WO2022118916A1 - ペースト - Google Patents
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- WO2022118916A1 WO2022118916A1 PCT/JP2021/044281 JP2021044281W WO2022118916A1 WO 2022118916 A1 WO2022118916 A1 WO 2022118916A1 JP 2021044281 W JP2021044281 W JP 2021044281W WO 2022118916 A1 WO2022118916 A1 WO 2022118916A1
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- WIPO (PCT)
- Prior art keywords
- paste
- curing agent
- powder
- metal element
- cured product
- Prior art date
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910008458 Si—Cr Inorganic materials 0.000 description 1
- 229910009038 Sn—P Inorganic materials 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 241001655798 Taku Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000828 alnico Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000702 sendust Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
- B22F9/008—Rapid solidification processing
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4453—Polyepoxides characterised by the nature of the curing agent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
- H01F1/28—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder dispersed or suspended in a bonding agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/02—Magnetic
Definitions
- One embodiment of the present invention relates to a paste. More specifically, the present invention relates to a paste capable of suppressing deterioration of properties in a cured product after heat curing.
- Patent Documents 1 to 4 disclose a magnetic powder paste containing a magnetic powder and a resin.
- Japanese Unexamined Patent Publication No. 2004-31786 Japanese Unexamined Patent Publication No. 8-273916 Japanese Unexamined Patent Publication No. 1-261897 Japanese Unexamined Patent Publication No. 2014-127624
- a metal powder paste containing a curable resin hereinafter, also referred to as a paste
- a molded body (cured product) containing the metal powder can be formed.
- the mixing ratio of the metal powder in the paste should be increased, and components other than the metal powder should be added.
- the ratio needs to be low.
- a method of adding a volatile component such as an organic solvent to the paste to adjust the viscosity is usually used.
- the amount of the organic solvent in the paste is large, a drying step is required after the paste is applied, and the volatilization of the organic solvent causes an environmental load.
- the volume shrinkage occurs due to the volatilization of the organic solvent, the base material may be exposed from a part of the paste-coated surface.
- the use of an organic solvent tends to cause deterioration of the characteristics of the cured product. For example, stress-strain accumulates inside the cured paste due to volume shrinkage due to volatilization of the organic solvent.
- the organic solvent when the organic solvent remains in the cured product, the ionic components and the like in the cured product tend to move, and the electrical insulating properties (hereinafter referred to as insulating properties) such as the insulating resistance value and the insulating reliability tend to decrease.
- insulating properties electrical insulating properties
- the amount of organic solvent used can be reduced, performance deterioration due to volatile components such as organic solvents in the cured product after heat curing can be suppressed, and characteristics such as excellent insulating properties can be easily obtained.
- Metal powder paste is desired.
- the coefficient of thermal expansion (CTE) of the cured product of the metal powder paste is also an important property.
- the cured product may warp due to the expansion difference during heating, or peeling may occur at the interface with the peripheral material. , The cured product is liable to crack or malfunction. Therefore, for example, in the case of an inductor, the CTE of the copper coil and the wiring board material on which the inductor is mounted is low, and it is desired that the CTE of the cured product of the metal powder paste is also low in accordance with these peripheral materials.
- the present invention has been made in view of the above circumstances, and can suppress performance deterioration due to volatile components such as organic solvents in the cured product after heat curing, and can obtain excellent properties such as insulation in the cured product.
- the embodiment of the present invention relates to the following.
- the present invention is not limited to the following embodiments and includes various embodiments.
- One embodiment relates to a paste containing a metal element-containing powder, an epoxy group-containing compound, and a curing agent, wherein the heat weight reduction rate after heat curing at 180 ° C. is 5% or less.
- the paste contains a metal element-containing powder, an epoxy group-containing compound, and a curing agent, has a thermal weight loss rate of 5% or less after heat curing at 180 ° C., and heat of the cured product.
- the expansion coefficient is preferably 40 ppm / ° C. or less.
- the curing agent preferably contains at least one selected from the group consisting of an amine-based curing agent and an imidazole-based curing agent.
- the amine-based curing agent preferably contains an aromatic amine.
- the epoxy group-containing compound preferably contains an epoxy resin that is liquid at 25 ° C.
- the curing agent preferably contains a curing agent that is liquid at 25 ° C.
- the content of the metal element-containing powder is preferably 70% by mass or more based on the total mass of the paste.
- the metal element-containing powder preferably contains a magnetic powder.
- the viscosity of the paste at 25 ° C. is preferably 1 Pa ⁇ s or more and 600 Pa ⁇ s or less.
- Another embodiment relates to the paste of the above embodiment used for screen printing.
- the disclosures of this application relate to the subject matter described in International Application No. PCT / JP2020 / 45278 filed December 4, 2020, all of which are incorporated herein by reference.
- a metal powder paste capable of reducing the amount of volatile components used such as an organic solvent.
- a metal powder paste capable of suppressing performance deterioration due to volatile components such as organic solvents in the cured product after heat curing and easily obtaining excellent properties such as insulating properties in the cured product.
- a cured product having a low CTE can be easily obtained.
- the present invention is not limited to the embodiments described below.
- the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
- the upper or lower limit of the numerical range at one stage may be optionally combined with the upper or lower limit of the numerical range at another stage.
- the materials exemplified in the present specification may be used alone or in combination of two or more.
- the content of each component in the composition is the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Means.
- the paste according to the embodiment of the present invention contains a metal element-containing powder, an epoxy group-containing compound, and a curing agent, and the paste can form a cured product by heat treatment. Since the paste of the above embodiment can suppress an increase in viscosity due to an increase in the amount of the metal element-containing powder and can reduce the content of volatile components such as an organic solvent, the mass of the paste when a cured product is formed from the paste is reduced. It is characterized by the fact that there are few.
- thermogravimetric reduction rate is 5% or less.
- the thermogravimetric reduction rate is more preferably 3% or less, further preferably 2% or less. Most preferably, the thermogravimetric reduction rate is 0%.
- the thermogravimetric reduction rate can be calculated from a measured value using a thermogravimetric differential thermal analyzer (TG-DTA).
- TG-DTA thermogravimetric differential thermal analyzer
- the coefficient of thermal expansion (CTE) of the cured product of the paste has a small difference from the CTE of the peripheral material of the cured product.
- the CTE of the cured product of the paste is preferably 40 ppm / ° C. or lower, more preferably 30 ppm / ° C. or lower, and further preferably 25 ppm / ° C. or lower. ..
- the cured product of the paste is obtained by maintaining the paste at 165 ° C. and 2 MPa for 30 minutes under vacuum conditions, then raising the temperature to 180 ° C., and then molding the paste under curing conditions in which the temperature is maintained for 1 hour. It may be a cured product. In molding the cured product, pre-molding may be performed prior to the curing. Preforming can be carried out, for example, by heating the paste at 100 ° C.
- CTE means the coefficient of linear thermal expansion in the region below the glass transition temperature measured under the conditions of a temperature range of 0 to 250 ° C. and a heating rate of 10 ° C./min.
- the metal element-containing powder may contain one kind of metal element or two or more kinds of metal elements.
- the metal element-containing powder may be, for example, at least one powder selected from the group consisting of elemental metals, alloys, and metal compounds.
- the metal element contained in the metal element-containing powder may be at least one selected from the group consisting of, for example, a base metal element, a noble metal element, a transition metal element, and a rare earth element.
- the metal elements include, for example, iron (Fe), copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), niobium (Nb), and aluminum (Al).
- Zinc (Sn), Chromium (Cr), Barium (Ba), Strontium (Sr), Lead (Pb), Silver (Ag), Praseodymium (Pr), Neodim (Nd), Samarium (Sm), and Dysprosium (Dy) ) May be at least one selected from the group consisting of.
- the metal element-containing powder may be a simple substance consisting of only one kind of metal element or an alloy composed of two or more kinds of metal elements.
- the alloy may contain at least one selected from the group consisting of solid solutions, eutectics, and intermetallic compounds.
- the alloy may be, for example, stainless steel such as a Fe—Cr based alloy and a Fe—Ni—Cr based alloy.
- it may be a copper alloy such as a Cu—Sn based alloy, a Cu—Sn—P based alloy, a Cu—Ni based alloy, and a Cu—Be based alloy.
- the metal element-containing powder may be a powder of a metal compound containing the metal element exemplified above and an element other than the above metal element.
- an element other than the above metal element for example, at least one selected from the group consisting of carbon (C), oxygen ( ⁇ ), beryllium (Be), phosphorus (P), boron (B), and silicon (Si).
- the metal compound may be, for example, a metal oxide such as iron oxide.
- the metal compound may be a magnetic substance containing a metal oxide as a main component and further mixed and sintered with a metal element such as cobalt, nickel, and manganese. Examples of the magnetic material include ferrite. It was
- the metal element-containing powder may be a magnetic powder.
- the magnetic material may be a soft magnetic alloy or a ferromagnetic alloy.
- the magnetic powder includes, for example, Fe—Si alloy, Fe—Si—Al alloy (Sendust), Fe—Ni alloy (Permalloy), and Fe—Cu—Ni alloy (Permalloy).
- Fe—Co alloys permenzur
- Fe—Cr—Si alloys electromagnetic stainless steel
- Nd—Fe—B alloys rare earth magnets
- Sm-Fe—N alloys rare earth magnets
- It may be at least one selected from the group consisting of an Al—Ni—Co alloy (alnico magnet) and ferrite.
- the ferrite may be, for example, spinel ferrite, hexagonal ferrite, or garnet ferrite.
- the metal element-containing powder may contain at least one selected from the group consisting of elemental substances, alloys, and metal compounds of the exemplified metal elements.
- the metal element-containing powder may contain at least one powder selected from the group consisting of elemental Fe and Fe-based alloys.
- the Fe-based alloys include, for example, Fe—Si based alloys, Fe—Si—Al based alloys, Fe—Ni based alloys, Fe—Cu—Ni based alloys, Fe—Co based alloys, Fe—Cr—Si based alloys, and Fe. It may be at least one selected from the group consisting of —Si—B based alloys and Fe—Si—B—P—Nb—Cr based alloys.
- the Fe-based alloy may be an Fe amorphous alloy.
- the Fe amorphous alloy powder is an amorphous powder obtained by quenching an alloy in which Fe as a main component is melted at a high temperature together with other elements such as Si, and is also known as metallic glass.
- the Fe amorphous alloy powder can be produced according to a method well known in the art.
- the Fe amorphous alloy powder can also be obtained as a commercial product.
- product names AW2-08 and KUAMET-6B2 manufactured by Epson Atmix Co., Ltd. product names DAPMS3, DAPMS7, DAPMSA10, DAPPB, DAPPC, DAPMKV49, DAP410L, DAP430L, and DAPHYB series manufactured by Daido Steel Co., Ltd., and Examples thereof include product names MH45D, MH28D, MH25D, and MH20D manufactured by Kobe Steel, Ltd.
- One of these Fe amorphous alloy powders may be used, or two or more thereof may be used in combination.
- each particle constituting the metal element-containing powder is not particularly limited.
