 1020160043260A KR 20160043260 A KR20160043260 A KR 20160043260A KR 20160121434 A KR20160121434 A KR 20160121434A
- Authority
- KR
- South Korea
- Prior art keywords
- sensitive adhesive
- adhesive layer
- pressure
- melting point
- dicing
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 40
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 40
- 239000000919 ceramic Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title description 12
- 238000002844 melting Methods 0.000 claims abstract description 42
- 230000008018 melting Effects 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000012790 adhesive layer Substances 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 73
- 239000010410 layer Substances 0.000 claims description 44
- -1 polyethylene terephthalate Polymers 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000004088 foaming agent Substances 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 102200061079 rs776498025 Human genes 0.000 description 3
- 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 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000103 Expandable microsphere Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- C09J7/02—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/14—Apparatus or processes for treating or working the shaped or preshaped articles for dividing shaped articles by cutting
-
- 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
- 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
- C09J133/10—Homopolymers or copolymers of methacrylic 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- 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
- C09J7/35—Heat-activated
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- 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
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- 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
- C09J2301/122—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 only on one side of the carrier, e.g. single-sided adhesive tape
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Structural Engineering (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Description
본 발명은 세라믹 전자 부품의 다이싱 공정에서 사용하는 다이싱용 감온성 점착 시트 및 이것을 사용하는 세라믹 전자 부품의 제조 방법에 관한 것이다.TECHNICAL FIELD The present invention relates to a pressure sensitive adhesive sheet for dicing used in a dicing step of a ceramic electronic component and a method of manufacturing a ceramic electronic component using the same.
세라믹 콘덴서는 통상, 세라믹의 분말과 바인더와 용제의 혼합물을 성형해서 얻은 세라믹 그린시트(세라믹 성형 시트)에 소정의 내부 전극을 인쇄하고, 이것을 대좌 상에 적층·압착하고(적층 공정), 이어서 얻어진 적층체를 다이싱 쏘(dicing saw)로 칩상으로 절단하고(다이싱 공정), 이 절단편을 박리시켜서(박리 공정), 소성하고, 최후에 절단편의 끝면에 외부 전극을 형성해서 제조되고 있다.The ceramic capacitor is usually produced by printing a predetermined internal electrode on a ceramic green sheet (ceramic formed sheet) obtained by molding a ceramic powder, a mixture of a binder and a solvent, laminating and pressing it on a pedestal (lamination step) The laminate is cut in a dicing saw with a dicing saw (dicing step), the cut pieces are peeled off (peeling step) and fired, and finally the external electrode is formed on the end face of the cutting piece.
상기 적층 공정 후의 다이싱 공정에서는 절단된 절단편이 비산하지 않도록 적층체가 대좌에 확실히 고정되어 있는 것이 필요하다. 이 때문에 절단 공정에서는 점착 시트를 이용하여 적층체를 대좌 상에 고정하고 있다. 한편, 절단편을 시트로부터 박리시키는 박리 공정에서는 점착 시트의 점착력을 저하시킬 필요가 있다.In the dicing step after the laminating step, the laminate should be firmly fixed on the pedestal so that the cut pieces are not scattered. Therefore, in the cutting step, the laminate is fixed on the pedestal using an adhesive sheet. On the other hand, in the peeling step of peeling the cut pieces from the sheet, it is necessary to lower the adhesive force of the pressure-sensitive adhesive sheet.
특히, 최근은 전자 부품의 소형화, 고성능화에 따라서, 세라믹 전자 부품 등의 피가공물의 다이싱 공정에 있어서도, 다이싱 정밀도의 향상이 요구되고 있다. 즉, 다이싱 시의 정밀도 향상을 위해서 강하게 고정하고, 그 후, 피가공물로의 데미지 방지를 위해서 이박리가 가능한 점착 테이프가 요구되고 있다.Particularly, in recent years, in accordance with miniaturization and high performance of electronic parts, improvement in dicing accuracy is required also in the dicing process of a workpiece such as a ceramic electronic part. That is, there is a demand for an adhesive tape which is firmly fixed to improve accuracy in dicing, and is then peeled off to prevent damage to the workpiece.
종래, 점착 시트로서는 발포 테이프, UV 테이프 등의 재박리 테이프가 사용되고 있지만, 실온에서의 점착제의 경도의 부족, 즉 저장 탄성률(G')이 낮음으로서, 다이싱 시에 피가공물에 어긋남이 발생하고, 전자 부품의 형상 정밀도가 저하하여 불량의 원인이 되고 있다.Conventionally, a peeling tape such as a foam tape or a UV tape is used as a pressure sensitive adhesive sheet. However, the lack of hardness of the pressure sensitive adhesive at room temperature, that is, the storage elastic modulus (G ') is low, , The shape precision of the electronic component is lowered, which is a cause of defects.
이러한 문제를 해결하기 위해서, 융점 이하에서 결정화하는 측쇄 결정성 폴리머를 함유하는 감온성 점착제 층에 발포제를 함유시킨 감온성 점착 시트를 사용하는 것이 제안되어 있다(특허문헌 1). 즉, 점착제 층이 측쇄 결정화 가능 폴리머를 함유하고 있기 때문에, 적층 공정에서는 측쇄 결정성 폴리머가 결정 상태이고, 점착 시트 상에 세라믹 그린 시트를 적층할 수 있고, 절단 공정에서는 점착 시트를 가열해서 점착성을 높여서 그린 시트의 적층체를 점착 시트 상에 고정할 수 있다. 한편, 다이싱 후의 박리 공정에서는 점착 시트를 더 가열해서 발포제를 발포시키고, 이 상태에서 융점 이하로 냉각시킴으로써, 점착 시트의 앵커 효과가 저감하여 절단편을 박리할 수 있다.In order to solve such a problem, it has been proposed to use a thermosensitive pressure-sensitive adhesive sheet containing a foaming agent in a thermosensitive pressure-sensitive adhesive layer containing a side chain crystalline polymer which crystallizes at a melting point or lower (Patent Document 1). That is, since the pressure-sensitive adhesive layer contains the side chain crystallizable polymer, the side chain crystalline polymer is in a crystalline state in the lamination step, and the ceramic green sheet can be laminated on the pressure sensitive adhesive sheet. So that the laminate of the green sheet can be fixed on the adhesive sheet. On the other hand, in the peeling step after dicing, the pressure sensitive adhesive sheet is further heated to foam the foaming agent, and the foaming agent is cooled to the melting point or lower in this state, whereby the anchoring effect of the adhesive sheet is reduced and the cut pieces can be peeled off.
그러나, 특허문헌 1에 개시된 감온성 점착 테이프는 발포제를 함유하고 있기 때문에, 다이싱 시에 피가공물의 들뜸이나, 어긋남 불량이 발생하기 쉽다. 즉, 발포제 첨가에 의해, 표면에 요철이 발생함으로써 밀착성이 저하하고, 다이싱 시에 피가공물의 들뜸이 발생한다. 또한, 발포제 첨가에 의해 23℃에서의 탄성력이 저하하고, 다이싱 시에 어긋남이 발생하고, 칩의 형상 불량, 전극의 어긋남의 불량이 발생한다. 들뜸은 다이싱 시 또는 다이싱 직후에, 목시로 확인한다. 어긋남은 칩 박리 후, 그 칩을 현미경으로 관찰하고, 형상의 변형이나 전극의 어긋남이 없는지를 목시 확인한다.However, since the thermosensitive adhesive tape disclosed in Patent Document 1 contains a foaming agent, the workpiece tends to be lifted and defective during deflection when dicing. That is, by the addition of the foaming agent, unevenness is generated on the surface, and the adhesiveness is lowered, and the workpiece is lifted during dicing. In addition, the addition of the foaming agent lowers the elasticity at 23 占 폚 and causes deviation during dicing, resulting in poor chip shape and defective electrode misalignment. The lifting is confirmed at the time of dicing or immediately after dicing. After the chips are peeled off, the chip is observed with a microscope to confirm whether there is a change in shape or an electrode shift.
