WO2023113560A1 - 전기강판 접착 코팅 조성물, 전기강판 적층체 및 이의 제조 방법 - Google Patents
전기강판 접착 코팅 조성물, 전기강판 적층체 및 이의 제조 방법 Download PDFInfo
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- WO2023113560A1 WO2023113560A1 PCT/KR2022/020643 KR2022020643W WO2023113560A1 WO 2023113560 A1 WO2023113560 A1 WO 2023113560A1 KR 2022020643 W KR2022020643 W KR 2022020643W WO 2023113560 A1 WO2023113560 A1 WO 2023113560A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- unsubstituted
- substituted
- weight
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- electrical steel
- Prior art date
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- 229910000976 Electrical steel Inorganic materials 0.000 title claims abstract description 97
- 239000000853 adhesive Substances 0.000 title claims abstract description 79
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 79
- 239000008199 coating composition Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 47
- 239000003822 epoxy resin Substances 0.000 claims abstract description 32
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 20
- 150000003077 polyols Chemical class 0.000 claims abstract description 20
- 239000010410 layer Substances 0.000 claims description 44
- 230000004927 fusion Effects 0.000 claims description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 29
- 239000012948 isocyanate Substances 0.000 claims description 24
- 150000002513 isocyanates Chemical class 0.000 claims description 23
- 239000011247 coating layer Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000007822 coupling agent Substances 0.000 claims description 13
- 239000000080 wetting agent Substances 0.000 claims description 12
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 10
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 10
- 125000004419 alkynylene group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-VVKOMZTBSA-N Dideuterium Chemical compound [2H][2H] UFHFLCQGNIYNRP-VVKOMZTBSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 19
- 229920001451 polypropylene glycol Polymers 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 238000007789 sealing Methods 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- -1 methacryloxy Chemical group 0.000 description 8
- 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 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 238000013016 damping Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000004080 punching Methods 0.000 description 5
- 229910000565 Non-oriented electrical steel Inorganic materials 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 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
- 239000003906 humectant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Definitions
- An embodiment of the present invention relates to an adhesive coating composition for electrical steel sheet, an electrical steel sheet laminate, and a manufacturing method thereof.
- one embodiment of the present invention is an electrical steel sheet adhesive coating composition formed with a fusion layer capable of bonding (joining) electrical steel sheets without using conventional fastening methods such as welding, clamping, and interlocking, and electrical steel sheet lamination. It relates to a sieve and a method for producing the same.
- an embodiment of the present invention is an electrical steel sheet adhesive coating composition, an electrical steel sheet laminate, and a method for manufacturing the same, which improve the adhesive strength and noise suppression properties of an electrical steel sheet laminate by controlling components of a fusion layer formed between electrical steel sheets. It is about.
- Non-oriented electrical steel sheet is a steel sheet with uniform magnetic properties in all directions on a rolled sheet and is widely used in motors, generator iron cores, electric motors, and small transformers.
- stress relief annealing For electrical steel sheets, stress relief annealing (SRA) must be performed to improve magnetic properties after punching, and stress relief annealing is omitted if the cost loss due to heat treatment is greater than the magnetic property effect by stress relief annealing. form can be distinguished.
- the insulating film is a film coated in the final manufacturing process of laminates such as motors, generator iron cores, electric motors, and small transformers, and generally requires electrical properties to suppress the occurrence of eddy currents.
- continuous punching processability, adhesion resistance, and surface adhesion are required.
- Continuous punching workability refers to the ability to suppress wear of a mold when forming an iron core by stacking a plurality of cores after punching into a predetermined shape.
- Adhesion resistance refers to the ability to prevent adhesion between iron core steel sheets after the stress relief annealing process in which the magnetic properties are restored by removing the processing stress of the steel sheet.
- Such an insulating film can be manufactured as an electrical steel laminate only when a separate fastening method such as welding, clamping, or interlocking is used.
- an electrical steel sheet laminate having a fusion bonding layer capable of bonding (joining) electrical steel sheets without using conventional fastening methods such as welding, clamping, and interlocking is provided.
- an electrical steel sheet adhesive coating composition, an electrical steel sheet laminate, and a method for manufacturing the same are provided, in which adhesion between electrical steel sheets is improved by controlling components of a fusion layer formed between electrical steel sheets.
- An adhesive coating composition for electrical steel sheet includes a mixed resin of a polyurethane resin and an epoxy resin, and the mixed resin includes 55 to 98 parts by weight of a polyurethane resin and an epoxy resin based on 100 parts by weight of the mixed resin. 2 to 45 parts by weight, and the polyurethane resin may be formed by reacting an aromatic diisocyanate monomer represented by Formula 1 below with a polyol.
- R 1 to R 10 are each independently hydrogen, heavy hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C5 to C20 heteroaryl group, or an isocyanate group.
- any one of R 1 to R 5 is an isocyanate group
- any one of R 6 to R 10 is an isocyanate group, except for the case where R 3 and R 8 are isocyanate groups at the same time
- L is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C5 to C20 heteroarylene group
- n is any one of 1 to 10 is an integer of
- any one of R 1 to R 5 is an isocyanate
- any one of R 6 to R 10 is an isocyanate, except for the case where R 3 and R 8 are simultaneously isocyanates, and R 1 and R 10 are isocyanates simultaneously. More cases may be excluded.