- the individual particles may be, for example, spherical, ellipsoidal, flat, plate-like, rod-like, and needle-like. From the viewpoint of the space factor of the metal element-containing particles in the cured product of the paste and the low viscosity of the paste, a spherical shape is preferable. From the viewpoint of thixotropic properties of the paste, a combination of flat particles and needle-shaped particles may be used.
- the average particle size of the metal element-containing powder may be 0.05 to 200 ⁇ m, more preferably 0.5 to 100 ⁇ m, and even more preferably 1 to 50 ⁇ m.
- the "average particle size" described in the present specification means the particle size at an integrated value of 50% (volume basis) in the particle size distribution.
- the average particle size of the metal element-containing powder including the coating film may be within the above range.
- the paste may contain a plurality of types of metal element-containing powders having different average particle diameters (D50). For example, two or more kinds of metal element-containing powders having different average particle diameters may be used in combination.
- the gaps formed between the metal element-containing powders having a large average particle size are easily filled with another metal element-containing powder having a small average particle size. Therefore, the space factor of the metal element-containing powder in the cured paste can be easily increased.
- the particle size distribution of the metal element-containing powder is calculated based on, for example, weight measurement by sieving and analysis using a measuring device such as a laser diffraction / scattering device.
- the metal element-containing powder may be entirely or partially covered with a surface treatment agent on the surface of the metal element-containing powder.
- the surface treatment agent is, for example, an inorganic oxide, a phosphoric acid compound and a phosphate compound, an inorganic surface treatment agent such as a silane coupling agent, an organic surface treatment agent such as Montan wax, and a cured resin product. It's okay.
- As the surface treatment agent a coupling agent described later can also be used.
- it is preferable that the entire or part of the surface of the metal-based magnetic powder such as Fe-based alloy is covered with an insulating material. Examples of the insulating material include silica, titania, calcium phosphate, montan wax, and a cured epoxy resin.
- the metal element-containing powder may contain a magnetic powder whose surface is coated with an insulating material (hereinafter referred to as an insulating coated magnetic powder).
- a paste containing an insulating coating magnetic powder can easily provide a cured product having excellent magnetic properties and insulating properties.
- the paste containing the insulating coated magnetic powder may contain two or more kinds of insulating coated magnetic powder, and the average particle diameters of the two or more kinds of insulating coated magnetic powder may be the same or different from each other.
- the paste containing the insulating coated magnetic powder may further contain a magnetic powder having no insulating coating (hereinafter referred to as uncoated magnetic powder) in addition to the insulating coated magnetic powder.
- the average particle size of the uncoated magnetic powder may be the same as or different from the average particle size of the insulating coated magnetic powder.
- the average particle size of the uncoated magnetic powder is preferably smaller than the average particle size of the insulating coated magnetic powder.
- the insulating coating magnetic powder may be an Fe amorphous alloy powder having an insulating coating.
- an Fe amorphous alloy powder having an insulating coating.
- "KUAMET9A4" Fe-Si-B alloy, D50: 20 ⁇ m, with insulation coating) manufactured by Epson Atmix Co., Ltd.
- "SAP-2C” Fe-Si-B-
- the magnetic powder used in combination with the Fe amorphous alloy powder having an insulating coating for example, the soft ferrite powder "BSN-125" (Ni—Zn based alloy, D50: 10 ⁇ m, no insulating coating) manufactured by Toda Kogyo Co., Ltd. is preferably used. can do.
- the content of the metal element-containing powder in the paste may be 70% by mass or more based on the total mass of the paste.
- the content of the metal element-containing powder is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 94% by mass or more.
- a molded product having excellent properties derived from the metal element-containing powder can be easily obtained.
- the metal element-containing powder is a magnetic powder, an inductor having excellent magnetic characteristics can be formed and excellent mechanical strength can be obtained.
- the content of the metal element-containing powder in the paste is less than 100% by mass and may be 99.9% by mass based on the total mass of the paste. From the viewpoint of the fluidity of the paste and the mechanical strength of the molded product, the content of the metal element-containing powder is preferably 99.8% by mass or less, more preferably 98% by mass or less, still more preferably 96. It may be mass% or less. In one embodiment, the content of the metal element-containing powder in the paste is preferably 80 to 99.9% by mass or more, more preferably 90 to 99.8% by mass or more, based on the total mass of the paste. , More preferably 94-96% by mass.
- the epoxy group-containing compound means a compound having one or more epoxy groups in the molecule, and may be in the form of a monomer and an oligomer or a polymer having a structural unit formed by polymerization of the monomer.
- the epoxy group-containing compound is cured by heat treatment and can function as a binder resin for binding the metal element-containing powder.
- Examples of epoxy group-containing compounds include oligomers and polymers having two or more epoxy groups in their molecules, commonly known as epoxy resins.
- an epoxy compound a compound having one or more epoxy groups in the molecule but not containing a structural unit formed by polymerization
- Such epoxy compounds are commonly known as reactive diluents.
- the epoxy group-containing compound preferably contains at least one selected from the group consisting of an epoxy resin and an epoxy compound.
- Epoxy resins include, for example, biphenyl type epoxy resin, stillben type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, naphthols and phenol.
- Copolymerization type epoxy resin aralkyl type phenol resin epoxide, bisphenol type epoxy resin, alcohols glycidyl ether type epoxy resin, paraxylylene and / or metaxylylene modified phenol resin glycidyl ether type epoxy resin, terpene modified phenol resin Glycidyl ether type epoxy resin, cyclopentadiene type epoxy resin, glycidyl ether type epoxy resin of polycyclic aromatic ring modified phenol resin, glycidyl ether type epoxy resin of naphthalene ring-containing phenol resin, glycidyl ester type epoxy resin, glycidyl type or methyl glycidyl Type epoxy resin, alicyclic epoxy resin, halogenated phenol novolac type epoxy resin, hydroquinone type epoxy resin, trimethylol propane type epoxy resin, and linear fat obtained by oxidizing an olefin bond with a peracid such as peracetic acid. It may be at least
- the molecular weight of the epoxy compound may be preferably 100 or more, more preferably 150 or more, and further preferably 200 or more.
- an epoxy compound having a molecular weight of 100 or more volatilization before reacting with the curing agent can be suppressed by setting appropriate curing conditions. Further, since the molecular weight is low, the distance between the cross-linking points after the reaction is short, and the occurrence of a problem that the cured product is easily cracked can be reduced.
- the molecular weight of the epoxy compound may be preferably 700 or less, more preferably 500 or less, and further preferably 300 or less. When an epoxy compound having a molecular weight of 700 or less is used, an appropriate viscosity can be easily obtained as a diluent.
- the molecular weight of the epoxy compound is preferably in the range of 100 to 700, more preferably in the range of 150 to 500, and even more preferably in the range of 200 to 300.
- an epoxy compound having a molecular weight in such a range is used, the viscosity of the paste can be easily adjusted.
- Epoxy compounds are different from components such as organic solvents that volatilize during heating, and are cured during heating and incorporated into the cured product. Therefore, when the epoxy compound is used, it contributes to the viscosity adjustment of the paste, and on the other hand, it is possible to suppress the deterioration of the characteristics of the cured product.
- the epoxy compound may contain one or more epoxy groups in the molecule.
- Epoxy compounds include, for example, n-butyl glycidyl ether, glycidyl ether, styrene oxide, ethylhexyl glycidyl ether, phenyl glycidyl ether, butyl phenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether.
- Diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether may be at least one selected from the group.
- the epoxy compound is preferably sufficiently purified and has a low content of ionic impurities.
- ionic impurities such as free Na ion and free Cl ion are preferably 500 ppm or less.
- the epoxy equivalent of the epoxy group-containing compound may be preferably 80 g / eq to 350 g / eq, more preferably 100 g / eq to 300 g / eq, and even more preferably 120 g / eq to 250 g / eq. It's okay. When the epoxy equivalent is within the above range, the viscosity of the epoxy group-containing compound itself becomes low, so that the viscosity of the paste can be easily adjusted.
- the epoxy group-containing compound preferably contains an epoxy group-containing compound that is liquid at 25 ° C.
- liquid at 25 ° C means that the viscosity of the epoxy group-containing compound at 25 ° C. is 200 Pa ⁇ s or less.
- the above viscosity is a value measured using an E-type viscometer under the conditions of temperature: 25 ° C., rotor: SPP, and rotation speed: 2.5 rpm.
- E-type viscometer for example, a TV-33 type viscometer manufactured by Toki Sangyo Co., Ltd. can be used.
- the viscosity of the epoxy group-containing compound may be preferably 100 Pa ⁇ s or less, more preferably 50 Pa ⁇ s or less, and further preferably 10 Pa ⁇ s or less. It's okay.
- the viscosity of the epoxy group-containing compound may exceed 0 Pa ⁇ s, may be 0.001 Pa ⁇ s or more, and may be 0.01 Pa ⁇ s or more.
- the viscosity of the epoxy compound is preferably lower than the viscosity of the liquid epoxy resin from the viewpoint of adjusting the paste viscosity.
- the viscosity of the epoxy compound may be preferably 1 Pa ⁇ s or less, more preferably 0.5 Pa ⁇ s or less, and further preferably 0.1 Pa ⁇ s or less.
- the viscosity of the epoxy compound may exceed 0 Pa ⁇ s, may be 0.001 Pa ⁇ s or more, and may be 0.01 Pa ⁇ s or more.
- the epoxy group-containing compound liquid at 25 ° C. may contain at least one selected from the group consisting of a liquid epoxy resin at 25 ° C. (hereinafter referred to as liquid epoxy resin) and a liquid epoxy compound at 25 ° C. Based on the total mass of the epoxy group-containing compound, the content of the liquid epoxy resin may be preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more. It may be present, and may be 100% by mass. However, the content of the liquid epoxy resin is not limited to the above range.
- the liquid epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, naphthalenediol type epoxy resin, hydrogenated bisphenol A type epoxy resin, and aminoglycidyl ether type. It may contain at least one liquid epoxy resin selected from epoxy resins. Among them, it is preferable to use at least one of a liquid bisphenol A type epoxy resin, a liquid bisphenol F type epoxy resin, and a liquid aminoglycidyl ether type epoxy resin.
- the liquid epoxy group-containing compound can also be obtained as a commercial product.
- it is sold by Nippon Steel Chemical Co., Ltd. as a liquid bisphenol A type epoxy resin and a liquid bisphenol F type epoxy resin.
- the product name "YDF-8170C” epoxy equivalent 165, viscosity 1,000 to 1,500 mPa ⁇ s
- the epoxy compound include a series of ADEKA glycyrrole (product name) manufactured by ADEKA Corporation.
- the product name “ADEKA Glycyrrol ED-503G” epoxy equivalent 135, viscosity 15 mPa ⁇ s
- ADEKA Glycyrrol ED-503G epoxy equivalent 135, viscosity 15 mPa ⁇ s
- the paste may further contain other resins in addition to the above epoxy group-containing compounds.