또한, 측쇄 결정화 가능 폴리머를 함유한 점착제 층을 갖는 통상의 점착 테이프에 있어서는 융점 이상에서의 점착제 층이 단단하면, 점착 시의 앵커 효과가 낮게, 게다가 실온 시의 점착제 층도 단단하면 실온에서의 점착력이 부족되고, 다이싱 시에 피가공물의 들뜸이 발생하기 쉽다. 또한, 융점 이상에서도 점착제 층이 단단한 채로 점착력을 발현하므로, 박리시에 전자 부품에 데미지를 줄 우려가 있다.Further, in a conventional adhesive tape having a pressure-sensitive adhesive layer containing a side chain crystallizable polymer, if the pressure-sensitive adhesive layer is hard at a temperature higher than the melting point, the anchor effect at the time of pressure-bonding is low. Furthermore, And the workpiece is liable to be lifted at the time of dicing. In addition, since the pressure-sensitive adhesive layer hardly exhibits adhesive force even at a melting point or higher, there is a possibility that damage to the electronic component is reduced at the time of peeling.
본 발명은 실온에서의 세라믹 전자 부품의 다이싱 시에는 피가공물을 들뜸이나 어긋나지 않게 강고하게 고정할 수 있고, 박리 시에는 이박리가 가능한 다이싱용 감온성 점착 시트 및 세라믹 전자 부품의 제조 방법을 제공하는 것을 목적으로 한다.The present invention provides a method for manufacturing a ceramic pressure sensitive adhesive sheet and a ceramic electronic component for dicing a ceramic electronic component at room temperature, wherein the workpiece can be firmly fixed without lifting or staggering, .
본 발명의 세라믹 전자 부품의 다이싱용 감온성 점착 시트는 측쇄 결정성 폴리머를 함유하는 감온성 점착제 층이 기재 필름의 적어도 편면에 형성되어 있다. 상기 측쇄 결정성 폴리머는 탄소수 18개 이상의 직쇄상 알킬기를 갖는 (메타)아크릴산 에스테르 30∼70중량부와, 탄소수 2∼8개의 알킬기를 갖는 (메타)아크릴산 에스테르 30∼70중량부와, 극성 모노머 0∼10중량부를 중합시켜서 얻어지고, 분자량이 400,000∼800,000이고, 융점이 40℃ 이상이다.In the thermosensitive adhesive sheet for dicing of ceramic electronic parts of the present invention, a thermosensitive pressure-sensitive adhesive layer containing a side chain crystalline polymer is formed on at least one surface of a base film. The side chain crystalline polymer is obtained by polymerizing 30 to 70 parts by weight of a (meth) acrylic acid ester having a straight chain alkyl group having at least 18 carbon atoms, 30 to 70 parts by weight of a (meth) acrylic acid ester having an alkyl group having 2 to 8 carbon atoms, To 10 parts by weight, and has a molecular weight of 400,000 to 800,000 and a melting point of 40 占 폚 or higher.
본 발명의 세라믹 전자 부품의 제조 방법은,A method of manufacturing a ceramic electronic component of the present invention includes:
상기 감온성 점착 시트에 있어서의 감온성 점착제 층의 표면에, 측쇄 결정성 폴리머가 결정화 상태에서 복수의 세라믹 성형 시트를 적층해서 적층체를 얻는 공정과,A step of laminating a plurality of ceramic formed sheets on the surface of the thermosensitive pressure-sensitive adhesive layer in the thermosensitive pressure-sensitive adhesive sheet in the crystallized state of the side chain crystalline polymer,
측쇄 결정성 폴리머의 융점 이상에서 감온성 점착 시트를 가열하고, 감온성 점착제 층의 점착력을 발현시켜서, 상기 적층체를 상기 감온성 점착 시트에 고정한 상태에서 적층체를 다이싱하는 공정과,A step of heating the thermosensitive adhesive sheet at a temperature equal to or higher than the melting point of the side chain crystalline polymer and developing the adhesive force of the thermosensitive adhesive layer to dice the laminate while fixing the laminate to the thermosensitive adhesive sheet,
다이싱 후, 감온성 점착 시트를 더 가열하여 다이싱한 절단편을 감온성 점착제 층의 표면으로부터 박리시키는 공정을 포함한다.After the dicing, the step of further heating the thermosensitive adhesive sheet to peel the cut pieces diced from the surface of the thermosensitive pressure-sensitive adhesive layer.
본 발명의 다이싱용 감온성 점착 시트는 실온에서의 다이싱 시에는 피가공물을 들뜨거나 어긋나지 않게 강고하게 고정할 수 있고, 박리시에는 이박리가 가능하다.The dicing pressure sensitive adhesive sheet for dicing according to the present invention can firmly fix the workpiece so as not to be lifted or shifted at the time of dicing at room temperature, and can be peeled off at the time of peeling.
본 발명에 따른 세라믹 전자 부품의 제조 방법에 의하면, 높은 형상 정밀도로 다이싱 및 박리가 가능하므로, 세라믹 전자 부품의 제조 효율이 향상한다.According to the method for manufacturing a ceramic electronic component according to the present invention, dicing and peeling can be performed with high shape accuracy, and thus the manufacturing efficiency of the ceramic electronic component is improved.
이하, 세라믹 전자 부품의 제조에 적용하는 본 발명의 실시형태에 따른 다이싱용 감온성 점착 시트를 상세하게 설명한다. 이 점착 시트는 융점 이하에서 결정화하는 측쇄 결정성 폴리머를 함유하는 감온성 점착제 층을, 기재 필름의 편면 또는 양면에 형성한 것이다.Hereinafter, the thermosensitive adhesive sheet for dicing according to the embodiment of the present invention applied to the production of ceramic electronic components will be described in detail. This pressure sensitive adhesive sheet is formed on one side or both sides of a base film with a pressure sensitive adhesive layer containing a side chain crystalline polymer which crystallizes at a melting point or lower.
또한, 본 실시형태에 있어서, 세라믹 전자 부품이란 세라믹 콘덴서, 세라믹 인덕터 등과 같이, 세라믹 성형 시트(이하, 그린 시트라고도 하는 경우가 있다)의 적층체를 다이싱하는 공정을 거쳐서 제조되는 전자 부품을 말한다.In the present embodiment, the ceramic electronic component refers to an electronic component manufactured through a step of dicing a multilayer body of a ceramic formed sheet (hereinafter also referred to as a green sheet) such as a ceramic capacitor or a ceramic inductor .