- any one of R 1 to R 5 is isocyanate
- any one of R6 to R10 is isocyanate
- any one of R 1 to R 5 and any one of R 6 to R 10 is symmetrically centered on L at the same time
- the case of isocyanate may be further excluded.
- the aromatic diisocyanate monomer represented by Chemical Formula 1 may be represented by Chemical Formula 2 below.
- L is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C5 to C20 heteroarylene group.
- the polyol may be a compound represented by Formula 3 below.
- R' is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C5 to C20 heteroaryl group.
- the polyurethane resin may include 30 to 50% by weight of an aromatic diisocyanate monomer and 50 to 70% by weight of a polyol.
- the epoxy resin may have a molecular weight of 5,000 to 20,000 and a hydroxyl value of 2 to 20 mgKOH/g.
- the adhesive coating composition for electrical steel sheet according to an embodiment of the present invention may further include at least one selected from the group consisting of a coupling agent, a wetting agent, a curing agent, and a curing catalyst.
- the coupling agent may include 0.2 to 3 parts by weight based on 100 parts by weight of the mixed resin.
- the curing agent may include 0.5 parts by weight to 2 parts by weight based on 100 parts by weight of the mixed resin.
- the curing catalyst may include 0.1 part by weight to 1 part by weight based on 100 parts by weight of the mixed resin.
- the wetting agent may include 0.05 to 0.5 parts by weight based on 100 parts by weight of the mixed resin.
- An electrical steel sheet laminate includes a plurality of electrical steel sheets; and a fusion layer positioned between the plurality of electrical steel sheets, wherein the fusion layer includes a mixed resin of a polyurethane resin and an epoxy resin, and the mixed resin contains 55 to 98 parts by weight of the polyurethane resin based on 100 parts by weight of the mixed resin. parts by weight and 2 to 45 parts by weight of an epoxy resin, and the polyurethane resin may be formed by reacting an aromatic diisocyanate monomer represented by Formula 1 below with a polyol.
- R 1 to R 10 are each independently hydrogen, heavy hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C5 to C20 heteroaryl group, or an isocyanate group.
- any one of R 1 to R 5 is an isocyanate group
- any one of R 6 to R 10 is an isocyanate group, except for the case where R 3 and R 8 are isocyanate groups at the same time
- L is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C5 to C20 heteroarylene group
- n is any one of 1 to 10 is an integer of
- a method of manufacturing an electrical steel sheet laminate according to an embodiment of the present invention includes applying an adhesive coating composition to one or both surfaces of an electrical steel sheet and then curing the adhesive coating composition to form an adhesive coating layer; and laminating a plurality of electrical steel sheets on which the adhesive coating layer is formed and heat-sealing them to form a fusion-sealing layer, wherein the adhesive coating composition includes a mixed resin of a polyurethane resin and an epoxy resin, and the mixed resin is a mixed resin.
- the polyurethane resin Based on 100 parts by weight, it includes 55 to 98 parts by weight of a polyurethane resin and 2 to 45 parts by weight of an epoxy resin, and the polyurethane resin may be formed by reacting an aromatic diisocyanate monomer represented by Formula 1 below with a polyol.
- R 1 to R 10 are each independently hydrogen, heavy hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C5 to C20 heteroaryl group, or an isocyanate group.
- any one of R 1 to R 5 is an isocyanate group
- any one of R 6 to R 10 is an isocyanate group, except for the case where R 3 and R 8 are isocyanate groups at the same time
- L is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C5 to C20 heteroarylene group
- n is any one of 1 to 10 is an integer of
- the adhesion between the electrical steel sheets may be improved by controlling the components of the fusion layer formed between the electrical steel sheets.
- electrical steel sheets can be bonded without using conventional fastening methods such as welding, clamping, and interlocking, so that the noise and vibration suppression effect of the electrical steel sheet laminate is more excellent.
- 1 is a schematic diagram of an electrical steel sheet laminate.
- FIG. 2 is a schematic view of a cross section of an electrical steel sheet laminate according to an embodiment of the present invention.
- first, second and third are used to describe, but are not limited to, various parts, components, regions, layers and/or sections. These terms are only used to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, a first part, component, region, layer or section described below may be referred to as a second part, component, region, layer or section without departing from the scope of the present invention.
- substitution is a compound in which at least one hydrogen is a C1 to C30 alkyl group; C1 to C10 alkoxy group; silane group; Alkylsilane group; an alkoxysilane group; It means substituted with an ethyleneoxyl group.
- hetero means an atom selected from the group consisting of N, O, S, and P, unless otherwise defined.
- the alkyl group may be a C1 to C20 alkyl group, specifically, a C1 to C6 lower alkyl group, a C7 to C10 intermediate alkyl group, or a C11 to C20 higher alkyl group.
