WO2021241515A1 - Composé, corps moulé et produit durci - Google Patents

Composé, corps moulé et produit durci Download PDF

Info

Publication number
WO2021241515A1
WO2021241515A1 PCT/JP2021/019655 JP2021019655W WO2021241515A1 WO 2021241515 A1 WO2021241515 A1 WO 2021241515A1 JP 2021019655 W JP2021019655 W JP 2021019655W WO 2021241515 A1 WO2021241515 A1 WO 2021241515A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
epoxy resin
resin
metal powder
mass
Prior art date
Application number
PCT/JP2021/019655
Other languages
English (en)
Japanese (ja)
Inventor
貴一 稲葉
翔平 山口
Original Assignee
昭和電工マテリアルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to CN202180037169.2A priority Critical patent/CN115698119A/zh
Priority to KR1020227044004A priority patent/KR20230015941A/ko
Priority to JP2022526538A priority patent/JPWO2021241515A1/ja
Publication of WO2021241515A1 publication Critical patent/WO2021241515A1/fr

Links

Classifications

    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • 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
    • H01F1/22—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 pressed, sintered, or bound together
    • H01F1/24—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 pressed, sintered, or bound together the particles being insulated
    • H01F1/26—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 pressed, sintered, or bound together the particles being insulated by macromolecular organic substances