상기 기재 필름으로서는 예를 들면, 폴리에틸렌, 폴리프로필렌, 폴리에스테르, 폴리아미드, 폴리이미드, 폴리카보네이트, 에틸렌아세트산비닐 공중합체, 에틸렌에틸아크릴레이트 공중합체, 에틸렌폴리프로필렌 공중합체, 폴리염화비닐 등의 합성 수지 필름의 단층체 또는 이들의 복층체로 이루어지는 두께가 5∼500㎛인 시트 등이 열거된다.Examples of the base film include polyethylene, polypropylene, polyester, polyamide, polyimide, polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene polypropylene copolymer, polyvinyl chloride A single layer of a resin film or a sheet having a thickness of 5 to 500 mu m made of a multilayer body of these layers.
기재 필름의 표면에는 점착제 층에 대한 밀착성을 향상시키기 위해서, 코로나방전 처리, 플라스마 처리, 블라스트 처리, 케미컬 에칭 처리, 프라이머 처리 등을 실시해도 좋다.The surface of the base film may be subjected to a corona discharge treatment, a plasma treatment, a blast treatment, a chemical etching treatment, a primer treatment or the like in order to improve the adhesion to the pressure-sensitive adhesive layer.
이 기재 필름의 적어도 편면에 감온성 점착제 층이 도포된다. 본 실시형태에 있어서의 감온성 점착제 층이란 온도 변화에 대응해서 유동 상태와 결정 상태를 가역적으로 일으키는 점착제 층을 말한다. 본 실시형태의 경우, 상기 감온성 점착제 층에 함유되는 측쇄 결정성 폴리머가 융점 이하에서는 결정화하고, 고탄성률이 되고, 융점을 초과하면 유동성을 나타내 점착성을 발현하도록 하는 성질을 갖는다.Sensitive adhesive layer is applied to at least one surface of the base film. Sensitive adhesive layer in the present embodiment refers to a pressure-sensitive adhesive layer that reversibly causes a fluidized state and a crystalline state in response to a temperature change. In the case of the present embodiment, the side chain crystalline polymer contained in the thermosensitive pressure-sensitive adhesive layer has a property of crystallizing at a melting point or less and exhibiting a high elastic modulus, and exhibiting fluidity and exhibiting stickiness when its melting point is exceeded.
즉, 측쇄 결정성 폴리머가 결정화 상태에서 세라믹 그린시트를 적층해서 적층체를 얻은 후, 측쇄 결정성 폴리머의 융점 이상의 온도로 해서, 측쇄 결정성 폴리머를 유동시키면, 감온성 점착제 층이 점착력을 발현하고, 적층체를 점착하는 것이 가능해진다. 또한, 상기 온도에서 측쇄 결정성 폴리머를 유동시키면, 감온성 점착제 층이 적층체의 표면에 존재하는 미세한 요철 형상에 양호하게 추종하게 된다.That is, when the side chain crystalline polymer is laminated on the ceramic green sheet in the crystallized state to obtain a laminate, when the side chain crystalline polymer is caused to flow at a temperature equal to or higher than the melting point of the side chain crystalline polymer, the thermosensitive pressure- It becomes possible to adhere the laminate. Further, when the side chain crystalline polymer flows at the above-mentioned temperature, the thermosensitive pressure-sensitive adhesive layer satisfactorily follows the fine concavo-convex shape present on the surface of the laminate.
이 상태로부터 감온성 점착제 층을 융점 미만의 온도로 냉각하면, 측쇄 결정성 폴리머가 결정화함으로써, 소위 앵커 효과가 발현되고, 그 결과, 적층체를 감온성 점착제 층의 표면에 고정하는 것이 가능해진다.When the thermosensitive pressure-sensitive adhesive layer is cooled to a temperature below the melting point from this state, the side chain crystalline polymer is crystallized, so-called anchor effect is exhibited, and as a result, the laminate can be fixed to the surface of the thermosensitive pressure-sensitive adhesive layer.
구체적으로는 상기 측쇄 결정성 폴리머는 융점이 35℃∼70℃, 바람직하게는 40∼60℃인 것이 좋다. 융점이 35℃ 이상이면, 실온 하에서 결정화하고 있으므로, 다이싱 시에 강고한 고정이 가능해진다.Concretely, the side chain crystalline polymer preferably has a melting point of 35 to 70 캜, preferably 40 to 60 캜. When the melting point is 35 占 폚 or more, since the crystallization is performed at room temperature, it is possible to firmly fix the film at the time of dicing.
감온성 점착제 층을 결정 상태 또는 유동 상태로 바꾸는 설정 온도는 그린 시트 적층체의 절단 시의 온도 등에 의해 변경할 수 있다. 예를 들면, 40℃ 미만의 온도에서는 거의 결정 상태가 되도록, 또 그 보다 높은 온도에서는 유동 상태가 되도록, 또는 50℃ 미만의 온도에서는 거의 결정 상태가 되도록, 또 그 보다 높은 온도에서는 유동 상태가 되도록 하여도 좋다. 이들 온도의 변경은 이하에 나타낸 바와 같이, 폴리머 구조, 접착제층의 처방 등을 변경함으로써 임의로 행할 수 있다.The set temperature for changing the thermosensitive pressure-sensitive adhesive layer into a crystalline state or a fluidized state can be changed by the temperature at the time of cutting the green sheet laminate. For example, in order to obtain a crystalline state at a temperature lower than 40 ° C and a flow state at a higher temperature, or to be in a crystalline state at a temperature lower than 50 ° C and at a higher temperature, . These temperature changes can be arbitrarily performed by changing the polymer structure, the prescription of the adhesive layer, and the like, as described below.
본 실시형태에 있어서, 「융점」이란, 어떤 평형 프로세스에 의해, 최초에는 질서있는 배열로 정합되어 있었던 폴리머의 특정 부분이 무질서 상태가 되는 온도를 말한다. 본 실시형태에 있어서의 융점은 시차 열주사 열량계(DSC)로, 10℃/분의 측정 조건에서 측정된다.In the present embodiment, the " melting point " refers to a temperature at which a certain portion of the polymer that has been initially aligned in an orderly arrangement becomes disordered by a certain balancing process. The melting point in the present embodiment is measured by a differential scanning calorimeter (DSC) at a measurement condition of 10 ° C / min.
측쇄 결정성 폴리머의 구체예로서는 탄소수 18개 이상, 바람직하게는 탄소수 18∼22개의 직쇄상 알킬기를 갖는 (메타)아크릴산 에스테르 30∼70중량부와, 탄소수 2∼8개의 알킬기를 갖는 (메타)아크릴산 에스테르 30∼70중량부와, 극성 모노머0∼10중량부를 중합시켜서 얻어지는 중합체인 것이 좋다.Specific examples of the side chain crystalline polymer include 30 to 70 parts by weight of a (meth) acrylic acid ester having a linear alkyl group having at least 18 carbon atoms, preferably 18 to 22 carbon atoms, and (meth) acrylic acid ester having an alkyl group having 2 to 8 carbon atoms 30 to 70 parts by weight of a polar monomer, and 0 to 10 parts by weight of a polar monomer.
또한, (메타)아크릴산 에스테르란 아크릴산 에스테르 또는 메타크릴산 에스테르를 의미한다.Further, (meth) acrylic acid ester means acrylic acid ester or methacrylic acid ester.