- the other resin may contain at least one selected from the group consisting of thermosetting resins (excluding epoxy resins) and thermoplastic resins.
- the thermosetting resin may be at least one selected from the group consisting of, for example, a phenol resin, an acrylic resin, a polyimide resin, and a polyamide-imide resin. When a phenol resin is used in addition to the epoxy group-containing compound, the phenol resin can also function as a curing agent for the epoxy group-containing compound.
- the thermoplastic resin may be at least one selected from the group consisting of, for example, acrylic resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate.
- the resin component may further contain a silicone resin in addition to the epoxy group-containing compound.
- the content of the other resin is preferably adjusted within a range that does not reduce the effect of the epoxy group-containing compound.
- the content of the other resin is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less, based on the total mass of the resin in the paste. good.
- the content of other resins is not limited to the above range.
- the blending amount can be adjusted within a range in which the viscosity of the mixture of the epoxy group-containing compound and the other resin is 50 Pa ⁇ s or less at 25 ° C.
- the above viscosity is a value measured using an E-type viscometer under the conditions of temperature: 25 ° C., rotor: cone plate, cone angle: 1 ° 34', and rotation speed: 2.5 rpm.
- E-type viscometer for example, a TV-33 type viscometer manufactured by Toki Sangyo Co., Ltd. can be used.
- the curing agent is not particularly limited, and may be any compound that can impart an appropriate viscosity to the paste and can react with the epoxy group of the epoxy group-containing compound to form a cured product. It may be a well-known curing agent generally used as a curing agent for an epoxy resin. Examples of the curing agent that can be used include a phenol-based curing agent, an acid anhydride-based curing agent, and an amine-based curing agent.
- the curing agent is classified into a curing agent that cures the epoxy resin in a temperature range from low temperature to room temperature and a heat-curing type curing agent that cures the epoxy resin with heating.
- the curing agent that cures the epoxy resin in the temperature range from low temperature to room temperature include aliphatic polyamines, polyaminoamides, and polymercaptans.
- the heat-curable curing agent include aromatic polyamines, acid anhydrides, phenol novolac resins, and dicyandiamides (DICY).
- a liquid curing agent at 25 ° C. from the viewpoint of reducing the viscosity of the paste.
- the liquid curing agent is at least one selected from the group consisting of, for example, an aliphatic or aromatic polyamine, an amine-based curing agent such as an aliphatic or aromatic amine, polymercaptan, an acid anhydride, and an imidazole-based curing agent. Seeds can be used. If the increase in the viscosity of the paste can be suppressed, a solid curing agent may be used at 25 ° C., or a liquid curing agent and a solid curing agent may be used in combination.
- solid curing agent for example, dicyandiamide, tertiary amine, imidazole-based curing agent, and imidazoline-based curing agent can be used.
- the illustrated solid curing agent is polyfunctional or acts catalytically, so that even a small amount can be fully functional.
- the curing agent preferably contains at least one selected from the group consisting of an amine-based curing agent, an imidazole-based curing agent, and an imidazoline-based curing agent. It is more preferable that the curing agent contains at least one selected from the group consisting of an amine-based curing agent and an imidazole-based curing agent. In one embodiment, the curing agent preferably contains at least an amine-based curing agent. Amine-based curing agents (more specifically, tertiary amines), imidazole-based curing agents, and imidazoline-based curing agents can also be used as curing accelerators in combination with other curing agents.
- the amine-based curing agent may be a compound having at least two amino groups in the molecule.
- the amine-based curing agent contains at least one selected from the group consisting of aliphatic amines and aromatic amines.
- the aliphatic amine may be a compound having a linear structure or a cyclic structure. For example, diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminobropyramine, cyclohexylamine, methylcyclohexylamine, isophoronediamine, 4,4'-diamino-dicyclohexylmethane, diazabicycloundecene, Can be mentioned.
- the aromatic amine may be a compound in which an amino group is substituted with an aromatic compound, and a compound having a structure in which a hydrogen of a benzene ring is substituted with an amino group is particularly preferable.
- benzyldimethylamine trisdimethylaminomethylphenol, metaphenylenediamine, benzyldimethylamine, 4,4'-diaminodiphenylmethane, 2-methylaniline, diaminodiphenylsulphon, polyamideamine, amine represented by the following formula (1).
- Examples of the compound include an amine compound represented by the following formula (2).
- thermogravimetric reduction tend to be easily adjusted.
- aromatic amines when aromatic amines are used, the viscosity and thermogravimetric reduction rate tend to be easier to adjust.
- the imidazole-based curing agent is a compound having an imidazole skeleton, and may be an imidazole-based compound in which a hydrogen atom in the molecule is substituted with a substituent.
- the imidazole-based curing agent may be a compound having an imidazole skeleton such as an alkyl group-substituted imidazole.
- Examples of the imidazole-based curing agent include imidazole, 2-methylimidazole, 2-ethylimidazole, and 2-isopropylimidazole.
- "Curesol 2E4MZ" (2-ethyl-4-methylimidazole) manufactured by Shikoku Chemicals Corporation can be preferably used.
- the imidazoline-based curing agent is a compound having an imidazoline skeleton, and may be an imidazoline-based compound in which a hydrogen atom in the molecule is substituted with a substituent. It may be a compound having an imidazoline skeleton such as an alkyl group substituted imidazoline.
- Examples of the imidazoline-based curing agent include imidazoline, 2-methylimidazoline, and 2-ethylimidazoline.
- the curing agent contains at least aromatic amine.
- the aromatic ring of the aromatic amine may have a substituent other than the amino group.
- it may have an alkyl group having 1 to 5 carbon atoms, or may have an alkyl group having 1 or 3 carbon atoms.
- the number of aromatic rings in the aromatic amine may be one or two or more. When the number of aromatic rings is 2 or more, the aromatic rings may be bonded to each other by a single bond or may be bonded via a linking group such as an alkylene group.
- the curing agent preferably contains a liquid aromatic amine from the viewpoint of the viscosity of the paste.
- a liquid aromatic amine from the viewpoint of the viscosity of the paste.
- at least one selected from the group consisting of the compound represented by the following formula (1) and the compound represented by the following formula (2) can be used.
- the compound represented by the formula (2) a compound in which a methyl group is replaced with an ethyl group can also be used.
- the compound represented by the following formula (1) can be preferably used.
- the liquid aromatic amine that can be used as a curing agent can also be obtained as a commercial product.
- product name "Grade: jER Cure WA” manufactured by Mitsubishi Chemical Corporation compound represented by formula (1), 2,6-diamino-3,5-diethyltoluene), product manufactured by Nippon Kayaku Corporation.
- the name "Kayahard AA” (3,3'-diethyl-4,4'-diaminodiphenylmethane) can be mentioned.
- the curing agent is 2,6-diamino-3,5-diethyltoluene, 3,3'-dimethyl (or diethyl) -4,4'-diaminodiphenylmethane, and 2-. It preferably contains at least one selected from the group consisting of ethyl-4-methylimidazole.
- the content of the curing agent in the paste is not particularly limited. It can be set in consideration of the ratio of the number of equivalents of the epoxy group of the epoxy group-containing compound such as the epoxy resin to the number of equivalents of the active group in the curing agent.
- the ratio of the curing agent to 1 equivalent of the epoxy group of the epoxy group-containing compound may be preferably 0.5 to 1.5 equivalents, more preferably 0.9 to 1.4 equivalents, and further. It may preferably be 1.0 to 1.2 equivalents.
- the ratio of the active group in the curing agent is 0.5 equivalent or more, the amount of OH per unit weight of the epoxy resin after heat curing is reduced, and it is possible to suppress the decrease in the curing rate of the epoxy resin. Further, it is possible to suppress a decrease in the glass transition temperature of the obtained cured product and a decrease in the elastic modulus of the cured product. Further, it is possible to suppress the deterioration of the insulation reliability of the cured product due to the unreacted resin component in the binder resin. On the other hand, when the ratio of the active group in the curing agent is 1.5 equivalents or less, it is possible to suppress a decrease in the mechanical strength of the molded product formed from the paste after heat curing.
- the ratio of the active group in the curing agent is not limited, and the effect according to the present invention can be obtained even outside the above range.
- the paste may further contain a curing accelerator, if necessary.
- the paste may contain a metal element-containing powder, an epoxy group-containing compound, a curing agent, and a curing accelerator.
- the paste may further contain additives such as, for example, coupling agents and flame retardants, in addition to the above components.
- additives such as, for example, coupling agents and flame retardants, in addition to the above components.
- the curing accelerator is not limited as long as it is a compound capable of accelerating the curing reaction between the epoxy resin and the curing agent.
- the curing accelerator include tertiary amines, imidazole-based curing accelerators, imidazoline-based curing accelerators, and phosphorus compounds.
- the imidazole-based curing accelerator and the imidazoline-based curing accelerator the compounds exemplified above as the imidazole-based curing agent and the imidazoline-based curing agent may be used.
- the liquid curing agents when a liquid acid anhydride is used, it is preferable to use a curing accelerator in combination.
- the paste may contain one or more curing accelerators. When a curing accelerator is used, the mechanical strength of the molded product formed from the paste can be improved, and the curing temperature of the paste can be easily lowered.
- the amount of the curing accelerator to be blended is not particularly limited as long as it can obtain the curing promoting effect.
- the amount of the curing accelerator is preferably 0.001 part by mass or more with respect to 100 parts by mass of the total of the epoxy resin and the curing agent. It may be there.
- the blending amount of the curing accelerator may be more preferably 0.01 part by mass or more, and further preferably 0.1 part by mass or more.
- the blending amount of the curing accelerator may be preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less.
- the blending amount of the curing accelerator is 0.001 part by mass or more, a sufficient curing promoting effect can be easily obtained.
- the blending amount of the curing accelerator is 5 parts by mass or less, excellent storage stability can be easily obtained in the paste.
- the effect according to the present invention can be obtained.
- the coupling agent may be, for example, at least one selected from the group consisting of a silane compound (silane coupling agent), a titanium compound, an aluminum compound (aluminum chelate), and an aluminum / zirconium compound.
- the silane coupling agent may be at least one selected from the group consisting of, for example, epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, acid anhydride-based silane, and vinylsilane.
- an aminophenyl-based silane coupling agent is preferable.
- the paste may contain at least one of the above coupling agents.
- the paste may contain the above two or more kinds of coupling agents.
- the paste may contain flame retardants.
- the flame retardant is selected from the group consisting of, for example, a brominated flame retardant, a phosphorus flame retardant, a hydrated metal compound flame retardant, a silicone flame retardant, a nitrogen-containing compound, a hindered amine compound, an organic metal compound and an aromatic engineering plastic. It may be at least one kind.
- the paste may contain one of the flame retardants exemplified above, or may contain two or more of them.
- the paste of the above embodiment may contain an organic solvent, if necessary.
- the organic solvent is not particularly limited.
- an organic solvent capable of dissolving the binder resin can be used.
- the organic solvent may be, for example, at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, carbitol acetate, butyl carbitol acetate, cyclohexanone, and xylene.