Definitions

  • One aspect of the present invention relates to compounds, molded bodies and cured products.
  • the compound containing metal powder and thermosetting resin is used as a raw material for various industrial products such as Indaku, depending on the physical characteristics of the metal powder (see Patent Documents 1 and 2 below).
  • the compound When an industrial product is manufactured from a compound, the compound is supplied and filled into the mold through a flow path, and parts such as coils are embedded in the compound in the mold.
  • the fluidity of the compound is required in these steps. If the compound does not have sufficient fluidity, it is difficult for the compound to be uniformly filled in the mold, and voids are likely to be formed in the molded body formed from the compound.
  • the fluidity of the compound increases as the content of the metal powder in the compound decreases.
  • the content (filling rate) of the metal powder in the compound is high.
  • the magnetic property values of a compound such as relative permeability and saturation magnetic flux density increase with increasing content of metal powder in the compound.
  • the compound becomes more difficult to flow.
  • the present invention has been made in view of the above problems, and an object of one aspect of the present invention is to provide a compound having excellent fluidity, a molded product containing the compound, and a cured product of the compound.
  • the compound according to one aspect of the present invention is a compound containing at least a metal powder and a resin composition, wherein the resin composition contains at least an epoxy resin and a phosphoric acid ester, and the content of the epoxy resin in the compound is. It is 1.0% by mass or more and 2.0% by mass or less.
  • the ratio of the phosphoric acid ester to 100 parts by mass of the metal powder may be 0.01 parts by mass or more and 0.05 parts by mass or less.
  • the melt viscosity of the compound at 140 ° C. may be 10 Pa ⁇ s or more and 1500 Pa ⁇ s or less.
  • the content of the metal powder in the compound may be 90% by mass or more and 98% by mass or less.
  • the compound according to one aspect of the present invention may be used for at least one of transfer molding and compression molding.
  • the molded body according to one aspect of the present invention includes the above compound.
  • the cured product according to one aspect of the present invention is a cured product of the above compound.
  • a compound having excellent fluidity, a molded product containing the compound, and a cured product of the compound are provided.
  • the compound according to this embodiment contains at least a metal powder and a resin composition. That is, the compound may be a mixture of a metal powder and a resin composition.
  • the compound may be paraphrased as a magnetic encapsulant.
  • Metal powder is composed of a large number of metal particles.
  • the metal powder may contain, for example, at least one selected from the group consisting of elemental metals (pure metals), alloys, amorphous powders and metal compounds.
  • the metal powder may be paraphrased as a filler made of metal.
  • the resin composition contains at least an epoxy resin and a phosphoric acid ester.
  • the epoxy resin melts at a temperature lower than the curing temperature, which improves the fluidity of the compound.
  • the epoxy resin binds metal powders to each other by thermosetting.
  • the epoxy resin electrically insulates the metal powders from each other.
  • the content of the epoxy resin in the compound is 1.0% by mass or more and 2.0% by mass or less. When the content of the epoxy resin in the compound is within the above range and the compound contains a phosphoric acid ester, the compound can have high fluidity (low melt viscosity). When the content of the epoxy resin in the compound is less than the lower limit, the compound is unlikely to have high fluidity.
  • the compound is unlikely to have high fluidity. If the content of the epoxy resin in the compound is greater than the upper limit, it is difficult to produce the compound. Since the compound tends to have high fluidity, the content of the epoxy resin in the compound may be 1.86% by mass or more and 1.90% by mass or less. In other words, the ratio of the epoxy resin to 100 parts by mass of the metal powder may be 1.92 parts by mass or more and 1.97 parts by mass or less.
  • the phosphoric acid ester may be represented, for example, OP (OR 1 ) (OR 2 ) (OR 3).
  • R 1 , R 2 and R 3 are each hydrogen or any hydrocarbon group, and at least one of R 1 , R 2 and R 3 is a hydrocarbon group.
  • the hydrocarbon group may be, for example, an alkyl group or an aryl group.
  • Phosphite ester is a compound different from phosphite ester.
  • the phosphite ester may be represented, for example, P (OR 1 ) (OR 2 ) (OR 3).
  • the resin composition may further contain a phosphite ester in addition to the phosphoric acid ester.
  • the resin composition may further contain other dispersants (eg, coupling agents).
  • the phosphoric acid ester may be a dispersant. Since the phosphoric acid group of the phosphoric acid ester has polarity, it easily easily selectively adsorbs to the surface of the metal particles. On the other hand, since the hydrocarbon group of the phosphoric acid ester has lipophilicity, the resin composition containing the epoxy resin is likely to intervene between the metal particles to which the phosphoric acid ester is adsorbed. Therefore, due to the phosphoric acid ester, the aggregation of the metal powder is suppressed, and each metal particle is easily dispersed in the compound.
  • the action of the phosphoric acid ester on the metal powder as a dispersant improves the fluidity of the compound.
  • the inclusion of phosphate in the compound reduces the melt viscosity of the compound.
  • the fluidity of a compound containing a phosphate ester tends to be better than the fluidity of a compound containing a dispersant other than the phosphate ester.
  • the direct friction between the metal particles may be evaluated based on the torque value measured by the gel time measuring device. The more the direct friction between the metal particles is suppressed, the lower the torque value is.
  • a CURELASTOMETER manufactured by JSR Corporation may be used.
  • the melt viscosity of the compound at 140 ° C. may be 10 Pa ⁇ s or more and 1500 Pa ⁇ s or less, preferably 401 Pa ⁇ s or more and 650 Pa ⁇ s or less.
  • the compound can have a low melt viscosity (high fluidity) as described above.
  • the melt viscosity of the compound is within the above range, the melted compound is easily filled into the mold without unevenness, and defects (voids or burrs, etc.) in the molded product and the cured product formed from the compound are suppressed. Easy to do. Therefore, a compound having a low melt viscosity as described above is suitable for transfer molding.