탄소수 18개 이상의 직쇄상 알킬기를 측쇄로 하는 (메타)아크릴산 에스테르로서는 스테아릴(메타)아크릴레이트, 에이코실(메타)아크릴레이트, 베헤닐(메타)아크릴레이트 등의 탄소수 18∼22개의 선상 알킬기를 갖는 (메타)아크릴산 에스테르가 바람직하게 사용된다.Examples of the (meth) acrylic acid ester having a straight chain alkyl group having at least 18 carbon atoms as a side chain include a linear alkyl group having from 18 to 22 carbon atoms such as stearyl (meth) acrylate, eicosyl (meth) acrylate and behenyl (Meth) acrylic acid ester having a hydroxyl group is preferably used.
탄소수 2∼8개의 알킬기를 갖는 (메타)아크릴산 에스테르로서는 예를 들면, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 헥실(메타)아크릴레이트가 열거된다.Examples of the (meth) acrylic acid ester having an alkyl group having 2 to 8 carbon atoms include ethyl (meth) acrylate, butyl (meth) acrylate and hexyl (meth) acrylate.
극성 모노머로서는 예를 들면, 아크릴산, 메타크릴산, 크로톤산, 이타콘산, 말레산, 푸말산 등의 카르복실기 함유 에틸렌 불포화 단량체; 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시헥실(메타)아크릴레이트 등의 히드록실기를 갖는 에틸렌 불포화 단량체 등이 사용된다.Examples of the polar monomer include a carboxyl group-containing ethylenically unsaturated monomer such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; An ethylenically unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 2-hydroxyhexyl (meth) acrylate is used.
상기 중합체의 중량 평균 분자량은 40만∼80만인 것이 좋다. 중합체의 중량 평균 분자량이 40만 미만이면, 응집력 부족에 의해 적층체의 절단 공정에 있어서 컷 정밀도가 악화할 우려가 있다. 또한, 중합체의 중량 평균 분자량이 80만을 초과하면, 용액 점도가 높게 되어 도포가 곤란해질 우려가 있다. 또한, 상기 중량 평균 분자량은 상기 중합체를 겔퍼미에이션크로마토그래피(GPC)로 측정하고, 얻어진 측정값을 폴리스티렌 환산한 값이다.The weight average molecular weight of the polymer is preferably from 400,000 to 800,000. If the weight average molecular weight of the polymer is less than 400,000, there is a fear that the cut precision in the step of cutting the laminate is deteriorated due to the lack of cohesive force. On the other hand, if the weight average molecular weight of the polymer exceeds 80,000, the viscosity of the solution becomes high and the coating may become difficult. In addition, the weight average molecular weight is a value obtained by measuring the polymer by gel permeation chromatography (GPC) and converting the measured value into polystyrene.
또한, 상기 감온성 점착제 층의 응집력을 높이기 위해서, 가교제를 첨가해도 좋다. 가교제로서는 이소시아네이트계 화합물, 아지리딘계 화합물, 에폭시계 화합물, 금속 킬레이트계 화합물 등이 열거된다. 또한, 감온성 점착제 층에는 필요에 따라서, 가소제, 점착 부여제(tackifier), 필러 등과 같은 임의의 성분을 첨가할 수 있다. 점착 부여제로서는 특수 로진 에스테르계, 테르펜 페놀계, 석유 수지계, 고수산기가 로진 에스테르계, 수소 첨가 로진 에스테르계 등이 열거된다.Further, in order to increase the cohesive force of the thermosensitive pressure-sensitive adhesive layer, a cross-linking agent may be added. Examples of the crosslinking agent include an isocyanate compound, an aziridine compound, an epoxy compound, and a metal chelate compound. Further, optional components such as a plasticizer, a tackifier, a filler and the like may be added to the thermosensitive pressure-sensitive adhesive layer, if necessary. Examples of the tackifier include special rosin ester-based, terpene-phenol-based, petroleum resin-based, and high-acid anhydride-based rosin ester-based and hydrogenated rosin ester-based ones.
또한, 융점 이하의 결정 상태에서, 적층체의 최하층이 보다 양호하게 밀착하기 위해서 아크릴계, 고무계의 일반적인 감압성 점착제를 소량 첨가해도 좋다.Further, a small amount of a general acrylic pressure-sensitive adhesive of the rubber type may be added in order to bring the lowest layer of the laminate into close contact with a crystalline state at a melting point or lower.
감온성 점착제 층을 기재 필름에 형성하기 위해서는 일반적으로는 나이프 코터, 롤 코터, 칼렌다 코터, 콤마 코터 등이 많이 사용된다. 또한, 도포 두께나 재료의 점도에 따라서는 그라비어 코터, 로드 코터에 의해 행할 수 있다. 감온성 점착제 층의 두께는 1∼100㎛, 바람직하게는 5∼50㎛인 것이 좋다.In general, a knife coater, a roll coater, a calender coater, a comma coater, or the like is widely used for forming the thermosensitive pressure-sensitive adhesive layer on the base film. Further, depending on the coating thickness and the viscosity of the material, it can be performed by a gravure coater or a rod coater. The thickness of the thermosensitive pressure-sensitive adhesive layer is preferably 1 to 100 m, and more preferably 5 to 50 m.
감온성 점착제 층은 측쇄 결정성 폴리머의 융점 이하인 23℃에 있어서의 저장 탄성률이 1×106∼1×109Pa인 것이 바람직하다. 탄성률이 1×106Pa 미만인 경우에는 응집력이 열악하기 때문에, 그린 시트 적층체의 다이싱 시에 어긋남이 생기고, 형상 불량, 전극의 어긋남 등이 발생하기 쉬워진다. 한편, 탄성률이 1×109Pa를 초과하는 것은 본 실시형태에서는 있을 수 없다.The thermosensitive pressure-sensitive adhesive layer preferably has a storage elastic modulus at 23 占 폚 of not higher than the melting point of the side chain crystalline polymer of 1 占06 to 1 占09 Pa. When the modulus of elasticity is less than 1 x 10 < 6 > Pa, the cohesive force is poor, so that deviation occurs in dicing the green sheet laminate, and defective shape and electrode displacement are likely to occur. On the other hand, the elastic modulus exceeding 1 x 10 9 Pa can not be present in the present embodiment.
또한, 감온성 점착제 층은 JIS Z0237에 준거해서 측정한 폴리에틸렌테레프탈레이트(PET)에 대한 점착 강도를 측정했을 때, 측쇄 결정성 폴리머의 융점 이하인 23℃에서의 점착 강도가 0.6N/25mm 이상이고, 측쇄 결정성 폴리머의 융점을 초과하는 온도에서, 동일하게 하여 측정한 점착 강도가 0.4N/25mm 이하이다.The pressure sensitive adhesive layer preferably has a pressure-sensitive adhesive strength of not less than 0.6 N / 25 mm at 23 ° C which is not higher than the melting point of the side chain crystalline polymer when the pressure-sensitive adhesive strength to polyethylene terephthalate (PET) measured according to JIS Z0237 is measured, The adhesive strength measured in the same manner at a temperature exceeding the melting point of the crystalline polymer is 0.4 N / 25 mm or less.