- a C1 to C4 alkyl group means that there are 1 to 4 carbon atoms in the alkyl chain, which is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl. indicates that it is selected from the group consisting of
- Typical alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
- An adhesive coating composition for electrical steel sheet includes a mixed resin of a polyurethane resin and an epoxy resin, and the mixed resin contains 55 to 98 parts by weight of the polyurethane resin based on 100 parts by weight of the mixed resin. and 2 to 45 parts by weight of the epoxy resin, and the polyurethane resin may be formed by reacting an aromatic diisocyanate monomer represented by Formula 1 below with a polyol.
- R 1 to R 10 are each independently hydrogen, heavy hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C5 to C20 heteroaryl group, or an isocyanate group.
- any one of R 1 to R 5 is an isocyanate group
- any one of R 6 to R 10 is an isocyanate group, except for the case where R 3 and R 8 are isocyanate groups at the same time
- L is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C5 to C20 heteroarylene group
- n is any one of 1 to 10 is an integer of
- the mixed resin may include 55 to 98 parts by weight of the polyurethane resin and 2 to 45 parts by weight of the epoxy resin based on 100 parts by weight of the mixed resin. If too much polyurethane resin is included, the high-temperature adhesive strength may be poor due to the low degree of crosslinking of the mixed resin layer, and if the polyurethane resin is included too little, the vibration suppression effect may be poor due to the low viscoelasticity of the mixed resin layer. can If too much epoxy resin is included, the vibration suppression effect may be deteriorated due to the decrease in viscoelastic properties due to the high crosslinking degree of the mixed resin layer. can get hot
- any one of R 1 to R 5 is an isocyanate
- any one of R 6 to R 10 is an isocyanate, except for the case where R 3 and R 8 are simultaneously isocyanates, and R 1 and R 10 are isocyanates simultaneously. More cases may be excluded.
- any one of R 1 to R 5 is isocyanate
- any one of R6 to R10 is isocyanate
- any one of R 1 to R 5 and any one of R 6 to R 10 is symmetrically centered on L at the same time
- the case of isocyanate may be further excluded.
- the aromatic diisocyanate monomer represented by Formula 1 may be represented by Formula 2 below.
- L is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C5 to C20 heteroarylene group.
- the polyol may be a compound represented by Formula 3 below.
- R' is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C5 to C20 heteroaryl group.
- the polyol may be polypropylene glycol.
- the polyol may have a number average molecular weight of 400 to 1000 g/mol.
- the polyurethane resin may include 30 to 50% by weight of an aromatic diisocyanate monomer and 50 to 70% by weight of a polyol. If the ratio of the aromatic diisocyanate monomer is too small, a problem of a decrease in high-temperature binding strength of the polyurethane resin may occur, and if the ratio is too large, a problem of a decrease in heat-sealability may occur. If the ratio of polyol is too small, the heat sealing property may be deteriorated, and if the ratio of polyol is too large, a problem of sticky defect may occur during long-term storage in a coiled state due to tacky characteristics.
- the epoxy resin may have a molecular weight of 5,000 to 20,000 and a hydroxyl value of 2 to 20 mgKOH/g.
- the adhesive coating composition for electrical steel sheet according to an embodiment of the present invention may further include at least one selected from the group consisting of a coupling agent, a wetting agent, a curing agent, and a curing catalyst.
- the electrical steel sheet adhesive coating composition according to an embodiment of the present invention may further include a coupling agent to enhance interfacial adhesion between the electrical steel sheet 10 and the fusion bonding layer 20 .
- the coupling agent may include a silane coupling agent, and more specifically, at least one of a vinyl-based silane coupling agent and a methacryloxy-based silane coupling agent.
- Examples of the vinyl-based silane coupling agent may include vinyl trimethoxy silane, vinyl triethoxy silane, and the like.
- Methacryloxy-based silane coupling agents include 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane (3-Methacyloxypropyl methyldiethoxysilane), 3-methacryloxypropyl triethoxysilane (3-Methacryloxpropyl triethoxysilane) may be present.
- the adhesive coating composition for electrical steel sheet may further include a silicon-based wetting agent in the adhesive coating composition to enhance interfacial adhesion between the electrical steel sheet 10 and the fusion bonding layer 20 .
- a silicon-based wetting agent may be polyether-modified polydimethylsiloxane.
- a humectant may be added to the bonding composition for electrical steel sheet in order to enhance interfacial adhesion between the electrical steel sheet and the fusion bonding layer.
- the adhesive coating composition for electrical steel sheet according to an embodiment of the present invention may further include a curing agent to adjust the reactivity of the surface of the adhesive coating layer.
- the curing agent may include an aliphatic amine-based, aromatic amine-based, amino amine-based, or imidazole-based curing agent. More specifically, a dicyandiamide-based curing agent may be included.
- the adhesive coating composition for electrical steel sheet according to an embodiment of the present invention may further contain a curing catalyst to improve sticky defects due to non-curing due to rapid curing reaction during coil coating.
- the curing catalyst may include an imidazole-based curing catalyst.