  • the ratio of the phosphoric acid ester to 100 parts by mass of the metal powder may be 0.01 parts by mass or more and 0.05 parts by mass or less.
  • the ratio of the phosphoric acid ester is 0.01 parts by mass (preferably 0.02 parts by mass) or more, high fluidity (low melt viscosity) of the compound due to the phosphoric acid ester can be easily obtained.
  • Phosphoric acid ester may inhibit the curing of the epoxy resin.
  • the ratio of the phosphoric acid ester is 0.05 parts by mass or less, the inhibition of curing of the epoxy resin due to the phosphoric acid ester is likely to be suppressed.
  • the ratio of the phosphate ester when the ratio of the phosphate ester is 0.05 parts by mass or less, the gelation time (curing time) of the compound is shortened.
  • the ratio of the phosphoric acid ester to 100 parts by mass of the metal powder may be 0.02 parts by mass or more and 0.03 parts by mass or less.
  • the content of the metal powder in the compound may be 90% by mass or more and 98% by mass or less, or 96% by mass or more and 97.5% by mass or less.
  • the relative permeability and the saturated magnetic flux density of the compound tend to increase.
  • Compounds with high relative permeability and high saturation magnetic flux density are suitable, for example, as encapsulants for inductors or raw materials for the core of inductors.
  • the compound becomes difficult to flow. If the content of the metal powder in the compound containing no phosphoric acid ester is 90% by mass or more, the melt viscosity of the compound is significantly increased.
  • the compound according to the present embodiment contains a phosphoric acid ester together with an epoxy resin, so that it has high fluidity (low melt viscosity). Can have.
  • the content of the metal powder in the compound is not more than the above upper limit value, high fluidity (low melt viscosity) due to the epoxy resin and the phosphoric acid ester can be easily obtained.
  • the resin composition is a component including an epoxy resin and a phosphoric acid ester, and may be the remaining components (nonvolatile components) other than the metal powder and the organic solvent among all the components constituting the compound. That is, the resin composition may further contain other components in addition to the epoxy resin and the phosphoric acid ester.
  • the resin composition may further contain a curing agent.
  • the resin composition may further contain a curing accelerator.
  • the resin composition may further contain a wax (release agent).
  • the resin composition may further contain additives.
  • the additive may be, for example, a coupling agent, a flame retardant, or the like.
  • the resin composition has a function as a binder of metal particles constituting the metal powder, and imparts mechanical strength to the molded body formed from the compound.
  • the resin composition contained in the compound is filled between the metal particles when the compound is molded at high pressure using a mold, and the metal particles are bound to each other.
  • the cured product of the resin composition binds the metal particles more firmly to each other, and a cured product of the compound having excellent mechanical strength can be obtained.
  • the resin composition may be attached to the surface of each metal particle constituting the metal powder.
  • the resin composition may cover a part of the surface of each metal particle, or may cover the entire surface of each metal particle.
  • the compound may include a metal powder and an uncured resin composition.
  • the compound may include a metal powder and a semi-cured product of the resin composition (eg, a B-stage resin composition).
  • the compound may contain both an uncured resin composition and a semi-cured resin composition.
  • the compound may be a powder.
  • the compound may be a tablet.
  • the compound may be a paste.
  • the content of the resin composition in the compound may be, for example, 2% by mass or more and 10% by mass or less.
  • the resin composition may contain a kind of phosphoric acid ester.
  • the resin composition may contain a plurality of types of phosphoric acid esters.
  • the phosphoric acid ester contained in the resin composition may be at least one kind of phosphoric acid ester selected from the group consisting of a phosphoric acid monoester, a phosphoric acid diester and a phosphoric acid triester.
  • the phosphoric acid ester contained in the resin composition is a phosphoric acid ester salt of a copolymer containing an acid group, a compound 1 represented by the following chemical formula 1, a compound 2 represented by the following chemical formula 2, and a following chemical formula 3. It may be at least one phosphoric acid ester selected from the group consisting of the compound 3 and the compound 4 represented by the following chemical formula 4.
  • the compound tends to have high fluidity.
  • the phosphoric acid ester salt of the copolymer containing an acid group is contained in the resin composition, the compound tends to have high fluidity.
  • the phosphoric acid ester salt of the copolymer containing an acid group may be, for example, disperbyk-111 (trade name) manufactured by BYK-Chemie GmbH.
  • the acid value of the phosphate ester salt of the copolymer containing an acid group may be 129.
  • the acid value of disperbyk-111 is 129.
  • the compound 1 represented by the following chemical formula 1 may be, for example, JP-504 manufactured by Johoku Chemical Industry Co., Ltd.
  • the compound 2 represented by the following chemical formula 2 may be, for example, JP-506H manufactured by Johoku Chemical Industry Co., Ltd.
  • the compound 3 represented by the following chemical formula 3 may be, for example, JP-508 manufactured by Johoku Chemical Industry Co., Ltd.
  • the compound 4 represented by the following chemical formula 4 may be, for example, JP-513 manufactured by Johoku Chemical Industry Co., Ltd.
  • (C 4 H 9 O) n OP (OH) 3-n (1) N in the above chemical formula 1 may be 1 or 2. N in the above chemical formula 1 may be 1 or more and 3 or less.
  • (C 4 H 9 OCH 2 CH 2 O) n OP (OH) 3-n (2) N in the above chemical formula 2 may be 1 or 2. N in the above chemical formula 2 may be 1 or more and 3 or less.
  • (C 4 H 9 C 2 H 5 CHCH 2 O) n OP (OH) 3-n (3) N in the above chemical formula 3 may be 1 or 2. N in the above chemical formula 3 may be 1 or more and 3 or less.
  • (Is Cincinnati-C 13 H 27 O) n OP (OH) 3-n (4) N in the above chemical formula 4 may be 1 or 2. N in the above chemical formula 4 may be 1 or more and 3 or less.
  • the resin composition contains at least an epoxy resin as a thermosetting resin.
  • the compound contains an epoxy resin having a relatively excellent fluidity among the thermosetting resins, the fluidity, filling property, storage stability, and moldability of the compound are improved.