23℃에서의 점착 강도가 0.6N/25mm 이상이면, 적층체의 다이싱 시에 있어서 강한 고정력에 의해 적층체의 들뜸이나 어긋남이 발생하는 것을 방지할 수 있다. 한편, 측쇄 결정성 폴리머의 융점을 초과하는 온도에서 점착 강도가 0.4N/25mm 이하이면, 이박리가 가능해지고, 전자 부품에 데미지를 주는 것을 억제할 수 있다.When the adhesive strength at 23 캜 is 0.6 N / 25 mm or more, it is possible to prevent the laminate from lifting or shifting due to a strong clamping force during dicing of the laminate. On the other hand, if the adhesive strength is 0.4 N / 25 mm or less at a temperature exceeding the melting point of the side chain crystalline polymer, the peeling becomes possible and the damage to the electronic component can be suppressed.
다음에 본 실시형태의 점착 시트를 이용하여 적층 세라믹 콘덴서를 제조하는 방법을 설명한다.Next, a method of manufacturing a multilayer ceramic capacitor using the pressure-sensitive adhesive sheet of the present embodiment will be described.
우선, 세라믹 분말의 슬러리를 닥터 블레이드로 얇게 펼쳐서 세라믹의 그린 시트를 형성하고, 상기 그린 시트의 표면에 전극을 인쇄한다. 다음에 대좌 상에 본 실시형태의 감온성 점착 시트를 통해서 복수의 그린 시트를 적층해서 그린 시트의 적층체를 형성한다. 이 때, 점착 시트의 온도는 상기 측쇄 결정성 폴리머가 융점 이하의 결정화 상태인 것이 좋다.First, a ceramic green sheet is formed by spreading a slurry of ceramic powder thinly with a doctor blade, and an electrode is printed on the surface of the green sheet. Next, a plurality of green sheets are laminated on the pedestal through the thermosensitive adhesive sheet of the present embodiment to form a green sheet laminate. At this time, it is preferable that the temperature of the pressure-sensitive adhesive sheet is in a crystallized state in which the side chain crystalline polymer has a melting point or lower.
다음에 감온성 점착 시트를 융점 이상에서 가열해서 그린 시트의 적층체를 대좌 상에 접착 고정한다. 가열은 예를 들면, 적층체에 열원(히터판)을 밀착시켜서 가열하거나, 또는 대좌마다 열분위기 중에 위치시키는 등해서 행한다. 가열 온도는 융점 이상의 비교적 높은 온도(예를 들면 50∼80℃)인 것이 좋고, 이것에 의해 측쇄 결정성 폴리머의 유동성이 높게 되고, 피가공물의 요철에 들어가고, 적층체는 감온성 점착 시트의 감온성 점착제 층에 양호하게 점착한다.Next, the thermosensitive adhesive sheet is heated at a temperature higher than the melting point to adhere and fix the laminate of the green sheet on the pedestal. The heating is carried out, for example, by heating the laminate with a heat source (heater plate) in close contact with the laminate, or by placing the laminate in a heat atmosphere for each pedestal. The heating temperature is preferably a relatively high temperature (for example, 50 to 80 占 폚) higher than the melting point, whereby the fluidity of the side chain crystalline polymer becomes high and enters the unevenness of the workpiece, It adheres well to the layer.
그 후, 융점 이하에서 냉각함으로써 측쇄 결정성 폴리머가 결정화하고, 감온성 점착제 층의 경도(저장 탄성률)가 크게 상승하고, 강고하게 고정한다. 고정 후, 적층체를 열압착하고, 다이싱 쏘(절단날)로 다이싱(절단)한다. 다이싱 시에, 생 시트가 다이싱 쏘에 밀려서 횡방향으로 이동하는 것을, 감온성 점착 시트에 의해 억제할 수 있다. 이렇게 하여 복수의 절단편(칩)을 형성한다.Thereafter, the side chain crystalline polymer is crystallized by cooling at a temperature not higher than the melting point, and the hardness (storage elastic modulus) of the thermosensitive pressure-sensitive adhesive layer is largely increased and firmly fixed. After fixing, the laminate is hot-pressed and diced (cut) with a dicing saw (cutting blade). At the time of dicing, it is possible to suppress the movement of the raw sheet in the lateral direction by being pushed by the dicing saw by the heat-sensitive adhesive sheet. Thus, a plurality of cut pieces (chips) are formed.
이 때, 본 실시형태에서는 상기한 특허문헌 1에 기재된 발포제를 함유하지 않고 있으므로, 융점 이하의 온도(실온 등)에서의 경도 부족에 의한 다이싱 시의 어긋남을 해소할 수 있다. 즉, 본 실시형태에 있어서의 감온성 점착제 층은 발포제를 함유하지 않음으로써, 융점 이하의 온도에서의 점착력 및 경도가 향상하고, 다이싱 시의 적층체의 들뜸이나, 어긋남을 억제할 수 있다. 즉, 발포제는 결정화한 측쇄 결정성 폴리머보다 탄성률이 낮기 때문에, 융점 이하의 온도에서의 경도가 저하하고, 또한 표면에 발포제에 의한 요철이 발생하는 것에 의해, 밀착성을 손상시키고, 융점 이하의 온도에서의 점착 강도가 충분 발현할 수 없게 된다.At this time, since the present embodiment does not contain the foaming agent described in Patent Document 1, deviation in dicing due to insufficient hardness at a temperature equal to or lower than the melting point (room temperature, etc.) can be eliminated. That is, since the thermosensitive pressure-sensitive adhesive layer in the present embodiment does not contain a foaming agent, the adhesive strength and hardness at a temperature lower than the melting point are improved, and lifting and shifting of the laminate at the time of dicing can be suppressed. That is, since the foaming agent has a lower elastic modulus than that of the crystallized side chain crystalline polymer, the hardness at a temperature lower than the melting point is lowered, and unevenness due to the foaming agent is generated on the surface, It is impossible to sufficiently exhibit the adhesive strength.
다음에, 감온성 점착 시트를 다시 융점 이상으로 가열함으로써 점착제가 크게 연화되고, 이박리가 된다. 이 때, 본 실시형태에 있어서의 감온성 점착제 층은 발포제를 함유하지 않고 있어도, 융점 이상의 탄성률의 저하가 큰 것보다, 데미지없이 박리할 수 있는 정도까지 점착 강도가 저하한다. 이렇게 하여 점착 시트의 감온성 점착제 층을 비점착성으로 한다. 이 상태에서 절단편을 점착 시트로부터 인출하고, 그 후, 절단편을 가소성 공정을 거쳐서 본 소성 공정으로 보내서 소성하고, 끝면에 외부 전극을 형성해서 칩형의 세라믹 전자 부품이 얻어진다. 점착 시트를 냉각할 때에는 예를 들면, 자연 방냉으로 박리 가능하다.Next, the pressure sensitive adhesive sheet is softened again by heating the pressure sensitive adhesive sheet again to a temperature higher than the melting point, and this peeling is carried out. At this time, the pressure-sensitive adhesive layer in the present embodiment does not contain a foaming agent, but its adhesive strength is lowered to such an extent that it can be peeled off without damage, as compared with a case where the lowering of the modulus of elasticity is higher than the melting point. Thus, the thermosensitive pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is made non-sticky. In this state, the cut pieces are taken out from the pressure-sensitive adhesive sheet, and then the cut pieces are subjected to the firing process through the firing process and fired, and external electrodes are formed on the end faces to obtain chip-type ceramic electronic parts. When the pressure-sensitive adhesive sheet is cooled, it can be peeled off by, for example, natural cooling.