- the electrical steel sheet adhesive coating composition according to an embodiment of the present invention may include 0.2 to 3 parts by weight of the coupling agent based on 100 parts by weight of the mixed resin. Specifically, it may include 0.2 parts by weight to 1 part by weight. If the coupling agent is included too little, the effect of enhancing the interfacial adhesion between the electrical steel sheet and the fusion bonding layer may not be sufficiently obtained. If too much coupling agent is included, a precipitate may occur in the adhesive coating composition due to a reaction between the coupling agents.
- the adhesive coating composition for electrical steel sheet may include 0.5 parts by weight to 2 parts by weight of the curing agent based on 100 parts by weight of the mixed resin. Specifically, it may include 0.8 parts by weight to 1.2 parts by weight.
- the curing agent serves to control the reactivity of the surface of the adhesive coating layer. If the curing agent is included too little, the curing reaction of the fusion bonding layer is lowered, and a problem in that the surface of the fusion bonding layer is sticky may occur. Conversely, if too much curing agent is added, the fastening force after low-temperature fusion may be deteriorated.
- the adhesive coating composition for electrical steel sheet according to an embodiment of the present invention may include 0.1 part by weight to 1 part by weight of the curing catalyst based on 100 parts by weight of the mixed resin. Specifically, it may include 0.3 parts by weight to 0.8 parts by weight. If the content of the curing catalyst is too large, a problem of poor clamping force after fusion may occur due to over-curing reaction, and if the content of the curing catalyst is too small, a problem of sticky property on the surface of the fusion layer may occur due to uncuring. there is.
- the adhesive coating composition for electrical steel sheet according to an embodiment of the present invention may include 0.05 part by weight to 0.5 part by weight of the wetting agent based on 100 parts by weight of the mixed resin. Specifically, it may include 0.05 parts by weight to 0.15 parts by weight. If the content of the wetting agent is too large, defects in the coating layer may occur due to excessive bubbles in the coating solution, and if the content of the wetting agent is too small, defects in the coating surface may occur due to deterioration in wettability of the coating layer.
- the adhesive coating composition may include a solvent to facilitate application and uniformly disperse the components.
- the solvent may include water, alcohol, and the like.
- the solvent may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the mixed resin.
- an electrical steel sheet laminate is provided.
- An electrical steel sheet laminate according to an embodiment of the present invention includes a plurality of electrical steel sheets; and a fusion bonding layer positioned between the plurality of electrical steel sheets.
- 1 shows a schematic diagram of an electrical steel sheet laminate according to an embodiment of the present invention. As shown in Figure 1, it is a form in which a plurality of electrical steel sheets are laminated.
- the electrical steel sheet laminate 100 according to an embodiment of the present invention includes a plurality of electrical steel sheets 10; and a fusion bonding layer 20 positioned between the plurality of electrical steel sheets.
- An electrical steel sheet laminate according to an embodiment of the present invention does not use conventional methods such as welding, clamping, and interlocking, and simply forms a fusion layer using the adhesive coating composition to form different electrical steel sheets. It may be a heat-sealed laminate.
- the electrical steel sheet laminate has excellent properties such as high-temperature adhesiveness and high-temperature oil resistance even after thermal fusion.
- the electrical steel sheet 10 a general non-oriented or grain-oriented electrical steel sheet may be used without limitation.
- the main configuration is to form the fusion layer 20 between the plurality of electrical steel sheets 10 to manufacture the electrical steel sheet laminate 100, a detailed description of the electrical steel sheet 10 omit
- the fusion layer 20 is formed between the plurality of electrical steel sheets 10 and has adhesive strength sufficient to bond the plurality of electrical steel sheets 10 without using conventional fastening methods such as welding, clamping, and interlocking. strong.
- the fusion layer 20 is coated with an adhesive coating composition on the surface, cured to form an adhesive coating layer, and laminated and heat-sealed to form the fusion layer 20 .
- resin components in the adhesive coating layer are thermally fused to form a fused layer.
- the fusion layer 20 includes a mixed resin of a polyurethane resin and an epoxy resin. Since the polyurethane resin, the epoxy resin, and the mixed resin have been described in detail with respect to the adhesive coating composition, duplicate descriptions will be omitted. In the process of forming the fusion layer, the mixed resin of the polyurethane resin and the epoxy resin remains as it is. In addition, a coupling agent, a curing agent, a curing catalyst, and a wetting additive also remain, and the content range thereof may be the same as that of the adhesive coating composition. Since the coupling agent, curing agent, curing catalyst, and wetting additive have been described in detail with respect to the adhesive coating composition, overlapping descriptions will be omitted.
- the fusion layer may include 100 parts by weight of the mixed resin, 0.5 parts by weight of a silane coupling agent, 0.1 part by weight of a silicone-based wetting agent, 1 part by weight of a dicyandiamide-based curing agent, and 0.5 parts by weight of an imidazole-based curing catalyst. .
- the thickness of the fusion layer 20 may be 1 ⁇ m to 8 ⁇ m. If the thickness of the fusion layer is too thin, the adhesive strength can be rapidly lowered, and if it is too thick, defects due to stickiness become a problem after winding the coating. More specifically, the thickness of the fusion layer 20 may be 4 ⁇ m to 6 ⁇ m.