- the organic solvent is preferably a liquid at room temperature (25 ° C.).
- the boiling point of the organic solvent is preferably 50 ° C. or higher and 160 ° C. or lower.
- the paste contains an organic solvent
- a drying step is required after the paste is applied, which causes an environmental load due to volatile components.
- an organic solvent having a boiling point lower than the heating temperature at the time of curing it may volatilize at the time of heating to generate voids in the cured paste.
- the organic solvent is difficult to volatilize at the time of heating and may remain in the paste as it is to deteriorate the characteristics of the cured product.
- the presence of voids in the cured product tends to reduce properties such as mechanical strength and magnetic properties.
- the organic solvent remains in the cured product, the ionic components and the like in the cured product tend to move, and the insulating properties such as the insulation resistance value and the insulation reliability tend to decrease.
- the content thereof is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total mass of the paste. It is more preferably 1% by mass or less.
- the paste is substantially free of organic solvents. As used herein, “substantially free” means that no organic solvent was intentionally added to the paste. Therefore, the paste may contain, for example, an organic solvent that is used in the production of the resin and remains in the resin.
- the paste of the above embodiment can be adjusted to an appropriate viscosity without using a volatile component such as an organic solvent, and has fluidity.
- the viscosity of the paste is preferably 1 Pa ⁇ s or more, more preferably 10 Pa ⁇ s or more, and further preferably 100 Pa ⁇ s or more.
- the viscosity of the paste may be preferably 600 Pa ⁇ s or less, more preferably 400 Pa ⁇ s or less, and further preferably 200 Pa ⁇ s or less. By adjusting the viscosity to 600 Pa ⁇ s or less, the paste becomes fluid and good coatability can be easily obtained.
- the viscosity of the paste when the paste is applied to screen printing, is preferably 10 Pa ⁇ s to 400 Pa ⁇ s, more preferably 50 Pa ⁇ s to 300 Pa ⁇ s, still more preferably 100 Pa ⁇ s. It may be up to 250 Pa ⁇ s.
- the viscosity of the paste can be freely adjusted by the structure and characteristics of the epoxy group-containing compound, the structure and characteristics of the curing agent, the combination and compounding ratio thereof, and the structure and compounding ratio of additives such as the curing accelerator and the coupling agent. Can be adjusted.
- the paste may contain additives such as viscosity modifiers, thixotropic agents, and dispersion stabilizers.
- the paste of the above embodiment can be easily adjusted to the viscosity in the above preferable range even when the content of the metal element-containing powder is increased, without substantially using an organic solvent.
- a paste having a thermogravimetric reduction rate of 5% or less when heat-treated at 180 ° C. suppresses deterioration of the performance of the cured product due to volatile components such as an organic solvent, and has characteristics such as insulation. It is possible to easily provide an excellent molded product.
- the paste of the above embodiment can be prepared, for example, by uniformly stirring and kneading a metal element-containing powder and a binder resin containing at least an epoxy group-containing compound and a curing agent.
- the method of stirring and kneading is not particularly limited, and for example, a stirring blade, a self-revolving stirring, a roll mill, a disc mill, and a ball mill can be used.
- the paste may be cured by heat treatment to prepare a B-stage molded product. Further heat treatment of the B-stage molded body may sufficiently cure the resin in the molded body. Alternatively, a C-stage molded product may be produced from the paste at once.
- Various properties such as electromagnetic properties or thermal conductivity of the molded product can be freely controlled according to the composition or combination of the metal element-containing powder contained in the paste, and the molded product can be used for various industrial products or their raw materials. be able to.
- Industrial products manufactured using the paste may be, for example, automobiles, medical equipment, electronic equipment, electrical equipment, information and communication equipment, home appliances, audio equipment, and general industrial equipment.
- a molded body for example, a sheet formed from a paste containing a magnetic powder such as a Fe—Si—Cr based alloy or ferrite can be used as a raw material (for example, a magnetic core) for an inductor such as an EMI filter.
- the paste containing the powder of a permanent magnet can be used as a raw material for a bonded magnet.
- a molded body for example, a sheet formed from a paste containing iron powder and copper powder can be used as an electromagnetic wave shield.
- the molded product (cured product) formed by using the paste has a low CTE of 40 ppm / ° C. or less, and therefore can be suitably used for inductor applications.
- a cured product when a cured product is applied to a peripheral material with a low CTE such as a wiring board material using a paste, problems such as warpage caused by the difference in CTE, peeling at the interface with the peripheral material, and cracking can be easily suppressed. Can be done and reliability can be improved.
- binder resin 40.00 g of liquid epoxy resin "ADEKA Glycyrrol ED-503G” manufactured by ADEKA Corporation, and 13.33 g of curing agent “jER Cure WA” (liquid aromatic amine) manufactured by Mitsubishi Chemical Corporation. Weighed and these raw materials were placed in a 250 ml ointment container. A binder was obtained by stirring and kneading all the raw materials in the ointment container using a self-revolving stirrer. As the self-revolving stirrer, "ARE-500” manufactured by Shinky Co., Ltd. was used.
- the stirring and kneading was carried out over 1 minute by setting the revolution speed of the self-revolving stirrer to 2000 rpm.
- the binder resin was stirred with a spatula, and then the revolution speed of the self-revolving stirrer was set to 2000 rpm again, and the mixture was stirred and kneaded for 1 minute to obtain the binder resin I.
- the raw material in the ointment container was stirred with a spatula, and then the paste 1-1 was prepared by stirring twice for 45 seconds at a revolution speed of 2000 rpm using a rotation orbiting stirrer.
- the content of the metal powder in the obtained paste 1-1 was 97% by mass.
- the content of the metal powder is a value calculated from m / (m + M), where the mass of the non-volatile component (solid content) other than the metal powder contained in the paste is "M" and the mass of the metal powder is "m”. ..
- Paste 1-2 was prepared in the same manner as in Example 1-1, except that the blending amount of the binder resin I was changed to 3.45 g. The content of the metal powder in the obtained paste 1-2 was 95% by mass.
- Pastes 1-3 to 1-6 having the content of the metal powder shown in Table 1 were prepared in the same manner as in Example 1-1 except that the blending amount of the binder resin I was changed.
- binder resin 40.00 g of liquid epoxy resin "YDF-8170C” manufactured by Nippon Steel Chemical Corporation and curing agent “jER Cure WA” (liquid aromatic amine) manufactured by Mitsubishi Chemical Corporation 11. 13 g of each was weighed. These were used as raw materials and placed in a 250 ml ointment container. A binder resin was obtained by stirring and kneading all the raw materials in the ointment container using a self-revolving stirrer. As the self-revolving stirrer, "ARE-500” manufactured by Shinky Co., Ltd. was used.
- the stirring and kneading was carried out over 1 minute by setting the revolution speed of the self-revolving stirrer to 2000 rpm.
- the binder resin was stirred with a spatula, and then the revolution speed of the self-revolving stirrer was set to 2000 rpm again, and the mixture was stirred and kneaded for 1 minute to obtain a binder resin II.
- (2) Preparation of paste Using 5.51 g of binder resin II as a metal powder, iron amorphous alloy powder "KUAMET 9A4" manufactured by Epson Atmix Co., Ltd.
- the paste 2-1 was prepared by stirring twice at a revolution speed of 2000 rpm for 45 seconds using a rotation revolution stirrer.
- the content of the metal powder in the obtained paste 2-1 was 93% by mass.
- the content of the metal powder is a value calculated from m / (m + M), where the mass of the non-volatile component (solid content) other than the metal powder contained in the paste is "M” and the mass of the metal powder is "m”. ..
- Example 2-2 to Example 2-4 Pastes 2-2 to 2-4 having the metal powder content shown in Table 1 were prepared in the same manner as in Example 2-1 except that the blending amount of the binder resin II was changed.
- Example 3 3 g of the binder resin I prepared in the same manner as in Example 1-1 and 7 g of the binder resin II prepared in the same manner as in Example 2-1 were weighed. These were placed in an ointment container and stirred and kneaded using a self-revolving stirrer in the same manner as in Example 1-1 to obtain a binder resin I-II. Then, paste 3 having a metal powder content of 94% by mass was obtained in the same manner as in Example 2-1 except that the binder resin I-II was used.
- Example 4 Weigh 0.86 g of solid epoxy resin "NC-3000-H” manufactured by Nippon Kayaku Corporation and 0.14 g of curing agent "jER Cure WA” (liquid aromatic amine) manufactured by Mitsubishi Chemical Corporation. did. These were placed in an ointment container and kneaded with stirring using a self-revolving stirrer in the same manner as in Example 1-1 to obtain a binder resin III. Next, 7 g of the binder resin I prepared in the same manner as in Example 1 and 9 g of the binder resin III prepared above were weighed.
- Example 1-1 a binder resin I-III. Further, a paste 4 having a metal powder content of 94% by mass was obtained in the same manner as in Example 2-1 except that the binder resin I-III was used.
- Example 5 28.00 g of the liquid epoxy resin "YDF-8170C” manufactured by Nippon Steel Chemical Co., Ltd. and 12.00 g of the liquid epoxy resin "ADEKA Glycyllol ED-503G” manufactured by ADEKA Corporation were weighed in a 100 ml ointment container. It was stirred for 2 minutes at a revolution speed of 2000 rpm using a self-revolution stirrer. After stirring the raw materials in the ointment container using a spatula, the mixture was again stirred at a revolution speed of 2000 rpm for 2 minutes using a revolution stirrer.
- a binder resin IV was prepared by adding 2.00 g of a liquid imidal-based curing agent "Curesol 2E4MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd. and stirring at a revolution speed of 2000 rpm for 2 minutes using a rotation revolution stirrer. Then, except that the binder resin IV obtained above was used, the paste 5 having a metal powder content of 94% by mass was obtained in the same manner as in Example 2-1.
- Example 6 In the preparation of the binder resin IV in Example 5, the curing agent was changed to 13.08 g of 4,4'-diaminodiphenylmethane manufactured by Tokyo Chemical Industry Co., Ltd. to prepare the binder resin V. Next, a paste 6 having a metal powder content of 94% by mass was obtained in the same manner as in Example 2-1 except that the binder resin V obtained above was used.
- Example 7 In the preparation of the binder resin IV in Example 5, the curing agent was changed to 6.44 g of triethylenetetramine manufactured by Tokyo Chemical Industry Co., Ltd. to prepare the binder resin VI. Next, a paste 7 having a metal powder content of 94% by mass was obtained in the same manner as in Example 2-1 except that the binder resin VI obtained above was used.
- Example 8> In the preparation of the binder resin IV in Example 5, the curing agent was changed to 10.82 g of isophorone diamine manufactured by Tokyo Chemical Industry Co., Ltd. to prepare the binder resin VII. Then, except that the binder resin VII obtained above was used, a paste 8 having a metal powder content of 94% by mass was obtained in the same manner as in Example 2-1.