또한, 상기에서는 기재 필름의 편면에 감온성 점착제 층을 형성해서 점착 시트를 구성했지만, 기재 필름의 타방의 면에도 점착제 층을 형성해서 양면 점착 시트로서 사용해도 좋다. 이 경우, 기재 필름의 타방의 면에 적층되는 제 2 점착제 층으로서는 (1) 시판의 감압 접착제 층, (2) 시판의 감압 접착제와 본 실시형태에서 사용하는 측쇄 결정성 폴리머 및 발포제의 혼합물로 이루어지는 점착제 층, 또는 (3) 본 실시형태에서 사용하는 감온성 점착제 층 등을 사용할 수 있다.In the above, the pressure sensitive adhesive layer is formed on one side of the base film to form the pressure sensitive adhesive sheet. However, the pressure sensitive adhesive layer may be formed on the other side of the base film to be used as the pressure sensitive adhesive double coated sheet. In this case, the second pressure-sensitive adhesive layer to be laminated on the other surface of the base film includes (1) a commercially available pressure-sensitive adhesive layer, (2) a mixture of a commercially available pressure-sensitive adhesive and the side chain crystalline polymer used in the present embodiment and a foaming agent A pressure sensitive adhesive layer, or (3) a pressure sensitive adhesive layer used in the present embodiment.
감압 접착제로서는 예를 들면, 천연 고무 접착제; 합성 고무 접착제; 스티렌/부타디엔 라텍스 베이스 접착제; 블록 공중합체형의 열가소성 고무; 부틸 고무; 폴리이소부틸렌; 아크릴 접착제; 비닐에테르의 공중합체 등이 열거된다.As the pressure-sensitive adhesive, for example, a natural rubber adhesive; Synthetic rubber adhesive; Styrene / butadiene latex base adhesive; Block copolymer type thermoplastic rubber; Butyl rubber; Polyisobutylene; Acrylic adhesive; Vinyl ether copolymers, and the like.
상기에서는 세라믹 전자 부품으로서 적층 세라믹 콘덴서의 제조에 관하여 설명했지만, 본 발명은 이것에 한정되는 것은 아니고, 세라믹 콘덴서, 세라믹 인덕터, 저항기, 페라이트, 센서 소자, 서미스터, 배리스터, 압전 세라믹 등의 세라믹 전자 부품의 제조에도 동일하게 하여 적용 가능하다.The present invention is not limited to this. The ceramic electronic component such as a ceramic capacitor, a ceramic inductor, a resistor, a ferrite, a sensor element, a thermistor, a varistor, and a piezoelectric ceramics may be used as the ceramic electronic component. The present invention can be applied to the manufacturing of the same.
이하, 실시예 및 비교예를 들어서 본 발명의 감온성 점착 시트를 상세하게 설명하지만, 본 발명은 이하의 실시예만으로 한정되는 것은 아니다. 또한, 이하의 설명에서 「부」는 중량부를 의미한다.Hereinafter, the thermosensitive adhesive sheet of the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, " parts " means parts by weight.
하기의 실시예 및 비교예에서 사용한 공중합체는 이하의 합성예 1∼3에서 얻은 3종류이다.The copolymers used in the following Examples and Comparative Examples are of the three kinds obtained in the following Synthesis Examples 1 to 3.
(합성예 1)(Synthesis Example 1)
베헤닐아크릴레이트(NOF Corporation 제품)을 45부, 아크릴산 부틸(NIPPON SHOKUBAI CO., LTD. 제품)을 50부, 아크릴산을 5부 및 퍼부틸 ND(NOF Corporation 제품)를 0.5부의 비율로 아세트산 에틸 230부에 혼합하고, 55℃에서 4시간 교반 후, 80℃로 승온하고, 이어서, 퍼헥실 PV(NOF Corporation 제품)를 0.5부 첨가하고, 2시간 교반하고, 이들의 모노머를 중합시켰다. 얻어진 공중합체의 중량 평균 분자량은 65만, 융점은 43℃이었다.45 parts of behenyl acrylate (NOF Corporation), 50 parts of butyl acrylate (manufactured by NIPPON SHOKUBAI CO., LTD.), 5 parts of acrylic acid and 0.5 parts of perbutyl ND (NOF Corporation) The mixture was stirred at 55 占 폚 for 4 hours and then heated to 80 占 폚. Then, 0.5 part of perhexyl PV (manufactured by NOF Corporation) was added and stirred for 2 hours to polymerize these monomers. The obtained copolymer had a weight average molecular weight of 650,000 and a melting point of 43 占 폚.
(합성예 2)(Synthesis Example 2)
베헤닐아크릴레이트(NOF Corporation 제품)를 45부, 아크릴산 부틸(NIPPON SHOKUBAI CO., LTD. 제품)을 50부, 아크릴산 2-에틸헥실(2HEA, NIPPON SHOKUBAI CO., LTD. 제품)을 5부 및 퍼부틸 ND(NOF Corporation 제품)을 0.5부의 비율로 아세트산 에틸 230부에 혼합하고, 55℃에서 4시간 교반 후, 80℃로 승온하고, 이어서, 퍼헥실 PV(NOF Corporation 제품)을 0.5부 첨가하고, 2시간 교반하고, 이들의 모노머를 중합시켰다. 얻어진 공중합체의 중량 평균 분자량은 65만, 융점은 42℃이었다.45 parts of behenyl acrylate (NOF Corporation), 50 parts of butyl acrylate (manufactured by NIPPON SHOKUBAI CO., LTD.), 5 parts of 2-ethylhexyl acrylate (2HEA, manufactured by NIPPON SHOKUBAI CO., LTD. And 0.5 parts of perbutyl ND (manufactured by NOF Corporation) were added to 230 parts of ethyl acetate. The mixture was stirred at 55 캜 for 4 hours and then heated to 80 캜. Then, 0.5 part of perhexyl PV (NOF Corporation) And stirred for 2 hours to polymerize these monomers. The obtained copolymer had a weight average molecular weight of 650,000 and a melting point of 42 占 폚.
(합성예 3)(Synthesis Example 3)
베헤닐아크릴레이트(NOF Corporation 제품)를 45부, 아크릴산 메틸(NIPPON SHOKUBAI CO., LTD. 제품)을 50부, 아크릴산을 5부 및 퍼부틸 ND(NOF Corporation 제품)를 0.5부의 비율로 아세트산 에틸 230부에 혼합하고, 55℃에서 4시간 교반 후, 80℃로 승온하고, 이어서, 퍼헥실 PV(NOF Corporation 제품)을 0.5부 첨가하고, 2시간 교반하고, 이들의 모노머를 중합시켰다. 얻어진 공중합체의 중량 평균 분자량은 65만, 융점은 54℃이었다.45 parts of behenyl acrylate (NOF Corporation), 50 parts of methyl acrylate (manufactured by NIPPON SHOKUBAI CO., LTD.), 5 parts of acrylic acid and 0.5 parts of perbutyl ND (manufactured by NOF Corporation) The mixture was stirred at 55 占 폚 for 4 hours and then heated to 80 占 폚. Then, 0.5 part of perhexyl PV (manufactured by NOF Corporation) was added and stirred for 2 hours to polymerize these monomers. The obtained copolymer had a weight average molecular weight of 650,000 and a melting point of 54 占 폚.