  • the compound may contain other resins in addition to the epoxy resin as long as the effects of the present invention are not impaired.
  • the resin composition may contain at least one of a phenol resin and a polyamide-imide resin as a thermosetting resin.
  • the resin composition may function as a curing agent for the epoxy resin.
  • the resin composition may further contain a thermoplastic resin in addition to the thermosetting resin.
  • the thermoplastic resin may be at least one selected from the group consisting of, for example, acrylic resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, and rubber (elastomer).
  • the resin composition may contain a silicone resin.
  • the epoxy resin may be, for example, a resin having two or more epoxy groups in one molecule.
  • the epoxy resin is, for example, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenylene aralkyl type epoxy resin, stilben type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy.
  • Resin salicylaldehyde type epoxy resin, copolymerized epoxy resin of naphthols and phenols, aralkyl type phenol resin epoxide, bisphenol type epoxy resin, epoxy resin containing bisphenol skeleton, 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, polycyclic aromatic ring-modified phenol resin glycidyl ether type epoxy resin, naphthalene ring containing Glycidyl ether type epoxy resin of phenol resin, glycidyl ester type epoxy resin, glycidyl type or methyl glycidyl type epoxy resin, alicyclic epoxy resin, halogenated phenol novolac type epoxy resin, orthocresol novolac type epoxy resin,
  • the epoxy resin includes biphenyl type epoxy resin, orthocresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol type epoxy resin, epoxy resin having a bisphenol skeleton, salicylaldehyde novolac type epoxy resin, and the like. And at least one selected from the group consisting of naphthol novolac type epoxy resin.
  • the epoxy resin may be a crystalline epoxy resin. Although the molecular weight of the crystalline epoxy resin is relatively low, the crystalline epoxy resin has a relatively high melting point and is excellent in fluidity.
  • the crystalline epoxy resin (highly crystalline epoxy resin) may be at least one selected from the group consisting of, for example, a hydroquinone type epoxy resin, a bisphenol type epoxy resin, a thioether type epoxy resin, and a biphenyl type epoxy resin.
  • Commercially available crystalline epoxy resins include, for example, Epicron 860, Epicron 1050, Epicron 1055, Epicron 2050, Epicron 3050, Epicron 4050, Epicron 7050, Epicron HM-091, Epicron HM-101, Epicron N-730A, Epicron N.
  • YX- It may be at least one selected from the group consisting of 4000, YX-4000H, YL4121H, and YX-8800 (hereinafter, trade name manufactured by Mitsubishi Chemical Co., Ltd.).
  • the resin composition may contain an isocyanate-modified epoxy resin as the epoxy resin.
  • the commercially available product of the isocyanate-modified epoxy resin may be, for example, AER-4001 manufactured by Asahi Kasei Corporation (formerly Asahi Kasei E-Materials Co., Ltd.).
  • the resin composition may contain one of the above epoxy resins.
  • the resin composition may contain a plurality of types of epoxy resins among the above.
  • the curing agent is classified into a curing agent that cures the epoxy resin in the range of 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 range of low temperature to room temperature is, for example, aliphatic polyamines, polyaminoamides, and polymercaptans.
  • the heat-curing type curing agent is, for example, aromatic polyamine, acid anhydride, phenol novolac resin, dicyandiamide (DICY) and the like.
  • the curing agent may be preferably a heat-curing type curing agent, more preferably a phenol resin, and further preferably a phenol novolac resin.
  • a phenol novolac resin as a curing agent, it is easy to obtain a cured product of an epoxy resin having a high glass transition point. As a result, the heat resistance and mechanical strength of the molded body are likely to be improved.
  • the phenol resin is, for example, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a salicylaldehyde type phenol resin, a novolak type phenol resin, a copolymerized phenol resin of a benzaldehyde type phenol and an aralkyl type phenol, a paraxylylene and / or a metaxylylene modification.
  • phenol resin From the group consisting of phenol resin, melamine-modified phenol resin, terpen-modified phenol resin, dicyclopentadiene-type naphthol resin, cyclopentadiene-modified phenol resin, polycyclic aromatic ring-modified phenol resin, biphenyl-type phenol resin, and triphenylmethane-type phenol resin. It may be at least one of the choices.
  • the phenol resin may be a copolymer composed of two or more of the above.
  • the phenol novolac resin may be, for example, a resin obtained by condensing or co-condensing phenols and / or naphthols and aldehydes under an acidic catalyst.
  • the phenols constituting the phenol novolak resin may be at least one selected from the group consisting of, for example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol.
  • the naphthols constituting the phenol novolak resin may be at least one selected from the group consisting of, for example, ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
  • the aldehydes constituting the phenol novolac resin may be at least one selected from the group consisting of, for example, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde.
  • the curing agent may be, for example, a compound having two phenolic hydroxyl groups in one molecule.
  • the compound having two phenolic hydroxyl groups in one molecule may be at least one selected from the group consisting of, for example, resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol.
  • the resin composition may contain one of the above phenolic resins.
  • the resin composition may contain a plurality of types of phenol resins among the above.
  • the resin composition may contain one of the above-mentioned curing agents.
  • the resin composition may contain a plurality of types of curing agents among the above.
  • the ratio of the active group (phenolic OH group) in the curing agent that reacts with the epoxy group in the epoxy resin is preferably 0.5 to 1.5 equivalents with respect to 1 equivalent of the epoxy group in the epoxy resin. It may be preferably 0.6 to 1.4 equivalents, more preferably 0.8 to 1.2 equivalents.
  • the ratio of active groups in the curing agent is less than 0.5 equivalent, it is difficult to obtain a sufficient elastic modulus of the obtained cured product.
  • the ratio of the active group in the curing agent exceeds 1.5 equivalents, the mechanical strength of the molded product formed from the compound after curing tends to decrease.
  • the curing accelerator is not limited as long as it is a composition that reacts with the epoxy resin to accelerate the curing of the epoxy resin, for example.