- Example 9 In the preparation of the binder resin IV in Example 5, the curing agent was changed to 2.00 g of trisdimethylaminomethylphenol manufactured by Tokyo Chemical Industry Co., Ltd. to prepare the binder resin VIII. Next, paste 9 having a metal powder content of 94% by mass was obtained in the same manner as in Example 2-1 except that the binder resin VIII obtained above was used.
- Example 10 In the preparation of the binder resin IV in Example 5, the curing agent was changed to 8.97 g of meta-phenylenediamine manufactured by Tokyo Chemical Industry Co., Ltd. to prepare the binder resin IX. Then, except that the binder resin IX obtained above was used, the paste 10 having a metal powder content of 94% by mass was obtained in the same manner as in Example 2-1.
- Example 11 In Example 5, 60.00 g of "KUAMET 9A4" (Fe—Si—B alloy having an insulating coating, D50: 20 ⁇ m) manufactured by Epson Atmix Co., Ltd. and “BSN” manufactured by Toda Kogyo Co., Ltd. were used as metal powders. -125 ”(Ni—Zn-based soft ferrite powder without insulating coating, D50: 10 ⁇ m) was used in an amount of 13.17 g. Except for this, paste 11 having a metal powder content of 94% by mass was obtained in the same manner as in Example 5.
- Binder Resin X 71.37 g of "Teisan Resin HTR-860-P3" (cyclohexanone solution having an acrylic resin content of 12.6 wt%) manufactured by Nagase ChemteX Corporation, manufactured by Nippon Kayaku Co., Ltd. Solid epoxy resin "NC-3000-H” 15.00g, curing agent "HP850N” (phenol novolac resin) manufactured by Showa Denko Materials Co., Ltd. (former Hitachi Kasei Co., Ltd.) 6.00g, manufactured by Shikoku Kasei Kogyo Co., Ltd.
- Binder resin varnish X was obtained by stirring and kneading all the raw materials in the ointment container with a self-revolving stirrer.
- the self-revolving stirrer "ARE-500” manufactured by Shinky Co., Ltd. was used. The stirring and kneading was carried out twice over 20 minutes by setting the revolution speed of the self-revolving stirrer to 2000 rpm.
- the NV (content of non-volatile component) of the obtained binder resin varnish X was 26.49% by mass.
- the component excluding the organic solvent (cyclohexanone or the like) is the binder resin X.
- the content of the metal powder is a value calculated from m / (m + M), where the mass of the non-volatile component (solid content) other than the metal powder contained in the paste 12 is "M” and the mass of the metal powder is "m”. Is.
- Viscosity classification 1: Viscosity is less than 1 Pa ⁇ s 2: Viscosity is 1 Pa ⁇ s or more, 10 Pa ⁇ s or less 3: Viscosity is 10 Pa ⁇ s or more, 400 Pa ⁇ s or less 4: Viscosity is 400 Pa ⁇ s or more, 600 Pa ⁇ s or less 5: Viscosity Exceeds 600 Pa ⁇ s
- thermogravimetric reduction rate of the paste was measured using a differential thermal weight simultaneous measuring device (TG-DSC) "NEXTA STA200RV" manufactured by Hitachi High-Tech Science Co., Ltd. Specifically, 15 mg of the paste was heated in a nitrogen atmosphere from 25 ° C. to 100 ° C. under the condition of 10 ° C./min and kept at 100 ° C. for 1 hour. Then, the temperature was raised from 100 ° C. to 180 ° C. under the condition of 3 ° C./min, and the amount of thermogravimetric reduction after heating while holding at 180 ° C. for 1 hour was measured.
- TG-DSC differential thermal weight simultaneous measuring device
- thermogravimetric reduction rate is calculated as the rate of weight loss (reduction rate) of the paste after heating at 180 ° C., based on the weight of the paste (before temperature rise) at 25 ° C. as a reference (100%).
- the content of volatile components in the paste can be evaluated by the thermogravimetric reduction rate. From the thermogravimetric reduction rate of the paste, when the following criteria of "AA", "A” or "B" are satisfied, it can be said that the content of the volatile component in the paste is small and good. The results are shown in Table 1.
- a vacuum press machine manufactured by Imoto Seisakusho Co., Ltd., manual hydraulic vacuum heating press, 1A31
- the insulation resistance was evaluated according to the following criteria. The results are shown in Table 1. When "A" or "B" is satisfied in the following criteria, the insulating property is good.
- the paste obtained in Examples and Comparative Examples was applied onto a comb-shaped wiring board having a line & space 200 ⁇ m / 200 ⁇ m pattern using the thickness of the polyimide tape as a spacer.
- the paste layer was then heated at 100 ° C. for 1 hour in a nitrogen atmosphere.
- the paste was prepared by raising the temperature from room temperature to 180 ° C. in 50 minutes under vacuum conditions in a vacuum dryer (Yamato Kagaku Co., Ltd., square vacuum constant temperature dryer, DP32) and maintaining the temperature for 60 minutes.
- Insulation resistance value of 10 6 ⁇ or more is 5 samples out of 5 samples
- B Insulation resistance value of 10 6 ⁇ or more is 4 samples out of 5 samples
- C Insulation resistance value is 10 6 ⁇ or more 3 samples or less out of 5 samples
- CTE Cost of thermal expansion
- the paste of the example was poured into the frame and preformed to obtain a paste layer.
- Preforming was carried out by heating the paste at 100 ° C. for 1 hour in a nitrogen atmosphere, subsequently heating to 150 ° C., then maintaining the temperature and heating for 20 minutes.
- a copper foil was put on the paste layer, and the paste layer was maintained at 165 ° C. and 2 MPa for 30 minutes using a vacuum press machine (manufactured by Imoto Seisakusho Co., Ltd., manual hydraulic vacuum heating press, 1A31).