합성예 1∼4의 공중합체를 표 1에 나타낸다.The copolymers of Synthesis Examples 1 to 4 are shown in Table 1.
(실시예 1)(Example 1)
합성예 1에서 얻어진 공중합체를 아세트산 에틸을 이용하여 고형분이 30%가 되도록 공중합체 용액을 조제했다. 이어서, 이 공중합체 용액에, 가교제로서 아지리딘 화합물(NIPPON SHOKUBAI CO., LTD.제작의 PZ-33)을 상기 공중합체 100부에 대하여 0.7부 첨가해서 감온성 점착제 조성물을 얻었다. 이 감온성 점착제 조성물을 기재 필름(두께 100㎛의 PET필름)의 편면에 도포, 건조시켜서 두께 40㎛의 감온성 점착제 층을 형성했다.The copolymer obtained in Synthesis Example 1 was treated with ethyl acetate to prepare a copolymer solution having a solid content of 30%. Next, 0.7 part of an aziridine compound (PZ-33 manufactured by NIPPON SHOKUBAI CO., LTD.) As a crosslinking agent to 100 parts of the copolymer was added to the copolymer solution to obtain a thermosensitive pressure-sensitive adhesive composition. The thermosensitive pressure-sensitive adhesive composition was applied to one side of a base film (PET film having a thickness of 100 mu m) and dried to form a thermosensitive pressure-sensitive adhesive layer having a thickness of 40 mu m.
(실시예 2)(Example 2)
합성예 1에서 얻어진 공중합체 대신에, 합성예 2에서 얻어진 공중합체를 사용하고, 가교제로서 아지리딘 화합물 대신에 이소시아네이트계 화합물(Nippon Polyurethane Industry Co.,Ltd.제작의 L45)을 상기 공중합체 100부에 대하여 2.5부 첨가한 것 이외는 실시예 1과 동일하게 하여 기재 필름의 편면에 두께 40㎛의 감온성 점착제 층을 형성했다.The copolymer obtained in Synthesis Example 2 was used in place of the copolymer obtained in Synthesis Example 1, and an isocyanate compound (L45 manufactured by Nippon Polyurethane Industry Co., Ltd.) was used in place of the aziridine compound as a crosslinking agent in 100 parts of the copolymer Sensitive adhesive layer having a thickness of 40 占 퐉 was formed on one side of the base film in the same manner as in Example 1,
[비교예 1][Comparative Example 1]
시판의 발포 테이프(점착제 층의 두께:45㎛)를 사용했다. 이 발포 테이프의 점착제 층은 두께 100㎛의 기재 필름(PET 필름)의 표면에 두께 45㎛의 점착제 층을 형성한 것이다.A commercially available foam tape (pressure-sensitive adhesive layer thickness: 45 m) was used. The pressure-sensitive adhesive layer of the foam tape was obtained by forming a pressure-sensitive adhesive layer having a thickness of 45 占 퐉 on the surface of a base film (PET film) having a thickness of 100 占 퐉.
[비교예 2][Comparative Example 2]
상기 합성예 1에서 얻어진 공중합체를, 아세트산 에틸을 이용하여 고형분이 30%가 되도록 공중합체 용액을 조제하고, 이 공중합체 용액에 가교제로서 아지리딘 화합물(NIPPON SHOKUBAI CO., LTD.제작의 PZ-33)을 상기 공중합체 100부에 대하여 0.5부 첨가하고, 또한 발포제로서 열팽창성 마이크로스피어(EXPANCEL사 제작의 「551DU40」, 발포 온도: 130℃, 평균 입경: 13㎛)를 고형분 총량에 대하여 40중량%가 되도록 첨가해서 감온성 점착제 조성물을 얻었다. 그 밖에는 실시예 1과 동일하게 하여, 기재 필름의 편면에 두께 40㎛의 감온성 점착제 층을 형성했다.The copolymer obtained in Synthesis Example 1 was treated with ethyl acetate to prepare a copolymer solution having a solid content of 30% and an aziridine compound (PZ- 33) was added in an amount of 0.5 part based on 100 parts of the copolymer, and thermally expandable microspheres ("551DU40" manufactured by EXPANCEL Co., Ltd., foaming temperature: 130 ° C., average particle size: 13 μm) % To obtain a thermosensitive pressure-sensitive adhesive composition. A pressure-sensitive adhesive layer having a thickness of 40 占 퐉 was formed on one side of the base film in the same manner as in Example 1 except for this.
[비교예 3][Comparative Example 3]
합성예 1에서 얻어진 공중합체 대신에, 상기 합성예 3에서 얻어진 공중합체를 사용하고, 가교제량을 0.5중량%가 되도록 첨가한 것 이외는 실시예 1과 동일하게 하여, 기재 필름의 편면에 두께 40㎛의 감온성 점착제 층을 형성했다.The same procedure as in Example 1 was carried out except that the copolymer obtained in Synthesis Example 3 was used instead of the copolymer obtained in Synthesis Example 1 and the amount of the crosslinking agent was added in an amount of 0.5 wt% Sensitive adhesive layer was formed.
실시예 및 비교예에서 얻어진 각 감온성 점착 시트를 이하의 평가 방법으로 평가했다.Sensitive adhesive sheets obtained in Examples and Comparative Examples were evaluated by the following evaluation methods.
(i) 점착 강도(i) Adhesive strength
감온성 점착 시트를 23℃ 및 60℃에서 가열했을 때의 PET 필름에 대한 점착 강도를 JIS Z0237에 준해서 측정했다. 즉, 우선, 60℃의 분위기 온도에 있어서, 감온성 점착 시트를 세퍼레이터를 상면으로 해서, 스테인레스 강판에 시판 양면 테이프을 통하여 고정했다. 다음에 세퍼레이터를 제거하고, 노출된 감온성 점착제 층의 표면에 두께 25㎛의 PET 필름을 점착했다. 그리고, 로드셀을 이용하여 300mm/분의 속도로 PET필름을 180°박리하고, 60℃에 있어서의 180°박리 강도를 평가했다. 다음에 23℃의 분위기 온도로 냉각하고, 동일하게 하여 180°박리하고, 23℃에 있어서의 180°박리 강도를 평가했다.The pressure-sensitive adhesive sheet was heated at 23 占 폚 and 60 占 폚 and the adhesive strength to the PET film was measured according to JIS Z0237. That is, first, the thermosensitive pressure-sensitive adhesive sheet was fixed to the stainless steel plate through a commercially available double-faced tape with the separator as the upper surface at an ambient temperature of 60 占 폚. Next, the separator was removed, and a PET film having a thickness of 25 mu m was adhered to the surface of the exposed thermosensitive adhesive layer. Then, the PET film was peeled at 180 ° at a rate of 300 mm / min using a load cell, and the 180 ° peel strength at 60 ° C was evaluated. Subsequently, the resultant was cooled to an atmospheric temperature of 23 캜, 180 ° peeled in the same manner, and 180 ° peel strength at 23 캜 was evaluated.
(ii) 저장 탄성률(ii) Storage modulus
23℃ 및 60℃에 있어서의 저장 탄성률(G')을 각각 이하와 같이 해서 측정했다.The storage elastic modulus (G ') at 23 占 폚 and 60 占 폚 were measured as follows.