- a method for manufacturing an electrical steel sheet laminate according to an embodiment of the present invention includes applying an adhesive coating composition to one or both surfaces of an electrical steel sheet and then curing the adhesive coating composition to form an adhesive coating layer; and forming a fusion bonding layer by laminating a plurality of electrical steel sheets on which the adhesive coating layer is formed and heat-sealing them.
- an adhesive coating composition is prepared. Since the adhesive coating composition has been described above, overlapping descriptions will be omitted.
- the adhesive coating composition is coated on the surface of the electrical steel sheet and cured to form an adhesive coating layer.
- This step may be performed in a temperature range of 150 to 250 °C for curing the adhesive coating composition.
- a plurality of electrical steel sheets having adhesive coating layers are laminated and heat-sealed to form the fusion layer 20 .
- the polymer components in the adhesive coating layer are heat-sealed to form a fusion layer.
- the heat-sealing step may be heat-sealed at a temperature of 150 to 250° C., a pressure of 0.05 to 5.0 MPa, and a pressing condition of 0.1 to 120 minutes. Each of the above conditions may be satisfied independently, and two or more conditions may be satisfied simultaneously. By adjusting conditions of temperature, pressure, and time in the heat-sealing step, dense heat-sealing can be performed between the electrical steel sheets without gaps or organic phases.
- the heat-sealing step includes a temperature-raising step and a fusion step, and the temperature-raising rate of the temperature-raising step may be 10°C/min to 1000°C/min.
- a non-oriented electrical steel sheet (50 X 50 mm, 0.35 mmt) was prepared as a blank specimen.
- the adhesive coating solution was applied to the top and bottom of each prepared blank specimen in a constant thickness using a bar coater and a roll coater, cured at 200 ° C for 20 seconds based on the plate temperature, and then slowly cooled in air to form an adhesive coating layer.
- an adhesive coating solution 100 parts by weight of a mixed resin of polyurethane resin and epoxy resin, 0.5 parts by weight of a silane coupling agent, 0.1 part by weight of a silicone-based wetting agent, 1 part by weight of a dicyandiamide-based curing agent and 0.5 part by weight of an imidazole-based curing catalyst Those containing parts by weight were used.
- the polyurethane resin was prepared by reacting 40% by weight of 2,4-methylene diphenyl diisocyanate monomer with 60% by weight of polypropylene glycol having a water molecular weight of 425 g/mol based on the total weight of the polyurethane resin, and then using the epoxy resin.
- the content ratio of the polyurethane resin and the epoxy resin used, and the type and content ratio of the isocyanate monomer and polyol used in the production of the polyurethane resin are shown in Table 1 below.
- a silane coupling agent based on 100 parts by weight of the polyurethane resin, 0.5 parts by weight of a silane coupling agent, 0.1 part by weight of a silicone-based wetting agent, 1 part by weight of a dicyandiamide-based curing agent and 0.5 parts by weight of an imidazole-based curing catalyst are included. did
- MDI means methylene diphenyl diisocyanate
- TDI means toluene diisocyanate
- PPG polypropylene glycol (moisture weight 425 g/mol).
- Electrical steel sheets coated with an adhesive coating layer were laminated to a height of 20 mm, pressed with a force of 0.5 MPa, and heat-sealed at 160° C. for 10 minutes to prepare an electrical steel laminate.
- the thickness of the fusion layer after thermal fusion was about 6 ⁇ m.
- the heat-sealed laminate was evaluated according to the mixing ratio of the mixed resin in the coating composition and the type of aromatic diisocyanate monomer used. Specifically, coating film adhesion, peel adhesion (T-peel, N / mm), ATF resistance, attenuation ratio and high temperature adhesion were evaluated and shown in Table 1 below.
- the measurement method of each characteristic is as follows.
- Coating film adhesion measurement method The specimen standard for measuring coating film adhesion was manufactured in accordance with ISO 1519. Make a sample of 30 x 300 mm of the coated specimen, bend it at an angle of 180° to an iron cylinder with a diameter of 10 mm, attach the tape to the area, and observe the peeling of the coating layer with the naked eye. When peeling occurred, it was evaluated as NG, and when peeling did not occur, it was judged as OK.
- Peel adhesion (T-peel, N/mm): The specimen standard for measuring the peel method (T-peel off) was prepared in accordance with ISO 11339. After bonding two 25 x 200 mm specimens with an area of 25 x 150 mm 2 , the unbonded area was bent at 90° to produce a T-shaped tensile specimen. A specimen manufactured by the peeloff method (T-Peeloff) was fixed to the upper/lower jig (JIG) with a constant force, and then pulled at a constant speed and measured using a device for measuring the tensile force of the stacked samples.
- JIG upper/lower jig
- the measured value was measured at the point where the interface with the minimum adhesive strength was eliminated among the interfaces of the stacked samples. After maintaining the temperature of the specimen at 60 °C through a heating device, the adhesive force was measured.