- the paste of the comparative example contains an organic solvent, it was carried out as follows. First, the paste was bar-coated on the release-treated surface of the PET film with an applicator and heated at 120 ° C. for 20 minutes to form a dry paste layer having a thickness of about 50 ⁇ m. This paste layer was peeled off from the PET film and laminated, or laminated by vacuum laminating to premold to a size of 7 cm square and a thickness of about 1.2 mm.
- the pastes of the examples have a thermogravimetric reduction rate of 5% or less, and excellent insulation resistance and insulation reliability can be obtained in the cured product.
- the pastes of the examples all have a thermogravimetric reduction rate of 5% or less and a small content of volatile components such as organic solvents (substantially free of organic solvents), but have appropriate fluidity. It can be seen that it is maintained and has excellent coatability.
- the pastes of the examples are all good from the viewpoint of CTE.
- the pastes of the comparative examples all had a thermogravimetric reduction rate of more than 5%, resulting in inferior insulation resistance and insulation reliability. It is probable that the paste of the comparative example contained a large amount of organic solvent, so that the organic solvent remained in the cured product even after the paste was heat-cured, and a short circuit was likely to occur in the insulation reliability test. The reason why the low CTE was obtained in the cured product of the paste of the example is not clear, but it is presumed that at least the thermogravimetric reduction rate of the paste and the use of the curing agent are related.
- the paste according to the embodiment of the present invention can be suitably used, for example, as a material for the magnetic core of an inductor or as a material for filling between conductors of a coil, and can easily provide a molded product having excellent insulating properties.
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Abstract
Description
さらに、有機溶剤の使用は、硬化物の特性低下を招きやすい。例えば、有機溶剤の揮発による体積収縮によって、ペースト硬化物の内部に応力ひずみが溜まる。また、硬化時の加熱温度よりも低沸点の有機溶剤を使用した場合は、加熱時に有機溶剤が揮発することによって硬化物にボイドが発生しやすい。硬化物中にボイドが存在すると、硬化物の機械的強度及び磁気特性といった特性が低下しやすい。一方、硬化時の加熱温度よりも高沸点の有機溶剤を使用した場合、有機溶剤は加熱時に揮発し難く、そのまま硬化物中に残留し、製品特性の低下を招きやすい。特に、硬化物に有機溶剤が残留すると、硬化物中のイオン成分等が移動しやすくなり、絶縁抵抗値及び絶縁信頼性等の電気絶縁性(以下、絶縁性という)が低下しやすくなる。
このようなことから、有機溶剤の使用量を低減でき、加熱硬化後の硬化物における有機溶剤等の揮発性成分による性能低下を抑制し、優れた絶縁性等の特性を容易に得ることができる金属粉ペーストが望まれている。また、金属粉ペーストの硬化物の熱膨張係数(CTE)も重要な特性である。金属粉ペーストの硬化物のCTEと、硬化物が適用される周辺材料のCTEとの差が大きいと、加熱時の膨張差によって硬化物が反ったり、周辺材料との界面で剥離が発生したり、硬化物が割れたり不具合が生じやすい。そのため、例えば、インダクタの場合、銅コイル、及びインダクタが実装される配線板材料などのCTEは低いため、これらの周辺材料に合わせて、金属粉ペーストの硬化物のCTEも低いことが望まれる。
本願の開示は、2020年12月4日に出願された国際出願番号PCT/JP2020/45278に記載の主題と関連しており、これらのすべての開示内容は引用によりここに援用される。
本明細書において、「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値と任意に組み合わせることができる。
本明細書に例示する材料は、特に断らない限り、1種を単独で又は2種以上を組み合わせて用いることができる。本明細書において、組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
本発明の一実施形態であるペーストは、金属元素含有粉と、エポキシ基含有化合物と、硬化剤とを含み、ペーストは加熱処理によって硬化物を形成することができる。上記実施形態のペーストは、金属元素含有粉の配合量の増加に伴う粘度上昇を抑制でき、有機溶剤等の揮発性成分の含有量を低減できるため、ペーストから硬化物を形成した時の質量減少が少ないことを特徴とする。
なお、上記ペーストの硬化物は、真空条件下、165℃、2MPaで30分間維持し、次いで、180℃に昇温した後、温度を1時間にわたって維持する硬化条件でペーストを成形することによって得られる硬化物であってよい。硬化物の成形にあたり、上記硬化に先立ち、予備成形を行ってもよい。予備成形は、例えば、窒素雰囲気中、ペーストを100℃、1時間にわたって加熱し、引き続き、150℃まで昇温した後に、温度を維持し、20分間にわたって加熱することによって実施することができる。上記CTEの値は、0~250℃の温度範囲、昇温速度10℃/minの条件で測定した、ガラス転移温度以下の領域における線熱膨張係数を意味する。
(金属元素含有粉)
金属元素含有粉は、1種の金属元素又は2種以上の金属元素を含んでよい。金属元素含有粉は、例えば、金属単体、合金、及び金属化合物からなる群より選ばれる少なくとも1種の粉末であってよい。金属元素含有粉に含まれる金属元素は、例えば、卑金属元素、貴金属元素、遷移金属元素、及び希土類元素からなる群から選択される少なくとも1種であってよい。
金属元素は、例えば、鉄(Fe)、銅(Cu)、チタン(Ti)、マンガン(Mn)、コバルト(Co)、ニッケル(Ni)、亜鉛(Zn)、ニオブ(Nb)、アルミニウム(Al)、スズ(Sn)、クロム(Cr)、バリウム(Ba)、ストロンチウム(Sr)、鉛(Pb)、銀(Ag)、プラセオジム(Pr)、ネオジム(Nd)、サマリウム(Sm)、及びジスプロシウム(Dy)からなる群より選ばれる少なくとも1種であってよい。
金属元素含有粉は、例示した金属元素の単体、合金、及び金属化合物からなる群から選択される少なくとも1種を含んでよい。
Feアモルファス合金粉は、市販品として入手することもできる。例えば、エプソンアトミックス株式会社製の製品名AW2-08、及びKUAMET-6B2、大同特殊鋼株式会社製の製品名DAPMS3、DAPMS7、DAPMSA10、DAPPB、DAPPC、DAPMKV49、DAP410L、DAP430L、及びDAPHYBシリーズ、並びに株式会社神戸製鋼所製の製品名MH45D、MH28D、MH25D、及びMH20Dが挙げられる。これらのFeアモルファス合金粉の1種を使用しても、又は2種以上を組合せて使用してもよい。
一実施形態において、例えば、Fe系合金等の金属系の磁性粉は、その表面の全体又は一部が絶縁性材料によって被覆されていることが好ましい。絶縁性材料として、例えば、シリカ、チタニア、リン酸カルシウム、モンタンワックス、及びエポキシ樹脂硬化物が挙げられる。
一実施形態において、ペーストにおける金属元素含有粉の含有量は、ペーストの全質量を基準として、好ましくは80~99.9質量%以上であり、より好ましくは90~99.8質量%以上であり、さらに好ましくは94~96質量%であってよい。
エポキシ基含有化合物は、分子内に1以上のエポキシ基を有する化合物を意味し、モノマー、並びにモノマーの重合化によって形成される構造単位を有するオリゴマー及びポリマーのいずれの形態であってもよい。エポキシ基含有化合物は、加熱処理によって硬化し、金属元素含有粉を結着するバインダー樹脂として機能することができる。
エポキシ基含有化合物の一例として、一般的にエポキシ樹脂として知られる、分子内に2以上のエポキシ基を有するオリゴマー及びポリマーが挙げられる。エポキシ基含有化合物の他の例として、分子内に1以上のエポキシ基を有するが、重合化によって形成される構造単位を含まない化合物(以下、エポキシ化合物と称す)が挙げられる。このようなエポキシ化合物は、一般的に反応性希釈剤として知られている。エポキシ基含有化合物は、エポキシ樹脂、及びエポキシ化合物からなる群から選択される少なくとも1種を含むことが好ましい。
一方、エポキシ化合物の分子量は、好ましくは700以下であってよく、より好ましくは500以下であってよく、さらに好ましくは300以下であってよい。分子量が700以下であるエポキシ化合物を使用した場合、希釈剤として適切な粘度を容易に得ることができる。
エポキシ化合物は、十分に精製され、イオン性不純物の含有量が少ないことが好ましい。例えば、エポキシ化合物において、遊離Naイオン、及び遊離Clイオンといったイオン性不純物は、500ppm以下であることが好ましい。
熱硬化性樹脂は、例えば、フェノール樹脂、アクリル樹脂、ポリイミド樹脂、及びポリアミドイミド樹脂からなる群より選ばれる少なくとも1種であってよい。エポキシ基含有化合物に加えてフェノール樹脂を使用した場合、フェノール樹脂は、エポキシ基含有化合物の硬化剤として機能することもできる。
熱可塑性樹脂は、例えば、アクリル樹脂、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、及びポリエチレンテレフタレートからなる群より選ばれる少なくとも1種であってよい。樹脂成分は、エポキシ基含有化合物に加えて、さらにシリコーン樹脂を含んでもよい。
一実施形態において、エポキシ基含有化合物とその他の樹脂との混合物の粘度が、25℃において50Pa・s以下となる範囲で、配合量を調整することができる。上記粘度は、E型粘度計を用いて、温度:25℃、ロータ:コーンプレート、コーン角度:1°34’、回転速度:2.5rpmの条件下で測定した値である。E型粘度計として、例えば、東機産業株式会社製のTV-33型粘度計を使用することができる。
硬化剤は、特に制限されず、ペーストに適度な粘性を付与し、かつエポキシ基含有化合物のエポキシ基と反応し硬化物を形成することができる化合物であればよい。エポキシ樹脂の硬化剤として一般的に使用される周知の硬化剤であってよい。使用できる硬化剤として、例えば、フェノール系硬化剤、酸無水物系硬化剤、及びアミン系硬化剤が挙げられる。
低温から室温の温度範囲でエポキシ樹脂を硬化させる硬化剤を用いた場合、エポキシ樹脂の硬化物のガラス転移点は低く、エポキシ樹脂の硬化物は軟らかい傾向がある。その結果、ペーストから形成された成形体も軟らかくなる傾向がある。成形体の耐熱性及び機械的強度を向上させる観点から、硬化剤は、加熱硬化型硬化剤を含むことが好ましい。
ペーストの粘度上昇を抑えることができれば、25℃において固形の硬化剤を使用してもよく、液状の硬化剤と固形の硬化剤とを併用してもよい。固形の硬化剤としては、例えば、ジシアンジアミド、三級アミン、イミダゾール系硬化剤、及びイミダゾリン系硬化剤を使用することができる。例示した固形の硬化剤は、多官能であるか、又は触媒的に作用するため、少量でも十分に機能することができる。