장치명: Thermo SCIENTIFIC HAAKE MARS Ⅲ, 하중: 1.00N, 주파수: 1.00Hz, 가열 속도: 5℃/min, 온도 프로세스: 0℃→150℃, 측정 두께: 800μmDevice: Thermo SCIENTIFIC HAAKE MARS Ⅲ, Load: 1.00N, Frequency: 1.00Hz, Heating rate: 5 ℃ / min, Temperature Process: 0 ℃ → 150 ℃, Measurement thickness: 800μm
(iii) 다이싱 들뜸(iii) dicing
세라믹 칩 콘덴서 제조 공정에 있어서, 그린 시트의 적층체를 다이싱 후에, 감온성 점착제 층의 표면에 점착된 그린 시트의 적층체에 들뜸이 없는지를 목시로 확인했다. 그 결과, 적층체에 들뜸이 없었던 것을 ○, 일부 들뜸이 발생한 것을 △, 전면에 들뜸이 발생한 것을 ×로 했다.In the process of manufacturing a ceramic chip capacitor, it was confirmed in the past that whether or not the stack of green sheets adhered to the surface of the thermosensitive pressure-sensitive adhesive layer was peeled off after dicing the green sheet laminate. As a result, it was found that no lamination occurred in the laminate, & cir &
(iv) 다이싱 어긋남(iv) Dicing Offset
세라믹 칩 콘덴서 제조 공정에 있어서, 적층체를 다이싱 후, 가온해서 칩을 박리하고, 그 칩을 현미경으로 관찰하고, 형상의 변형이나 전극의 어긋남이 없는지를 목시 확인했다. 그 결과, 형상의 변형, 전극의 어긋남이 없는 것을 ○, 형상의 변형, 전극의 어긋남이 있는 것을 ×로 했다.In the process of manufacturing a ceramic chip capacitor, after dicing the laminate, the chip was peeled off by heating, and the chip was observed with a microscope to confirm whether the shape was deformed or the electrode was misaligned. As a result, it was found that the shape was not deformed, the electrode was not displaced, the shape was deformed, and the electrode was misaligned.
(v) 박리성(v) peelability
세라믹 칩 콘덴서 제조에 있어서의 박리 공정에 있어서, 모두 박리된 것을 ○, 일부 박리되지 않은 것을 △, 전혀 박리되는 않은 것을 ×로 했다. 또한, 다이싱한 칩의 박리는 실시예 1, 2, 비교예 3에서는 감온성 점착제 층을 60℃에서 가열하여 행했지만, 비교예 1, 2에서는 발포제를 발포시키기 위해서, 130℃까지 더 가열하여 행했다.In the peeling step in the production of the ceramic chip capacitor, all of the peeled portions were marked with?, Those with some peeled portions were marked with?, And those with no peeled portions were marked with?. Further, in the peeling of the diced chip, the thermosensitive adhesive layer was heated at 60 DEG C in Examples 1 and 2 and Comparative Example 3, but in Comparative Examples 1 and 2, the foaming was further heated to 130 DEG C .
이들의 시험 결과를 표 2에 나타낸다.The results of these tests are shown in Table 2.
Peelability
표 2로부터, 이하의 점이 확인된다.From Table 2, the following points are confirmed.
비교예 1은 융점 이하(23℃)에서의 저장 탄성률이 부족하기 때문에, 다이싱 시에 어긋남의 문제가 있다. In Comparative Example 1, since the storage modulus at a temperature lower than the melting point (23 DEG C) is insufficient, there is a problem of deviation in dicing.
비교예 2는 융점 이하(23℃)에서의 점착 강도 및 저장 탄성률이 부족하기 때문에, 다이싱 시의 들뜸, 어긋남의 문제가 있다(23℃ 접착력, 탄성률 부족).In Comparative Example 2, since the adhesive strength and the storage elastic modulus at the melting point (23 캜) were insufficient, there was a problem of lifting and shifting at the time of dicing (23 캜 adhesive strength, insufficient elasticity).
비교예 3은 융점 이하(23℃)에서의 점착 강도가 부족하기 때문에, 다이싱 시의 들뜸의 문제가 있고, 또한 박리성에도 문제가 있다.In Comparative Example 3, since the adhesive strength at the lower melting point (23 캜) was insufficient, there was a problem of lifting at the time of dicing, and there was also a problem in peelability.
이에 대하여 실시예 1, 2의 감온성 점착 시트는 다이싱 들뜸이나, 어긋남이 없고, 박리성도 양호했다.On the other hand, the thermosensitive adhesive sheets of Examples 1 and 2 had no dicing entanglement, no deviation, and good peelability.
Claims (5)
상기 감온성 점착제 층의 두께가 1∼100㎛인 감온성 점착 시트.The method according to claim 1,
Sensitive adhesive layer has a thickness of 1 to 100 m.
상기 감온성 점착제 층은 23℃에 있어서의 저장 탄성률이 1×106∼1×109Pa인 감온성 점착 시트.3. The method according to claim 1 or 2,
Sensitive adhesive layer has a storage elastic modulus at 23 캜 of 1 x 10 6 to 1 x 10 9 Pa.
상기 감온성 점착제 층은 JIS Z0237에 준거해서 측정한 폴리에틸렌테레프탈레이트에 대한 23℃에서의 점착 강도가 0.6N/25mm 이상이고, 상기 측쇄 결정성 폴리머의 융점을 초과하는 온도에서의 점착 강도가 0.4N/25mm 이하인 감온성 점착 시트.3. The method according to claim 1 or 2,
Sensitive adhesive layer has an adhesive strength of not less than 0.6 N / 25 mm to polyethylene terephthalate measured at 23 DEG C in accordance with JIS Z0237 and an adhesive strength at a temperature exceeding the melting point of the side chain crystalline polymer of 0.4 N / Sensitive adhesive sheet having a thickness of 25 mm or less.
상기 측쇄 결정성 폴리머의 융점 이상의 온도로 상기 감온성 점착 시트를 가열하고, 상기 감온성 점착제 층의 점착력을 발현시키고, 이어서 융점 이하의 온도로 냉각하고, 상기 적층체를 상기 감온성 점착 시트에 고정한 상태에서 상기 적층체를 다이싱하는 공정과,
다이싱 후, 상기 감온성 점착 시트를 다시 융점 이상의 온도로 가열하고, 다이싱한 절단편을 상기 감온성 점착제 층의 표면으로부터 박리시키는 공정을 포함하는 것을 특징으로 하는 세라믹 전자 부품의 제조 방법.A process for producing a pressure sensitive adhesive sheet, comprising the steps of: laminating a plurality of ceramic formed sheets on a surface of a thermosensitive pressure-sensitive adhesive layer of the thermosensitive pressure-sensitive adhesive sheet according to claim 1 or 2,
Sensitive adhesive sheet is heated to a temperature equal to or higher than the melting point of the side chain crystalline polymer to thereby develop the adhesive force of the thermosensitive pressure-sensitive adhesive layer and then cooled to a temperature not higher than the melting point, A step of dicing the laminate,
Heating the thermosensitive adhesive sheet to a temperature higher than the melting point after dicing, and peeling the diced cutting piece from the surface of the thermosensitive pressure-sensitive adhesive layer.
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