WO2022210919A1 - Powder, production method therefor, and resin composition production method - Google Patents
Powder, production method therefor, and resin composition production method Download PDFInfo
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- WO2022210919A1 WO2022210919A1 PCT/JP2022/016128 JP2022016128W WO2022210919A1 WO 2022210919 A1 WO2022210919 A1 WO 2022210919A1 JP 2022016128 W JP2022016128 W JP 2022016128W WO 2022210919 A1 WO2022210919 A1 WO 2022210919A1
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- Prior art keywords
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- powder
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- alkali
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- 239000000843 powder Substances 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000011342 resin composition Substances 0.000 title claims description 15
- 239000002245 particle Substances 0.000 claims abstract description 172
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims description 57
- 239000011347 resin Substances 0.000 claims description 57
- 239000003513 alkali Substances 0.000 claims description 29
- 239000010419 fine particle Substances 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000010332 dry classification Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 abstract description 9
- 238000007667 floating Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 238000000465 moulding Methods 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000011810 insulating material Substances 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910020175 SiOH Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- -1 glycidyl ester Chemical class 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 238000009725 powder blending Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010333 wet classification Methods 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
- C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Definitions
- the present invention relates to powders suitable for fillers of insulating materials for semiconductors.
- it relates to powders comprising hollow particles having cavities inside non-porous shells.
- materials used in communication devices are required to have a low dielectric constant (low Dk) and a low dielectric loss tangent (low Df).
- low Dk dielectric constant
- low Df low dielectric loss tangent
- an insulating material having a low dielectric constant and a low dielectric loss tangent is required for printed wiring boards on which semiconductor elements are mounted. If the dielectric constant of the insulating material is high, dielectric loss will occur, and if the dielectric loss tangent of the insulating material is high, not only the dielectric loss but also the amount of heat generated may increase.
- resin materials which are the main insulating materials, are being developed.
- Epoxy-based resins, polyphenylene ether-based resins, fluorine-based resins, and the like have been proposed as such resin materials (see Patent Documents 1 to 5, for example).
- Fillers are added to such resin materials in terms of durability (rigidity) and heat resistance. It is known to use metal oxides such as silica, boron nitride, talc, kaolin, clay, mica, alumina, zirconia, and titania as fillers (see, for example, Patent Document 3).
- silica is superior in terms of low dielectric constant and low dielectric loss tangent.
- the capacity and speed of data communication are rapidly increasing, further reductions in dielectric constant and dielectric loss tangent are required.
- hollow particles that do not contain microparticles and satisfy predetermined conditions can achieve a low dielectric constant and a low dielectric loss tangent of insulating materials.
- the powder according to the present invention contains hollow particles having a cavity inside a nonporous outer shell, has an average particle size (D50) of 2.0 to 10.0 ⁇ m, and has a particle size of 2.0 ⁇ m. less than 20% by volume of microparticles.
- D50 average particle size
- the suspended particles are 7.0 to 25.0% by mass
- the suspended particles are 0 to 4.0% by mass
- the sedimented particles are 71.0 to 93.0% by mass. .
- the method for producing a powder according to the present invention includes a first step of preparing particles by spray-drying an aqueous alkali silicate solution in a hot air stream, a second step of removing alkali contained in the particles, and a second step of removing alkali. and a third step of firing the particles, and a classification step of removing fine particles of less than 2.0 ⁇ m is provided between the first and third steps.
- the powder of the present invention makes it possible to reduce the dielectric constant and dielectric loss tangent of the insulating material, thereby increasing the transmission speed of semiconductors and reducing transmission loss.
- the powder of the present invention contains hollow particles having cavities inside nonporous outer shells, and has an average particle size of 2.0 to 10.0 ⁇ m. Furthermore, the content of microparticles having a particle diameter of less than 2.0 ⁇ m is 20% by volume or less. When this powder is suspended in water, the suspended particles are 7.0 to 25.0% by mass, the suspended particles are 0 to 4.0% by mass, and the sedimented particles are 71.0 to 93.0% by mass. be.
- the powders of the present invention may also contain small amounts of solid particles. This is because there is a possibility that solid particles are also produced unexpectedly during the production of hollow particles. Since solid particles without internal cavities have a high specific gravity, they are basically thought to be latent in sedimented particles. It is preferable that 90 mass % or more of the particles contained in the powder are hollow particles.
- particles that disperse in water when suspended in water are defined as suspended particles, and particles with a low specific gravity floating in the upper layer (near the water surface) are defined as suspended particles.
- Such suspended particles usually have a high porosity. Therefore, the dielectric constant and dielectric loss tangent of the resin product decrease as the number of suspended particles mixed in the resin material increases. In general, particles with higher porosity have larger particle diameters (smaller particle diameters have lower porosity). Therefore, controlling the amount of suspended particles to 7.0 to 25.0% by mass of the total particles controls (reduces) the amount of coarse particles. Since there are not many coarse particles, the resin composition for molding resin products (insulating materials, etc.) has good filterability and injectability.
- microparticles have a low porosity
- the dielectric constant can be lowered without increasing the number of large particles with a high porosity. Fewer microparticles also reduce the total surface area of all particles. As a result, the amount of SiOH groups is reduced, so that the dielectric constant and dielectric loss tangent can be lowered.
- the powder of the present invention as a filler, the filterability and injectability of the resin composition for molding are improved, and a resin product with good surface smoothness can be obtained.
- a powder containing few microparticles has low adhesiveness and improved fluidity. Therefore, handleability and dispersibility are also improved.
- the content of microparticles is preferably 15% by volume or less, more preferably 10% by volume or less, even more preferably 5% by volume or less, and most preferably 3% by volume or less.