  • the curing accelerator may be, for example, an alkyl group-substituted imidazole or an imidazole such as benzimidazole.
  • the resin composition may contain a kind of curing accelerator.
  • the resin composition may contain a plurality of types of curing accelerators. When the resin composition contains a curing accelerator, the moldability and releasability of the compound are likely to be improved.
  • the mechanical strength of the molded product (for example, an electronic component) manufactured by using the compound is improved, and the compound is used in a high temperature and / or high humidity environment.
  • the storage stability of the product is improved.
  • imidazole-based curing accelerators include, for example, 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ-CN, 2PZ.
  • -At least one selected from the group consisting of CN, C11Z-CNS, 2P4MHZ, TPZ, and SFZ (above, trade name manufactured by Shikoku Chemicals Corporation) may be used.
  • 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 0.1 part by mass or more and 30 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • it may be more preferably 1 part by mass or more and 15 parts by mass or less.
  • the content of the curing accelerator is preferably 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass in total of the mass of the epoxy resin and the curing agent (for example, phenol resin).
  • the blending amount of the curing accelerator is less than 0.1 parts by mass, it is difficult to obtain a sufficient curing promoting effect.
  • the blending amount of the curing accelerator exceeds 30 parts by mass, the storage stability of the compound tends to decrease.
  • the coupling agent improves the adhesion between the resin composition and the metal particles constituting the metal powder, and improves the flexibility and mechanical strength of the molded product formed from the compound.
  • 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.
  • the resin composition may contain one of the above-mentioned coupling agents, and may contain a plurality of of the above-mentioned coupling agents.
  • Commercially available coupling agents include, for example, vinyltrimethoxysilane (KBM-1003), vinyltriethoxysilane (KBE-1003), 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane (KBM-303), 3 -Glysidoxypropylmethyldimethoxysilane (KBM-402), 3-Glysidoxypropyltrimethoxysilane (KBM-403), p-styryltrimethoxysilane (KBM-1403), 3-methacryloxypropylmethyldimethoxysilane (KBM-403) KBM-502), 3-methacryloxypropyltrimethoxysilane (KBM-503), 3-methacryloxypropylmethylmethyldimethoxysilane (KBM-503), 3-me
  • phenyltriethoxysilane KBE-103
  • n-propyltrimethoxysilane KBM-3033
  • n-propyltriethoxysilane KBE-3033
  • hexyltrimethoxysilane KBM-3063
  • hexyltriethoxysilane KBE-3063
  • Octyltriethoxysilane KBE-3083
  • decyltrimethoxysilane KBM-3103C
  • 1,6- (trimethoxysilyl) hexane KBM-3066
  • trifluoropropyltrimethoxysilane KBM-7103
  • hexamethyl It may be at least one selected from the group consisting of disilazan (SZ-31) and hydrolyzable group-containing siloxane (KPN-3504) (hereinafter, trade name manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
  • the coupling agent may be a silicone alkoxy oligomer (a silicone oligomer having an alkoxy group).
  • the silicone alkoxy oligomer may have at least one of a methoxy group and an ethoxy group.
  • the silicone alkoxy oligomer may have at least one organic substituent selected from the group consisting of an epoxy group, a methyl group, a mercapto group, an acryloyl group, a methacryloyl group, a vinyl group, and a phenyl group.
  • Silicone alkoxy oligomers include, for example, KR-517, X-41-1059A, X-24-9590, KR-516, X-41-1805, X-41-1818, X-41-1810, KR-513, X. -40-9296, KR-511, KC-89S, KR-515, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-41N, X-40-9227, KR It may be at least one selected from the group consisting of -510, KR-9218, and KR-213 (hereinafter, trade names manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the wax enhances the fluidity of the compound in the molding of the compound (for example, transfer molding) and functions as a mold release agent.
  • the wax may be at least one of fatty acids such as higher fatty acids, fatty acid esters and fatty acid salts.
  • the wax is, for example, fatty acids such as montanic acid, stearic acid, 12-oxystearic acid, lauric acid or esters thereof; zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, zinc laurate. , Fatty acid salts such as calcium laurate, zinc linoleate, calcium lysinolate, zinc 2-ethylhexoate; stearic acid amide, oleate amide, erucic acid amide, behenic acid amide, palmitate amide, lauric acid amide, hydroxystearic acid amide. .
  • fatty acids such as montanic acid, stearic acid, 12-oxystearic acid, lauric acid or esters thereof
  • zinc stearate calcium stearate, barium stearate, aluminum stearate, magnesium stearate, zinc laurate.
  • Fatty acid salts such as calcium laurate, zinc
  • N-stearyl erucate amide methylol stearic acid amide, methylol behenic acid amide and other fatty acid amides
  • fatty acid esters such as butyl stearate
  • alcohols such as ethylene glycol and stearyl alcohol
  • polysiloxanes such as silicone oil and silicon grease
  • fluorine compounds such as fluorine-based oil, fluorine-based grease and fluorine-containing resin powder
  • paraffin wax polyethylene wax, amido wax, etc. It may be at least one selected from the group consisting of waxes such as polypropylene wax, ester wax, carnauba and microwax;
  • the compound may contain a flame retardant.
  • the flame retardant is at least selected from the group consisting of, for example, a bromine-based flame retardant, a phosphorus-based flame retardant, a hydrated metal compound-based flame retardant, a silicone-based flame retardant, a nitrogen-containing compound, a hindered amine compound, an organic metal compound, and an aromatic empra. It may be a kind.
  • the resin composition may contain one of the above flame retardants, and may contain a plurality of of the above flame retardants.
  • the metal powder may contain, for example, at least one selected from the group consisting of elemental metals (pure metals) and alloys.
  • the metal powder may consist of, for example, at least one selected from the group consisting of elemental metals (pure metals), alloys, amorphous powders and metal compounds.
  • the alloy may contain at least one selected from the group consisting of solid solutions, eutectic and intermetallic compounds.
  • the alloy may be, for example, stainless steel (Fe—Cr based alloy, Fe—Ni—Cr based alloy, etc.).
  • the metal powder may contain one kind of metal element or a plurality of kinds of metal elements.
  • the metal element contained in the metal powder may be, for example, a base metal element, a noble metal element, a transition metal element, or a rare earth element.