- Anti-ATF characteristic evaluation method When a drive motor is used in a car, a lot of heat is generated during long-term rotation at high speed, and ATF (Automotive Transmission Fluid, automotive transmission oil) is used to cool it. Therefore, in order to secure adhesion reliability during long-term use, it is important that the adhesive strength of the laminated coil is maintained in a state impregnated with high-temperature ATF. Accordingly, the anti-ATF properties were evaluated. Shear adhesion was tested after immersing the prepared laminated coil in ATF at a temperature of 150° C. for 500 hours. The shear adhesion to measure the ATF properties in the above was measured by the shear method (Shear Strength).
- Specimen specifications for shear method measurement were prepared in accordance with ISO 4587. Two 25 x 100 mm specimens were bonded with an area of 12.5 x 25 mm 2 and heat-sealed under the above conditions to prepare a shear method specimen. After fixing the specimen manufactured by the shear method to the upper and lower jigs (JIG) with a constant force, it was measured using a device for measuring the tensile force of the stacked samples while pulling at a constant speed. At this time, in the case of the shear method, the measured value was measured at the point where the interface with the minimum adhesive strength was eliminated among the interfaces of the stacked samples.
- JIG jigs
- a ring type motor core was manufactured to evaluate the noise characteristics generated in the motor core unit among drive motors.
- a ring core having an outer diameter of 128 mm, an inner diameter of 90 mm, and a height of 45 mm was manufactured by punching and heat-sealing a product coated with a coating agent on a 0.27 mm non-oriented electrical steel sheet.
- the dynamic characteristics of the thus-manufactured ring core in the axial direction were measured.
- a transfer function which is a function that applies an external force and obtains a dynamic response to it, is used.
- F the frequency response function
- FRF the frequency response function
- the damping ratio was measured through this FRF characteristic analysis. The higher the damping ratio, the better the vibration absorption, so less vibration and noise occur.
- Shear adhesion for measuring high-temperature adhesion was measured by a shear method. Specimen specifications for shear method measurement were prepared in accordance with ISO 4587. Two 25 x 100 mm specimens were bonded with an area of 12.5 x 25 mm 2 using a coating agent and heat-sealed under the above-described conditions to prepare shear specimens. The specimen produced by the shear method is set at a high ambient temperature in a tensioner with a heating furnace, fixed to the upper and lower jigs (JIG) with a certain force, and then pulled at a constant speed to measure the tensile force of the stacked samples. measured using the device.
- JIG jigs
- the measured value was measured at the point where the interface with the minimum adhesive force was eliminated among the interfaces of the stacked samples. After maintaining the temperature of the specimen at 160 °C through a heating device, the adhesive strength was measured.
- Comparative Example 1 when only polyurethane resin was used without mixing epoxy resin, the coating film adhesion, peel adhesion, and vibration absorption were excellent, but the high-temperature adhesion showed a value of less than 1 MPa, which was inferior, and it was confirmed that the ATF resistance was also inferior.