アミン系硬化剤(より具体的には第3級アミン)、イミダゾール系硬化剤、及びイミダゾリン系硬化剤は、他の硬化剤との組合せにおいて硬化促進剤として使用することもできる。
脂肪族アミンとしては、直鎖構造又は環状構造を有する化合物であってよい。例えば、ジエチレントリアミン、トリエチレンテトラミン、n-プロピルアミン、2-ヒドロキシエチルアミノブロピルアミン、シクロへキシルアミン、メチルシクロヘキシルアミン、イソホロンジアミン、4,4’-ジアミノ-ジシクロへキシルメタン、ジアザビシクロウンデセン、が挙げられる。
芳香族アミンとしては、芳香族化合物にアミノ基が置換した化合物であってよく、特に、ベンゼン環の水素とアミノ基が置換した構造を有する化合物が好ましい。例えば、ベンジルジメチルアミン、トリスジメチルアミノメチルフェノール、メタフェニレンジアミン、ベンジルジメチルアミン、4,4’-ジアミノジフェニルメタン、2-メチルアニリン、ジアミノジフェニルスルフォン、ポリアミドアミン、下式(1)で表されるアミン化合物、下式(2)で表されるアミン化合物が挙げられる。
特に限定するものではないが、アミン系硬化剤を使用した場合、粘度及び熱重量減少量の調整が容易となる傾向がある。なかでも、芳香族アミンを使用した場合は、粘度及び熱重量減少率の調整がより容易となる傾向がある。
イミダゾリン系硬化剤は、イミダゾリン骨格を有する化合物であり、分子内の水素原子を置換基で置換したイミダゾリン系化合物であってよい。アルキル基置換イミダゾリン等のイミダゾリン骨格を有する化合物であってよい。イミダゾリン系硬化剤として、例えば、イミダゾリン、2-メチルイミダゾリン、及び2-エチルイミダゾリンが挙げられる。
一方、硬化剤中の活性基の比率が1.5当量以下である場合、ペーストから形成される加熱硬化後の成形体の機械的強度の低下を抑制できる。また、未反応の硬化剤によって硬化物の絶縁性が低下することを抑制できる。ただし、上記実施形態において、硬化剤中の活性基の比率は限定されず、上記範囲外であっても、本発明に係る効果を得ることはできる。
硬化促進剤は、エポキシ樹脂と硬化剤との硬化反応を促進できる化合物であれば限定されない。硬化促進剤として、例えば、第3級アミン、イミダゾール系硬化促進剤、イミダゾリン系硬化促進剤、及びリン化合物が挙げられる。イミダゾール系硬化促進剤及びイミダゾリン系硬化促進剤として、イミダゾール系硬化剤及びイミダゾリン系硬化剤として先に例示した化合物を使用してもよい。液状の硬化剤のなかでも、液状の酸無水物を使用した場合は、硬化促進剤を併用することが好ましい。ペーストは、1種又は2種以上の硬化促進剤を含んでよい。硬化促進剤を使用した場合、ペーストから形成された成形体の機械的強度を向上させ、またペーストの硬化温度を容易に低下させることができる。
カップリング剤を使用した場合、ペースト中の金属元素含有粉の分散性の向上、及びペースト粘度の制御が容易となる。また、バインダー樹脂と、金属元素含有粉との密着性の向上が容易となる。さらに、ペーストから形成される硬化物の基材に対する密着性、可撓性、機械的強度の向上が容易となる。カップリング剤は、例えば、シラン系化合物(シランカップリング剤)、チタン系化合物、アルミニウム化合物(アルミニウムキレート類)、及びアルミニウム/ジルコニウム系化合物からなる群より選ばれる少なくとも1種であってよい。シランカップリング剤は、例えば、エポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン、酸無水物系シラン及びビニルシランからなる群より選ばれる少なくとも1種であってよい。特に、アミノフェニル系のシランカップリング剤が好ましい。ペーストは、上記カップリング剤の少なくとも1種を含んでよい。ペーストは、上記2種以上のカップリング剤を含んでもよい。
ペーストの環境安全性、リサイクル性、成形加工性及び低コストのために、ペーストは難燃剤を含んでよい。難燃剤は、例えば、臭素系難燃剤、リン系難燃剤、水和金属化合物系難燃剤、シリコーン系難燃剤、窒素含有化合物、ヒンダードアミン化合物、有機金属化合物及び芳香族エンジニアリングプラスチックからなる群より選ばれる少なくとも1種であってよい。ペーストは、上記で例示した難燃剤の1種を含んでも、又は2種以上を含んでもよい。
一方、ペーストの粘度は、好ましくは600Pa・s以下、より好ましくは400Pa・s以下、さらに好ましくは200Pa・s以下であってよい。粘度を600Pa・s以下に調整することで、ペーストに流動性が生じ、良好な塗布性を容易に得ることができる。
粘度を上記範囲に調整した場合、スクリーン印刷においては、版の開口部をペーストが透過しなくなる不具合の発生を抑制することができる。ペーストの粘度は、エポキシ基含有化合物の構造及び特性、硬化剤の構造及び特性、並びにこれらの組合せ及び配合比、さらに硬化促進剤及びカップリング剤等の添加剤の構造及び配合比等によって自在に調整することができる。ペーストは、粘度調整剤、チキソ性付与剤、及び分散安定剤等の添加剤を含んでもよい。
上記実施形態のペーストは、例えば、金属元素含有粉と、少なくともエポキシ基含有化合物及び硬化剤を含むバインダー樹脂とを均一に撹拌混練することによって作製することができる。撹拌混錬の方法特に限定されず、例えば、撹拌羽根、自公転式撹拌、ロールミル、ディスクミル、及びボールミルを使用することができる。
上記実施形態のペーストから成形体を形成する場合、加熱処理によってペーストの硬化を進めBステージの成形体を作製してよい。Bステージの成形体の更なる加熱処理によって、成形体中の樹脂を十分に硬化させてよい。あるいは、ペーストから一気にCステージの成形体を作製してもよい。
ペーストに含まれる金属元素含有粉の組成又は組合せに応じて、成形体の電磁気的特性又は熱伝導性等の各種特性を自在に制御し、成形体を様々な工業製品又はそれらの原材料に利用することができる。
ペーストを用いて製造される工業製品は、例えば、自動車、医療機器、電子機器、電気機器、情報通信機器、家電製品、音響機器、及び一般産業機器であってよい。例えば、Fe-Si-Cr系合金又はフェライト等の磁性粉を含むペーストから形成された成形体(例えばシート)は、EMIフィルタ等のインダクタの原材料(例えば磁心)として利用することができる。永久磁石の粉末を含むペーストは、ボンド磁石の原材料として利用することができる。鉄粉と銅粉とを含むペーストから形成された成形体(例えばシート)は、電磁波シールドとして利用することができる。一実施形態では、ペーストを用いて形成した成形体(硬化物)は、40ppm/℃以下の低いCTEとなるため、インダクタの用途で好適に使用することができる。例えば、配線板材料などのCTEが低い周辺材料にペーストを用いて硬化物を適用した場合、CTEの差によって生じる反り、周辺材料との界面での剥離、及び割れといった不具合の発生を容易に抑制することができ、信頼性を高めることができる。
(1)バインダー樹脂の調製
株式会社ADEKA製の液状エポキシ樹脂「アデカグリシロールED-503G」40.00g、三菱ケミカル株式会社製の硬化剤「jERキュアWA」(液状の芳香族アミン)13.33gを秤量し、これら原料を250mlの軟膏容器に入れた。
軟膏容器内の全原料を、自公転撹拌機を用い撹拌混練することによって、バインダーを得た。自公転撹拌機としては、シンキー株式会社製の「ARE-500」を用いた。撹拌混練は、自公転撹拌機の公転速度を2000rpmに設定し、1分間にわたって実施した。上記バインダー樹脂を、薬さじを用いて撹拌した後、再び、自公転撹拌機の公転速度を2000rpmに設定し、1分間にわたって撹拌混練することによって、バインダー樹脂Iを得た。
(2)ペーストの調製
上記バインダー樹脂Iを2.26g、金属元素含有粉(以下、金属粉という)として、エプソンアトミックス株式会社製の鉄アモルファス合金粉「KUAMET 9A4」(絶縁被覆を有するFe-Si-B系合金、D50:20μm)を60.00g、及び新東工業株式会社製の金属ガラス磁性粉「SAP-2C」(絶縁被覆を有するFe-Si-B-P-Nb-Cr系合金、D50:2.2μm)を13.17g、並びに信越シリコーン株式会社製のシランカップリング剤「KBM-573」を0.22g、それぞれ秤量し、これら原料を50mlの軟膏容器に入れた。
軟膏容器内の原料を、自公転撹拌機を用いて公転速度2000rpmで45秒にわたって撹拌した。薬さじを用いて軟膏容器内の原料を撹拌した後、自公転撹拌機を用いて公転速度2000rpmで45秒にわたって2回撹拌することによって、ペースト1-1を調製した。
得られたペースト1-1中の金属粉の含有量は97質量%であった。金属粉の含有量は、ペーストに含まれる金属粉以外の不揮発性成分(固形分)の質量を「M」、金属粉の質量を「m」とし、m/(m+M)から算出した値である。
バインダー樹脂Iの配合量を3.45gに変更したことを除き、全て実施例1-1と同様にしてペースト1-2を調製した。得られたペースト1-2中の金属粉の含有量は95質量%であった。
バインダー樹脂Iの配合量を変更したことを除き、全て実施例1-1と同様にして、表1に示した金属粉の含有量となるペースト1-3~1-6を調製した。
(1)バインダー樹脂の調製
新日鐵化学製の液状エポキシ樹脂「YDF-8170C」を40.00g、及び三菱ケミカル株式会社製の硬化剤「jERキュアWA」(液状の芳香族アミン)を11.13g、それぞれ秤量した。これらを原料として、250mlの軟膏容器に入れた。
軟膏容器内の全原料を、自公転撹拌機を用いて撹拌混練することによって、バインダー樹脂を得た。自公転撹拌機としては、シンキー株式会社製の「ARE-500」を用いた。撹拌混練は、自公転撹拌機の公転速度を2000rpmに設定し、1分間にわたって実施した。上記バインダー樹脂を、薬さじを用いて撹拌した後、再び、自公転撹拌機の公転速度を2000rpmに設定し、1分間にわたって撹拌混練することによって、バインダー樹脂IIを得た。
(2)ペーストの調製
バインダー樹脂IIを5.51g、金属粉として、エプソンアトミックス株式会社製の鉄アモルファス合金粉「KUAMET 9A4」(絶縁被覆を有するFe-Si-B系合金、D50:20μm)を60.00g、及び新東工業株式会社製の金属ガラス磁性粉「SAP-2C」(絶縁被覆を有するFe-Si-B-P-Nb-Cr系合金、D50:2.2μm)を13.17g、並びに信越シリコーン株式会社製のシランカップリング剤「KBM-573」を0.22g、それぞれ秤量した。これらを原料として、50mlの軟膏容器に入れた。
軟膏容器内の全原料を、自公転撹拌機を用いて公転速度2000rpmで45秒にわたって撹拌混練した。次いで、薬さじを用いて軟膏容器内の原料を撹拌した後、自公転撹拌機を用いて公転速度2000rpmで45秒にわたって2回撹拌し、ペースト2-1を調製した。
得られたペースト2-1中の金属粉の含有量は93質量%であった。金属粉の含有量は、ペーストに含まれる金属粉以外の不揮発性成分(固形分)の質量を「M」、金属粉の質量を「m」とし、m/(m+M)から算出した値である。
バインダー樹脂IIの配合量を変更したことを除き、全て実施例2-1と同様にして、表1に示した金属粉含有量となるペースト2-2~2-4を調製した。
実施例1-1と同様にして調製したバインダー樹脂Iを3g、実施例2-1と同様にして調製したバインダー樹脂IIを7g、それぞれ秤量した。これらを軟膏容器に入れ、実施例1-1と同様にして自公転撹拌機を用いて撹拌混練することによって、バインダー樹脂I-IIを得た。
次いで、バインダー樹脂I-IIを使用したことを除き全て実施例2-1と同様にして、金属粉の含有量が94質量%のペースト3を得た。
日本化薬株式会社製の固形エポキシ樹脂「NC-3000-H」を0.86g、及び三菱ケミカル株式会社製の硬化剤「jERキュアWA」(液状の芳香族アミン)を0.14g、それぞれ秤量した。これらを軟膏容器に入れ、実施例1-1と同様にして自公転撹拌機を用いて撹拌混練することによって、バインダー樹脂IIIを得た。
次いで、実施例1と同様にして調製したバインダー樹脂Iを7g、先に調製したバインダー樹脂IIIを9g、それぞれ秤量した。これらを軟膏容器に入れ、実施例1-1と同様にして自公転撹拌機を用いて撹拌混練することによって、バインダー樹脂I-IIIを得た。
さらに、バインダー樹脂I-IIIを使用したことを除き、全て実施例2―1と同様にして、金属粉の含有量が94質量%であるペースト4を得た。
新日鐵化学製の液状エポキシ樹脂「YDF-8170C」を28.00g、及び株式会社ADEKA製の液状エポキシ樹脂「アデカグリシロールED-503G」12.00gを100mlの軟膏容器にそれぞれ秤量した。自公転撹拌機を用いて公転速度2000rpmで2分間撹拌した。薬さじを用いて軟膏容器内の原料を撹拌した後、再度自公転撹拌機を用いて公転速度2000rpmで2分間撹拌した。四国化成工業株式会社製の液状のイミダール系硬化剤「キュアゾール2E4MZ」2.00gを加え、自公転撹拌機を用いて公転速度2000rpmで2分間撹拌することによって、バインダー樹脂IVを調製した。