  • the compound may contain one kind of metal powder and may contain a plurality of kinds of metal powder.
  • the metal elements contained in the metal powder are, for example, iron (Fe), copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), and aluminum (Al). , Tin (Sn), Chromium (Cr), Barium (Ba), Strontium (Sr), Lead (Pb), Silver (Ag), Placeozim (Pr), Neodim (Nd), Samarium (Sm) and Dysprosium (Dy) It may be at least one selected from the group consisting of.
  • the metal powder may contain an element other than the metal element.
  • the metal powder may contain oxygen ( ⁇ ), beryllium (Be), phosphorus (P), boron (B), or silicon (Si).
  • the metal powder may be a magnetic powder.
  • the metal powder may be a soft magnetic alloy or a ferromagnetic alloy.
  • the metal powder is, for example, Fe-Si alloy, Fe—Si—Al alloy (Sendust), Fe—Ni alloy (Permalloy), Fe—Cu—Ni alloy (Permalloy), Fe—Co alloy (Permalloy). Menzur), Fe-Cr-Si alloy (electromagnetic stainless steel), Nd-Fe-B alloy (rare earth magnet), Sm-Fe-N alloy (rare earth magnet), and Al-Ni-Co alloy (rare earth magnet). It may be a magnetic powder consisting of at least one selected from the group consisting of an alloy magnet).
  • the metal powder may be a copper alloy such as a Cu—Sn-based alloy, a Cu—Sn—P-based alloy, a Cu—Ni-based alloy, or a Cu—Be-based alloy.
  • the metal powder may consist of only one element or composition.
  • the metal powder may contain a plurality of elements or compositions.
  • the metal powder may be Fe alone (pure iron).
  • the metal powder may be an alloy containing iron (Fe-based alloy).
  • the Fe-based alloy may be, for example, a Fe-Si-Cr-based alloy, an Nd-Fe-B-based alloy, or a Sm-Fe-N-based alloy.
  • the metal powder may be at least one of amorphous iron powder and carbonyl iron powder. When the metal powder contains at least one of Fe simple substance and Fe-based alloy, it is easy to produce a molded product having a high space factor and excellent magnetic properties from the compound.
  • the metal powder may be an Fe amorphous alloy.
  • Fe amorphous alloy powders include, for example, AW2-08, KUAMET-6B2 (above, trade name manufactured by Epson Atmix Co., Ltd.), DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, DAP MKV49. , DAP 410L, DAP 430L, DAP HYB series (above, product name manufactured by Daido Special Steel Co., Ltd.), MH45D, MH28D, MH25D, and MH20D (above, product name manufactured by Kobe Steel Co., Ltd.). At least one may be used.
  • the average particle size of the metal powder is not particularly limited, but may be, for example, 1 ⁇ m or more and 300 ⁇ m or less.
  • the average particle size may be measured, for example, by a particle size distribution meter.
  • the shape of the individual metal particles constituting the metal powder is not limited, but may be spherical, flat, prismatic, or needle-shaped, for example.
  • the compound may contain a plurality of metal powders having different average particle sizes.
  • the compound may be used for at least one of transfer molding and compression molding.
  • Transfer molding is a kind of injection molding method for thermosetting resin. Transfer molding may be paraphrased as pumping molding. Transfer molding consists of a step of heating the compound in the heating chamber to fluidize it, a step of supplying (press-fitting) the fluidized compound from the heating chamber into the mold through a casting runner, and a compound in the mold. May include a step of heating and curing.
  • Transfer molding involves heating the compound in the heating chamber to fluidize it, supplying the fluidized compound powder from the heating chamber into the plunger, and supplying the compound from the plunger into the mold through the runner ( It may include a step of press-fitting) and a step of heating and curing the compound in the mold.
  • the pressure acting on the compound in transfer molding may be, for example, 3 MPa or more and 100 MPa or less. Since the compound according to the present embodiment exhibits excellent fluidity and filling property by heating, it easily flows in a narrow runner and is easily filled in a space (cavity) in a mold without unevenness. Therefore, by processing the compound by transfer molding, it becomes possible to produce a molded product and a cured product having few defects such as voids or burrs.
  • the compound molding method may be compression molding.
  • the molded body formed from the compound may contain at least one of an uncured resin composition and a B-stage resin composition (semi-cured product of the resin composition).
  • the molded body may consist only of the compound.
  • the cured product of the compound or the molded product may contain a C-stage resin composition (cured product of the resin composition).
  • Industrial products manufactured using the compound may be, for example, automobiles, medical equipment, electronic equipment, electrical equipment, information and communication equipment, home appliances, audio equipment, and general industrial equipment.
  • the compound when the compound contains a permanent magnet such as a Sm-Fe-N alloy or an Nd-Fe-B alloy as a metal powder, the compound may be used as a material for a bonded magnet.
  • the compound when the compound contains a soft magnetic material such as a Fe—Si—Cr based alloy as a metal powder, the compound may be utilized as a material (for example, a sealing material or a magnetic core) for an inductor (for example, an EMI filter) or a transformer.
  • a sheet-shaped molded body or a cured product formed from the compound may be used as an electromagnetic wave shield.
  • the compound is obtained by mixing the metal powder and the resin composition while heating.
  • the metal powder and the resin composition may be kneaded with a kneader, a roll, a stirrer or the like while heating.
  • the resin composition adheres to a part or the whole of the surface of each metal particle constituting the metal powder to cover each metal particle.
  • a part or all of the epoxy resin in the resin composition may become a semi-cured product.
  • metal powder, epoxy resin, phosphoric acid ester (dispersant), curing agent, curing accelerator, coupling agent and wax may be kneaded together in a tank. After mixing the metal powder with at least one of the phosphoric acid ester and the coupling agent in the tank, the metal powder, the epoxy resin, the phosphoric acid ester, the curing agent, the curing accelerator, the coupling agent and the wax are mixed in the tank. You may further knead with. After kneading the metal powder, epoxy resin, phosphoric acid ester, curing agent, coupling agent and wax in the tank, the mixture thereof and the curing accelerator may be further kneaded in the tank.
  • An epoxy resin, a phosphoric acid ester, a curing agent, a curing accelerator and a wax may be mixed in advance to prepare a resin mixed powder.