- Comparative Example 2 is a case in which only an epoxy resin is used without mixing a polyurethane resin, and the coating film adhesion, ATF resistance, and high-temperature adhesion are excellent, but the peel adhesion is poor and the damping ratio is less than 0.03, resulting in a noise and vibration suppression effect. You can check what's hot.
- Comparative Example 3 is a case where the content of the polyurethane resin is low and the content of the epoxy resin is high, and it can be seen that the coating film adhesion, ATF resistance and high temperature adhesion are excellent, but the peel adhesion and vibration absorption are poor.
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Abstract
Description
구분 | 혼합 수지 (100 중량부) | 폴리우레탄 수지 | 도막밀착성 | 박리접착력 (N/mm) |
내ATF 특성 (MPa) |
감쇠비 | 고온 접착력 (MPa) | |||||
폴리우레탄 수지 (중량부) | 에폭시 수지 (중량부) | 방향족 디이소시아네이트 | 폴리올 | |||||||||
종류 | 함량(중량%) | 종류 | 함량(중량%) | |||||||||
실시예 1 | 95 | 5 | 2,4'-MDI | 40 | PPG | 60 | OK | 3 | 2.0 | 0.1 | 1.5 | |
실시예 2 | 80 | 20 | 2,4'-MDI | 40 | PPG | 60 | OK | 2.5 | 3.0 | 0.07 | 2 | |
실시예 3 | 60 | 40 | 2,4'-MDI | 40 | PPG | 60 | OK | 1.5 | 5.0 | 0.05 | 4 | |
비교예 1 | 100 | 0 | 2,4'-MDI | 40 | PPG | 60 | OK | 3.5 | 0.5 | 0.12 | 0.05 | |
비교예 2 | 0 | 100 | 2,4'-MDI | 40 | PPG | 60 | OK | 0.5 | 8.0 | 0.01 | 9 | |
비교예 3 | 50 | 50 | 2,4'-MDI | 40 | PPG | 60 | OK | 0.7 | 7.0 | 0.02 | 6 | |
비교예 4 | 95 | 5 | 2,4'-TDI | 30 | PPG | 70 | OK | 0.5 | 3.0 | 0.02 | 2.5 | |
비교예 5 | 95 | 5 | 2,2’-MDI | 40 | PPG | 60 | OK | 0.7 | 2.5 | 0.02 | 2.0 | |
비교예 6 | 95 | 5 | 4,4’-MDI | 40 | PPG | 60 | OK | 0.8 | 1.5 | 0.05 | 0.7 | |
비교예 7 | 80 | 20 | 2,4'-TDI | 30 | PPG | 70 | OK | 0.4 | 3.5 | 0.01 | 3.2 | |
비교예 8 | 80 | 20 | 2,2’-MDI | 40 | PPG | 60 | OK | 0.6 | 3.2 | 0.01 | 3.0 | |
비교예 9 | 80 | 20 | 4,4’-MDI | 40 | PPG | 60 | OK | 0.7 | 1.7 | 0.04 | 2.0 | |
비교예 10 | 60 | 40 | 2,4'-TDI | 30 | PPG | 70 | OK | 0.3 | 4.0 | 0.01 | 3.3 | |
비교예 11 | 60 | 40 | 2,2’-MDI | 40 | PPG | 60 | OK | 0.5 | 3.3 | 0.01 | 3.5 | |
비교예 12 | 60 | 40 | 4,4’-MDI | 40 | PPG | 60 | OK | 0.6 | 1.8 | 0.03 | 2.0 |
Claims (14)
- 폴리우레탄 수지 및 에폭시 수지의 혼합 수지를 포함하고,상기 혼합 수지는, 혼합 수지 100 중량부를 기준으로, 상기 폴리우레탄 수지 55 내지 98 중량부 및 상기 에폭시 수지 2 내지 45 중량부를 포함하고,상기 폴리우레탄 수지는 하기 화학식 1로 표시되는 방향족 디이소시아네이트 모노머 및 폴리올이 반응하여 형성되는 것인, 전기강판 접착 코팅 조성물.[화학식 1]상기 화학식 1 에서,R1 내지 R10은 각각 독립적으로, 수소, 중수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C6 내지 C20 아릴기, 치환 또는 비치환된 C5 내지 C20 헤테로아릴기, 또는 이소시아네이트기이고,R1 내지 R5 중 어느 하나는 이소시아네이트기이고,R6 내지 R10 중 어느 하나는 이소시아네이트기이고,R3 및 R8이 동시에 이소시아네이트기인 경우는 제외되고,L은 치환 또는 비치환된 C1 내지 C10 알킬렌기, 치환 또는 비치환된 C2 내지 C10 알키닐렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기, 또는 치환 또는 비치환된 C5 내지 C20 헤테로아릴렌기이고,n은 1 내지 10 중 어느 하나의 정수이다.
- 제1항에 있어서,상기 화학식 1에서 R1 내지 R5 중 어느 하나는 이소시아네이트이고, R6 내지 R10 중 어느 하나는 이소시아네이트이며,R3 및 R8 이 동시에 이소시아네이트인 경우는 제외되고,R1 및 R10 이 동시에 이소시아네이트인 경우가 더 제외되는, 전기강판 접착 코팅 조성물.
- 제1항에 있어서,상기 화학식 1에서R1 내지 R5 중 어느 하나는 이소시아네이트이고, R6 내지 R10 중 어느 하나는 이소시아네이트이며,R1 내지 R5 중 어느 하나 및 R6 내지 R10 중 어느 하나가 L을 중심으로 대칭으로 동시에 이소시아네이트인 경우가 더 제외되는, 전기강판 접착 코팅 조성물.
- 제1항에 있어서,상기 폴리우레탄 수지는 상기 방향족 디이소시아네이트 모노머를 30 내지 50 중량% 및 상기 폴리올을 50 내지 70 중량% 포함하는, 전기강판 접착 코팅 조성물.
- 제1항에 있어서,상기 에폭시 수지는, 분자량은 5,000 내지 20,000이고, 수산기값은 2 내지 20 mgKOH/g인, 전기강판 접착 코팅 조성물.
- 제1항에 있어서,커플링제, 습윤제, 경화제 및 경화촉매로 이루어진 군에서 선택되는 1종 이상을 더 포함하는, 전기강판 접착 코팅 조성물.
- 제8항에 있어서,상기 커플링제는, 상기 혼합 수지 100 중량부 기준으로, 0.2 중량부 내지 3 중량부를 포함하는, 전기강판 접착 코팅 조성물.
- 제8항에 있어서,상기 경화제는, 상기 혼합 수지 100 중량부 기준으로, 0.5 중량부 내지 2 중량부를 포함하는, 전기강판 접착 코팅 조성물.
- 제8항에 있어서,상기 경화촉매는, 상기 혼합 수지 100 중량부 기준으로, 0.1 중량부 내지 1 중량부를 포함하는, 전기강판 접착 코팅 조성물.
- 제8항에 있어서,상기 습윤제는, 상기 혼합 수지 100 중량부 기준으로, 0.05 중량부 내지 0.5 중량부를 포함하는, 전기강판 접착 코팅 조성물.