次いで、先に得たバインダー樹脂IVを使用したことを除き、全て実施例2-1と同様にして、金属粉の含有量が94質量%のペースト5を得た。
実施例5におけるバインダー樹脂IVの調製において、硬化剤を東京化成工業株式会社製の4,4’-ジアミノジフェニルメタン13.08gに変更し、バインダー樹脂Vを調製した。
次いで、先に得たバインダー樹脂Vを使用したことを除き、全て実施例2-1と同様にして、金属粉の含有量が94質量%のペースト6を得た。
実施例5におけるバインダー樹脂IVの調製において、硬化剤を東京化成工業株式会社製のトリエチレンテトラミン6.44gに変更し、バインダー樹脂VIを調製した。
次いで、先に得たバインダー樹脂VIを使用したことを除き、全て実施例2-1と同様にして、金属粉の含有量が94質量%のペースト7を得た。
実施例5におけるバインダー樹脂IVの調製において、硬化剤を東京化成工業株式会社製のイソホロンジアミン10.82gに変更し、バインダー樹脂VIIを調製した。
次いで、先に得たバインダー樹脂VIIを使用したことを除き、全て実施例2-1と同様にして、金属粉の含有量が94質量%のペースト8を得た。
実施例5におけるバインダー樹脂IVの調製において、硬化剤を東京化成工業株式会社製のトリスジメチルアミノメチルフェノール2.00gに変更し、バインダー樹脂VIIIを調製した。
次いで、先に得たバインダー樹脂VIIIを使用したことを除き、全て実施例2-1と同様にして、金属粉の含有量が94質量%のペースト9を得た。
実施例5におけるバインダー樹脂IVの調製において、硬化剤を東京化成工業株式会社製のメタフェニレンジアミン8.97gに変更し、バインダー樹脂IXを調製した。
次いで、先に得たバインダー樹脂IXを使用したことを除き、全て実施例2-1と同様にして、金属粉の含有量が94質量%のペースト10を得た。
実施例5において、金属粉としてエプソンアトミックス株式会社製の「KUAMET 9A4」(絶縁被覆を有するFe-Si-B系合金、D50:20μm)を60.00g、及び戸田工業株式会社製の「BSN-125」(絶縁被覆なしのNi-Zn系ソフトフェライト粉、D50:10μm)を13.17g使用した。これ以外は、全て実施例5と同様にして、金属粉の含有量が94質量%のペースト11を得た。
(1)バインダー樹脂Xの調製
ナガセケムテックス株式会社製の「テイサンレジンHTR-860-P3」(アクリル樹脂含有量が12.6重量%のシクロヘキサノン溶液)71.37g、日本化薬株式会社製の固形エポキシ樹脂「NC-3000-H」15.00g、昭和電工マテリアルズ株式会社(旧日立化成株式会社)製の硬化剤「HP850N」(フェノールノボラック樹脂)6.00g、四国化成工業株式会社製の硬化促進剤「2E4MZ」0.15g、及び富士フイルム和光純薬株式会社製の「シクロヘキサノン」21.30gをそれぞれ秤量した。これら原料を、250mlの軟膏容器に入れた。
軟膏容器内の全原料を自公転撹拌機で撹拌混練することによって、バインダー樹脂ワニスXを得た。自公転撹拌機としては、シンキー株式会社製の「ARE-500」を用いた。撹拌混練は、自公転撹拌機の公転速度を2000rpmに設定し、20分間にわたって2回実施した。得られたバインダー樹脂ワニスXのNV(不揮発性成分の含有量)は、26.49質量%であった。バインダー樹脂ワニスXのうち、有機溶剤(シクロヘキサノン等)を除く成分がバインダー樹脂Xとなる。
(2)ペーストの調製
バインダー樹脂ワニスXを8.54g、金属粉として、エプソンアトミックス株式会社製の「KUAMET 9A4」(絶縁被覆を有するFe-Si-B系合金、D50:20μm)を60.00g、及び新東工業株式会社製の「SAP-2C」(絶縁被覆を有するFe-Si-B-P-Nb-Cr系合金、D50:2.2μm)を13.17g、並びに信越シリコーン株式会社製のシランカップリング剤「KBM-573」を0.22g、それぞれ秤量した。これらを原料として、50mlの軟膏容器に入れた。
軟膏容器内の全原料を、自公転撹拌機を用いて公転速度2000rpmで45秒にわたって撹拌混練した。次いで、薬さじを用いて、軟膏容器内の原料を撹拌した。さらに、自公転撹拌機を用いて公転速度2000rpmで45秒にわたって2回撹拌することによって、ペースト12を調製した。
得られたペースト12の全固形分を基準とする金属粉の含有量は97質量%であった。上記金属粉の含有量は、ペースト12に含まれる金属粉以外の不揮発性成分(固形分)の質量を「M」、金属粉の質量を「m」とし、m/(m+M)から算出した値である。
バインダー樹脂ワニスXの配合量を変更したことを除き、全て比較例1と同様にして、金属粉を84質量%含むペースト13を調製した。
実施例及び比較例で得た各ペーストについて、以下に記載する方法に従い各種特性を評価した。
<粘度の評価>
実施例及び比較例で得た各ペーストについて、東機産業株式会社製のTV-33型粘度計を用い、温度:25℃、ロータ:SPP、及び回転速度:2.5rpmの条件下で粘度を測定した。測定値を以下の基準に従って評価した。結果を表1に示す。スクリーン印刷を想定した場合、区分2、3及び4であれば良好な塗布性を容易に得ることができる。なかでも、区分3が最も好ましい。
(粘度区分)
1:粘度が1Pa・s未満
2:粘度が1Pa・s以上、10Pa・s以下
3:粘度が10Pa・s以上、400Pa・s以下
4:粘度が400Pa・s以上、600Pa・s以下
5:粘度が600Pa・sを超える
ペーストの熱重量減少率は、日立ハイテクサイエンス株式会社製の示差熱熱重量同時測定装置(TG-DSC)「NEXTA STA200RV」を用いて測定した。具体的には、15mgのペーストを、窒素雰囲気中、25℃から100℃まで10℃/分の条件で昇温し、100℃で1時間保持した。その後、100℃から180℃まで3℃/分の条件で昇温し、180℃で1時間保持しながら加熱した後の熱重量減少量を測定した。
熱重量減少率は、25℃における(昇温前の)ペーストの重量を基準(100%)とする、180℃における加熱後のペーストの重量減少の割合(減少率)として算出される。熱重量減少率によって、ペースト中の揮発性成分の含有量を評価することができる。ペーストの熱重量減少率から、下記「AA」、「A」又は「B」の基準を満たした場合は、ペーストにおける揮発成分の含有量が少なくて良好といえる。結果を表1に示す。
(評価基準)
AA:熱重量減少率が0%以上、1.0%以下
A:熱重量減少率が1.0%より大きく、3.0%以下
B:熱重量減少率が3.0%より大きく、5.0%以下
C:熱重量減少率が5.0%より大きい
Uniontape社製のポリイミドテープ(厚さ125μm)を8枚重ねて銅箔上に貼り付け、7cm角の四角形の枠を作製した。その枠内にペーストを流し入れ、ペースト層を窒素雰囲気中、100℃で、1時間にわたって加熱した。引き続き、150℃まで昇温した後に、温度を維持し、20分間にわたって加熱した。
次に、ペースト層の上から、他の銅箔を被せて、真空プレス機(株式会社井元製作所製、手動油圧真空加熱プレス、1A31)を用い、真空条件下、165℃、及び2MPaで30分間維持した。次いで、180℃に昇温した後、1時間にわたって温度を維持し、ペースト層を硬化させた。
次に、上下面両方の銅箔を剥離し、ペーストの硬化物からなるサンプル板を得た。サンプル板(ペーストの硬化物)の膜厚は1mmであった。サンプル板の体積抵抗率を、4端針面抵抗測定器で測定した面抵抗値と、マイクロメーターから求めた膜厚とから計算した。絶縁抵抗(絶縁性)を下記基準にしたがって評価した。結果を表1に示す。下記基準において「A」又は「B」を満たした場合、絶縁性が良好である。
(評価基準)
A:体積抵抗率が1.0×1012μΩ・cm以上
B:体積抵抗率が1.0×1011μΩ・cm以上、1.0×1012μΩ・cm未満
C:体積抵抗率が1011μΩ・cm未満
株式会社タク技研製のメタルスキージを用い、ポリイミドテープの厚みをスペーサーとして、ライン&スペース200μm/200μmのパターンを有する櫛型配線基板の上に、実施例及び比較例で得たペーストを塗布した。次いで、ペースト層を、窒素雰囲気中、100℃、1時間にわたって加熱した。次いで、減圧乾燥機(ヤマト科学株式会社製、角型真空定温乾燥機、DP32)内で真空条件下、50分間で室温から180℃まで昇温し、温度を60分間にわたって維持することによって、ペーストを硬化させ、配線基板上に膜厚100μmの硬化物層(絶縁磁性層)を形成した。
上述のようにして得た硬化物層を有する配線基板をサンプルとして使用し、初期の絶縁抵抗値と、絶縁抵抗のマイグレーション試験後の絶縁抵抗値を測定した。マイグレーション試験では、温度85℃、湿度85%、12V印加の条件で、500時間にわたってサンプルを放置した。
初期の絶縁抵抗値が106Ω以上である5つのサンプルについて、マイグレーション試験後の絶縁抵抗値が106Ω以上となるサンプルの割合を調べ、配線間の絶縁信頼性を評価した。具体的には、下記基準にしたがって絶縁信頼性を評価した。結果を表1に示す。下記基準において「A」又は「B」を満たした場合、絶縁信頼性は良好である。
(評価基準)
A:絶縁抵抗値106Ω以上の割合が全5サンプル中、5サンプル
B:絶縁抵抗値106Ω以上の割合が全5サンプル中、4サンプル
C:絶縁抵抗値106Ω以上の割合が全5サンプル中、3サンプル以下
Uniontape社製のポリイミドテープ(厚さ125μm)を8枚重ねて銅箔上に貼り付け、7cm角の四角状の枠を設けた。その枠内に実施例のペーストを流し入れ、予備成形しペースト層を得た。予備成形は、窒素雰囲気中、ペーストを100℃で1時間にわたって加熱し、引き続き、150℃まで昇温した後に、温度を維持し、20分間にわたって加熱することによって実施した。次に、ペースト層の上に銅箔を被せて、真空プレス機(株式会社井元製作所製、手動油圧真空加熱プレス、1A31)を用い、真空条件下、165℃、2MPaで30分間にわたって維持した。次いで、180℃に昇温した後、温度を1時間にわたって維持し、ペースト層を硬化させた(膜厚1mm)。
一方、比較例のペーストについては、有機溶剤を含有するため、以下のように実施した。先ず、PETフィルムの離型処理面上に、ペーストをアプリケーターでバーコートし、120℃で20分間にわたって加熱することによって、厚さ50μm程度の乾燥したペースト層を形成した。このペースト層をPETフィルムから剥離して、重ねるか、あるいは真空ラミネートで貼り合せることによって、7cm角、厚さ1.2mm程度に予備成形した。次に、Uniontape社製のポリイミドテープ(厚さ125μm)を8枚重ねて銅箔上に貼り付け、7cm角の四角状の枠を設けた。枠内に先に予備成形したペースト層を置き、上から銅箔を被せて、真空プレス機(株式会社井元製作所製、手動油圧真空加熱プレス、1A31)を用い、真空条件下、165℃、2MPaで30分間維持した。次いで、180℃に昇温した後、温度を1時間にわたって維持し、ペースト層を硬化させた(膜厚1mm)。
次に、上述のようにして硬化させたペースト層の上下面両方の銅箔を剥離し、実施例及び比較例のペーストの硬化物からなるサンプル板をそれぞれ得た。このサンプル板から10mm角のサンプル片を切り出した。サンプル片のCTE(熱膨張係数)を、TMA(TA Instruments社製、熱機械分析装置、TMA-Q400)を用いて測定した。測定は、0~250℃の範囲を昇温速度10℃/minの条件で行い、ガラス転移温度以下の領域における線膨張係数α1(ppm/℃)を算出した。得られたα1の値に基づき下記基準にしたがってCTEを評価した。結果を表1に示す。下記基準において「AA」、「A」及び「B」を満たした場合、CTEは良好である。
(評価基準)
AA:α1が25ppm/℃以下
A:α1が25ppm/℃超過、30ppm/℃以下
B:α1が30ppm/℃超過、40ppm/℃以下
C:α1が40ppm/℃超過
Claims (10)
- 金属元素含有粉と、エポキシ基含有化合物と、硬化剤とを含有するペーストであって、180℃における加熱硬化後の熱重量減少率が5%以下であるペースト。
- 前記硬化剤が、アミン系硬化剤、及びイミダゾール系硬化剤からなる群から選択される少なくとも1種を含む、請求項1に記載のペースト。
- 前記エポキシ基含有化合物が、25℃において液状であるエポキシ樹脂を含む、請求項1又は2に記載のペースト。
- 前記硬化剤が、25℃において液状である硬化剤を含む、請求項1~3のいずれか1項に記載のペースト。
- ペーストの全質量を基準として、前記金属元素含有粉の含有量が、70質量%以上である、請求項1~4のいずれか1項に記載のペースト。
- 前記金属元素含有粉が、磁性粉を含む、請求項1~5のいずれか1項に記載のペースト。
- 25℃における粘度が、1Pa・s以上、600Pa・s以下である、請求項1~6のいずれか1項に記載のペースト。
- 前記アミン系硬化剤が、芳香族アミンを含む、請求項1~7のいずれか1項に記載のペースト。
- 硬化物の熱膨張係数が40ppm/℃以下である、請求項1~8のいずれか1項に記載のペースト。
- スクリーン印刷に使用される、請求項1~9のいずれか1項に記載のペースト。
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