  • the metal powder and the coupling agent may be mixed in advance to prepare a metal mixed powder.
  • the metal mixed powder and the above resin mixed powder may be kneaded to obtain a compound.
  • the kneading time depends on the type of kneading machine, the volume of the kneading machine, and the amount of compound produced.
  • the kneading time is, for example, preferably 1 minute or longer, more preferably 2 minutes or longer, and even more preferably 3 minutes or longer.
  • the kneading time is preferably 20 minutes or less, more preferably 15 minutes or less, and even more preferably 10 minutes or less. If the kneading time is less than 1 minute, the kneading is insufficient, the moldability of the compound is impaired, and the degree of curing of the compound varies.
  • the resin composition for example, epoxy resin and phenol resin
  • the heating temperature is, for example, a semi-cured epoxy resin (B-stage epoxy resin) and a cured epoxy resin (C-stage epoxy resin). It suffices as long as it is a temperature at which the formation of the epoxy is suppressed.
  • the heating temperature may be lower than the activation temperature of the curing accelerator.
  • the heating temperature is, for example, preferably 50 ° C. or higher, more preferably 60 ° C.
  • the heating temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower.
  • the resin composition in the tank softens and easily covers the surface of the metal particles constituting the metal powder, and a semi-cured epoxy resin is easily formed. Complete curing of the resin is likely to be suppressed.
  • Epoxy resin 1 epoxy resin 2, dispersant (phosphate ester), curing agent 1, curing agent 2, curing accelerator, mold release agent 1 (wax), and mold release agent 2 (wax) are put into a plastic container (plastic). It was contained in the resin). A resin mixture was prepared by mixing the contents of the plastic container for 10 minutes. The resin mixture corresponds to all the other components of the resin composition except the coupling agent.
  • the epoxy resin 1 NC-3000 (biphenylene aralkyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. was used.
  • As the epoxy resin 2 TECHMORE VG3101L (trifunctional epoxy resin) manufactured by Printec Co., Ltd. was used.
  • dispersant disperbyk-111 manufactured by BYK-Chemie GmbH was used.
  • curing agent 1 MEHC-7500-3S (triphenol methane type phenol resin) manufactured by Meiwa Kasei Co., Ltd. was used.
  • MEHC-7851SS bisphenylene aralkyl type phenol resin manufactured by Meiwa Kasei Co., Ltd. was used.
  • curing accelerator U-CAT 3512T manufactured by Sun Appro Co., Ltd. was used.
  • mold release agent powder base L (zinc laurate) manufactured by NOF CORPORATION was used.
  • release agent 2 Licowax OP manufactured by Clariant Chemicals Co., Ltd. was used. LicowaxOP is a montanic acid ester partially saponified with calcium hydroxide.
  • the iron powder 1 and the iron powder 2 were uniformly mixed for 5 minutes with a pressurized twin-screw kneader to prepare a metal powder. Both iron powder 1 and iron powder 2 were amorphous.
  • As the iron powder 1 KUAMET 9A4-II 075C03 manufactured by Epson Atmix Co., Ltd. was used. The average particle size of the iron powder 1 was 24 ⁇ m.
  • As the pressurized 2-axis kneader a pressurized 2-axis kneader manufactured by Nihon Spindle Manufacturing Co., Ltd. was used. The capacity of the pressurized twin-screw kneader was 5 L.
  • the coupling agent 1, the coupling agent 2, and the additive were added to the metal powder in the twin-screw kneader. Subsequently, the contents of the twin-screw kneader were heated to 90 ° C., and the contents of the twin-screw kneader were mixed for 10 minutes while maintaining the temperature of the contents. Subsequently, the above resin mixture was added to the contents of the twin-screw kneader. The contents were kneaded for 15 minutes while maintaining the temperature of the contents at 120 ° C.
  • the kneaded product was crushed with a hammer until the kneaded product had a predetermined particle size.
  • the coupling agent 1 KBM-5803 (methacryloxyoctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used.
  • the coupling agent 2 KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used.
  • DBL-C32 caprolactone-modified dimethyl silicone manufactured by Gelest Co., Ltd. was used.
  • the compound of Example 1 was prepared by the above method.
  • the mass (unit: g) of each component constituting the compound is shown in Table 1 below.
  • the content (unit: mass%) of the metal powder in the compound is shown in Table 1 below.
  • the content (unit: mass%) of the epoxy resin in the compound is shown in Table 1 below.
  • the ratio (unit: parts by mass) of the epoxy resin to 100 parts by mass of the metal powder is shown in Table 1 below.
  • the ratio (unit: parts by mass) of the phosphoric acid ester (dispersant) to 100 parts by mass of the metal powder is shown in Table 1 below.
  • Example 2 to 4 and Comparative Example 1 The masses of the respective components constituting the compounds of Examples 2 to 4 and Comparative Example 1 are shown in Table 1 below.
  • Compounds of Examples 2 to 4 and Comparative Example 1 were prepared in the same manner as in Example 1 except for the mass of each component constituting the compound.
  • the content of the metal powder in the compound was the value shown in Table 1 below.
  • the content of the epoxy resin in the compound was the value shown in Table 1 below.
  • the ratio of the epoxy resin to 100 parts by mass of the metal powder was the value shown in Table 1 below.
  • the ratio of the phosphoric acid ester (dispersant) to 100 parts by mass of the metal powder was the value shown in Table 1 below.
  • the melt viscosity, disk flow, and gel time of each of the compounds of Examples 2 to 4 and Comparative Example 1 were measured by the same method as in Example 1.
  • the melt viscosities, disk flows, and gel times of the compounds of Examples 2 to 4 and Comparative Example 1 were the values shown in Table 1 below.
  • the compound according to the present invention is excellent in fluidity and filling property, it is possible to manufacture industrial products having various shapes such as inductors by molding the compound.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un composé contenant au moins une poudre métallique et une composition de résine, cette composition de résine contenant au moins une résine époxy et un ester phosphorique. La teneur en résine époxy de ce composé est supérieure à 1,0% en poids et inférieure ou égale à 2,0% en poids.
PCT/JP2021/019655 2020-05-26 2021-05-24 Composé, corps moulé et produit durci WO2021241515A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202180037169.2A CN115698119A (zh) 2020-05-26 2021-05-24 复合物、成型体及固化物
KR1020227044004A KR20230015941A (ko) 2020-05-26 2021-05-24 콤파운드, 성형체 및 경화물
JP2022526538A JPWO2021241515A1 (fr) 2020-05-26 2021-05-24