- 복수의 전기강판; 및상기 복수의 전기강판 사이에 위치하는 융착층;을 포함하고,상기 융착층은 폴리우레탄 수지 및 에폭시 수지의 혼합 수지를 포함하고,상기 혼합 수지는, 혼합 수지 100 중량부를 기준으로, 상기 폴리우레탄 수지 55 내지 98 중량부 및 상기 에폭시 수지 2 내지 45 중량부를 포함하고,상기 폴리우레탄 수지는 하기 화학식 1로 표시되는 방향족 디이소시아네이트 모노머 및 폴리올이 반응하여 형성되는 것인, 전기강판 적층체.[화학식 1]상기 화학식 1 에서,R1 내지 R10은 각각 독립적으로, 수소, 중수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C6 내지 C20 아릴기, 치환 또는 비치환된 C5 내지 C20 헤테로아릴기, 또는 이소시아네이트기이고,R1 내지 R5 중 어느 하나는 이소시아네이트기이고,R6 내지 R10 중 어느 하나는 이소시아네이트기이고,R3 및 R8이 동시에 이소시아네이트기인 경우는 제외되고,L은 치환 또는 비치환된 C1 내지 C10 알킬렌기, 치환 또는 비치환된 C2 내지 C10 알키닐렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기, 또는 치환 또는 비치환된 C5 내지 C20 헤테로아릴렌기이고,n은 1 내지 10 중 어느 하나의 정수이다.
- 전기강판의 일면 또는 양면에 접착 코팅 조성물을 도포한 후, 경화시켜 접착 코팅층을 형성하는 단계; 및상기 접착 코팅층이 형성된 복수의 전기강판을 적층하고, 열융착하여 융착층을 형성하는 단계;를 포함하고,상기 접착 코팅 조성물은 폴리우레탄 수지 및 에폭시 수지의 혼합 수지를 포함하고,상기 혼합 수지는, 혼합 수지 100 중량부를 기준으로, 상기 폴리우레탄 수지 55 내지 98 중량부 및 상기 에폭시 수지 2 내지 45 중량부를 포함하고,상기 폴리우레탄 수지는 하기 화학식 1로 표시되는 방향족 디이소시아네이트 모노머 및 폴리올이 반응하여 형성되는 것인, 전기강판 적층체의 제조 방법.[화학식 1]상기 화학식 1 에서,R1 내지 R10은 각각 독립적으로, 수소, 중수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 치환 또는 비치환된 C6 내지 C20 아릴기, 치환 또는 비치환된 C5 내지 C20 헤테로아릴기, 또는 이소시아네이트기이고,R1 내지 R5 중 어느 하나는 이소시아네이트기이고,R6 내지 R10 중 어느 하나는 이소시아네이트기이고,R3 및 R8이 동시에 이소시아네이트기인 경우는 제외되고,L은 치환 또는 비치환된 C1 내지 C10 알킬렌기, 치환 또는 비치환된 C2 내지 C10 알키닐렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기, 또는 치환 또는 비치환된 C5 내지 C20 헤테로아릴렌기이고,n은 1 내지 10 중 어느 하나의 정수이다.
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JPH07336969A (ja) * | 1994-06-09 | 1995-12-22 | Nkk Corp | 接着鉄心用電磁鋼板およびその製造方法 |
JP2002166496A (ja) * | 2000-11-30 | 2002-06-11 | Nisshin Steel Co Ltd | 耐水シール性に優れた積層部品用塗装金属板 |
JP2009203402A (ja) * | 2008-02-29 | 2009-09-10 | Konishi Co Ltd | 2液型硬化性組成物 |
JP2017179233A (ja) * | 2016-03-31 | 2017-10-05 | Jfeスチール株式会社 | 耐熱接着性絶縁被膜用組成物および絶縁被膜付き電磁鋼板 |
JP2017186542A (ja) * | 2016-03-31 | 2017-10-12 | Jfeスチール株式会社 | 耐熱接着性絶縁被膜用組成物および絶縁被膜付き電磁鋼板 |
CN110669415A (zh) * | 2019-10-15 | 2020-01-10 | 北京盈和瑞环境科技股份有限公司 | 一种有机涂层钢板及其制造方法和应用 |
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JPH07336969A (ja) * | 1994-06-09 | 1995-12-22 | Nkk Corp | 接着鉄心用電磁鋼板およびその製造方法 |
JP2002166496A (ja) * | 2000-11-30 | 2002-06-11 | Nisshin Steel Co Ltd | 耐水シール性に優れた積層部品用塗装金属板 |
JP2009203402A (ja) * | 2008-02-29 | 2009-09-10 | Konishi Co Ltd | 2液型硬化性組成物 |
JP2017179233A (ja) * | 2016-03-31 | 2017-10-05 | Jfeスチール株式会社 | 耐熱接着性絶縁被膜用組成物および絶縁被膜付き電磁鋼板 |
JP2017186542A (ja) * | 2016-03-31 | 2017-10-12 | Jfeスチール株式会社 | 耐熱接着性絶縁被膜用組成物および絶縁被膜付き電磁鋼板 |
CN110669415A (zh) * | 2019-10-15 | 2020-01-10 | 北京盈和瑞环境科技股份有限公司 | 一种有机涂层钢板及其制造方法和应用 |
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