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020091366 2020-05-26
JP2020-091366 2020-05-26

Publications (1)

Publication Number Publication Date
WO2021241515A1 true WO2021241515A1 (fr) 2021-12-02

Family

ID=78744413

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/019655 WO2021241515A1 (fr) 2020-05-26 2021-05-24 Composé, corps moulé et produit durci

Country Status (5)

Country Link
JP (1) JPWO2021241515A1 (fr)
KR (1) KR20230015941A (fr)
CN (1) CN115698119A (fr)
TW (1) TW202214784A (fr)
WO (1) WO2021241515A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023190373A1 (fr) * 2022-03-29 2023-10-05 住友ベークライト株式会社 Matériau magnétique souple, article moulé et procédé de production d'article moulé

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61152004A (ja) * 1984-12-26 1986-07-10 Toshiba Corp 鉄心
WO2013145608A1 (fr) * 2012-03-29 2013-10-03 住友ベークライト株式会社 Composition de résine et dispositif à semi-conducteur
JP2015125189A (ja) * 2013-12-25 2015-07-06 太陽インキ製造株式会社 導電性樹脂組成物及びその硬化物
JP2017179351A (ja) * 2016-03-29 2017-10-05 積水化学工業株式会社 樹脂組成物の硬化物、樹脂組成物及び多層基板
JP2018024832A (ja) * 2016-07-29 2018-02-15 住友ベークライト株式会社 半導体封止用エポキシ樹脂組成物および半導体装置
WO2019069870A1 (fr) * 2017-10-04 2019-04-11 日立化成株式会社 Composition de résine durcissable, et dispositif de composant électronique ainsi que procédé de fabrication de celui-ci
JP2019104954A (ja) * 2017-12-11 2019-06-27 日立化成株式会社 金属元素含有粉及び成形体
WO2019203048A1 (fr) * 2018-04-16 2019-10-24 住友ベークライト株式会社 Procédé de fabrication de dispositif électronique

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011211026A (ja) 2010-03-30 2011-10-20 Panasonic Corp 複合磁性材料
JP6662065B2 (ja) 2016-01-28 2020-03-11 東洋インキＳｃホールディングス株式会社 絶縁処理された軟磁性材料、軟磁性材料を含む圧粉磁心

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61152004A (ja) * 1984-12-26 1986-07-10 Toshiba Corp 鉄心
WO2013145608A1 (fr) * 2012-03-29 2013-10-03 住友ベークライト株式会社 Composition de résine et dispositif à semi-conducteur
JP2015125189A (ja) * 2013-12-25 2015-07-06 太陽インキ製造株式会社 導電性樹脂組成物及びその硬化物
JP2017179351A (ja) * 2016-03-29 2017-10-05 積水化学工業株式会社 樹脂組成物の硬化物、樹脂組成物及び多層基板
JP2018024832A (ja) * 2016-07-29 2018-02-15 住友ベークライト株式会社 半導体封止用エポキシ樹脂組成物および半導体装置
WO2019069870A1 (fr) * 2017-10-04 2019-04-11 日立化成株式会社 Composition de résine durcissable, et dispositif de composant électronique ainsi que procédé de fabrication de celui-ci
JP2019104954A (ja) * 2017-12-11 2019-06-27 日立化成株式会社 金属元素含有粉及び成形体
WO2019203048A1 (fr) * 2018-04-16 2019-10-24 住友ベークライト株式会社 Procédé de fabrication de dispositif électronique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023190373A1 (fr) * 2022-03-29 2023-10-05 住友ベークライト株式会社 Matériau magnétique souple, article moulé et procédé de production d'article moulé

Also Published As

Publication number Publication date
JPWO2021241515A1 (fr) 2021-12-02
KR20230015941A (ko) 2023-01-31
CN115698119A (zh) 2023-02-03
TW202214784A (zh) 2022-04-16

Similar Documents

Publication Publication Date Title
JP7103413B2 (ja) コンパウンド及び成形体
JP7081612B2 (ja) コンパウンド及びタブレット
JP2022174132A (ja) 金属元素含有粉及び成形体
JP2022109291A (ja) コンパウンド粉
JP7099515B2 (ja) コンパウンド粉
JP7136121B2 (ja) コンパウンド粉
WO2021241515A1 (fr) Composé, corps moulé et produit durci
WO2021241521A1 (fr) Composé, corps moulé et produit durci
WO2021112135A1 (fr) Composé et objet moulé
JP2021172685A (ja) コンパウンド、成形体、及びコンパウンドの硬化物
EP3960801B1 (fr) Composé, article moulé et produit durci
JP7231017B2 (ja) コンパウンドの製造方法
WO2021241513A1 (fr) Composé, corps moulé et produit durci
WO2021153688A1 (fr) Composé, article durci de ce composé, et corps moulé
JP2023049648A (ja) 成形体の製造方法及び半導体装置の製造方法
JP2022042742A (ja) コンパウンド、成形体、及びコンパウンドの硬化物
JP2021120432A (ja) コンパウンド、成形体、及びコンパウンドの硬化物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21812082

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022526538

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20227044004

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21812082

Country of ref document: EP

Kind code of ref document: A1