- Suspended particles tend to have low particle strength because the ratio (t/d) of the particle diameter (d) to the shell thickness (t) is small. Therefore, there is a risk that the particles will break during the process of mixing the resin material and the particles until the resin product is molded (that is, during the manufacturing process). Cracked particles hinder low dielectric constant and low dielectric loss tangent, and deteriorate the fluidity of the resin composition, reduce the uniformity of the resin product (molded product), It becomes a factor that causes voids. However, by controlling the amount of suspended particles, cracking of the particles can be suppressed.
- the amount of suspended particles while ensuring the favorable properties of particles with high porosity (e.g., low dielectric constant and low dielectric loss tangent), unfavorable properties of high porosity particles (e.g., occurrence of cracks) can be suppressed to the extent that there is no problem.
- the suspended particles there are particles with a high porosity even if they have a small diameter. Such particles are less likely to crack than large-diameter particles in the manufacturing process. characteristics can be suppressed as much as possible.
- the content of suspended particles is preferably 8.0 to 24.0% by mass, more preferably 8.0 to 23.0% by mass, even more preferably 8.0 to 22.0% by mass, and 8.0 to 15.0% by weight is most preferred.
- the content of the sedimented particles is preferably 72.0 to 92.0% by mass, more preferably 73.0 to 92.0% by mass, even more preferably 74.0 to 92.0% by mass, and 81.0% by mass. ⁇ 92.0% by weight is most preferred.
- the average particle size (D50) of the powder is in the range of 2.0 to 10.0 ⁇ m. If the average particle diameter is less than 2.0 ⁇ m, a large number of fine particles are contained, resulting in a high specific surface area (high SiOH group content), making it difficult to obtain excellent dielectric properties. Also, powders with an average particle size exceeding 10 ⁇ m are unsuitable for use in semiconductors. For semiconductor applications, the average particle size is preferably 2.5 to 10.0 ⁇ m, more preferably 3.0 to 10.0 ⁇ m.
- the maximum particle diameter (D100) is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, and even more preferably 30 ⁇ m or less.
- the maximum particle size (D100) is preferably 10 times or less, more preferably 8 times or less, the average particle size (D50). Usually, it is 2 times or more, and may exceed 5 times as long as the requirements of the present invention are satisfied.
- the porosity of the powder is preferably 20% by volume or more, more preferably 30% by volume or more, and even more preferably 40% by volume or more. Also, it is preferably 70% by volume or less, more preferably 65% by volume or less, even more preferably 60% by volume or less, and most preferably 55% by volume or less. With such a porosity, it is possible to achieve a low dielectric constant and a low dielectric loss tangent, and at the same time, it is possible to effectively suppress cracking of the particles by maintaining the particle strength above a predetermined level.
- silica-based particles containing silica as a main component are suitable for the particles that make up the powder. Therefore, the hollow particles (outer shell) contained in the powder may contain inorganic oxides such as alumina, zirconia, and titania in addition to silica.
- the content of silica in the particles is preferably 70% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably consisting essentially of silica.
- a resin composition is prepared by blending the powder and the resin material described above.
- Such a resin composition is an insulating material for electronic materials such as semiconductors, and more specifically, copper-clad laminates, prepregs, build-up films, etc. for forming printed wiring boards (including rigid boards and flexible boards). can be used for It can also be used for semiconductor package-related materials such as mold resins, mold underfills, and underfills, adhesives for flexible substrates, and the like.
- curable resins that are generally used in electronic materials such as semiconductors can be used.
- a photocurable resin may be used, but a thermosetting resin is preferred.
- curable resins include epoxy-based resins, polyphenylene ether-based resins, fluorine-based resins, polyimide-based resins, bismaleimide-based resins, acrylic-based resins, methacrylic-based resins, silicone-based resins, BT resins, and cyanate-based resins. can.
- epoxy resins bisphenol-type epoxy resins, novolak-type epoxy resins, triphenolalkane-type epoxy resins, epoxy resins having a biphenyl skeleton, epoxy resins having a naphthalene skeleton, dicyclopentadiene phenol novolak resins, and phenol aralkyl-type epoxy resins.
- epoxy resins bisphenol-type epoxy resins, novolak-type epoxy resins, triphenolalkane-type epoxy resins, epoxy resins having a biphenyl skeleton, epoxy resins having a naphthalene skeleton, dicyclopentadiene phenol novolak resins, and phenol aralkyl-type epoxy resins.
- glycidyl ester type epoxy resins alicyclic epoxy resins, heterocyclic epoxy resins, and halogenated epoxy resins. These resins may be used alone or in combination of two or more.
- the resin composition preferably contains the powder A and the curable resin B at a mass ratio (A/B) of 10/100 to 95/100. Thereby, the function as a filler can be sufficiently exhibited while maintaining the characteristics of the resin composition such as fluidity.
- the mass ratio (A/B) is more preferably 30/100 to 80/100.
- the resin composition preferably contains a curing agent such as a phenol compound, an amine compound, or an acid anhydride.
- a curing agent such as a phenol compound, an amine compound, or an acid anhydride.
- a resin having two or more phenolic hydroxyl groups in one molecule bisphenol type resin, novolak resin, triphenol alkane type resin, resol type phenol resin, phenol aralkyl resin, phenolic resins such as biphenyl-type phenolic resins, naphthalene-type phenolic resins, and cyclopentadiene-type phenolic resins
- acid anhydrides such as methylhexahydrophthalic acid, methyltetrahydrophthalic acid, and methylnadic anhydride.
- additives colorants, stress relaxation agents, antifoaming agents, leveling agents, coupling agents, flame retardants, curing accelerators, etc.
- a curable resin, powder, a curing agent, additives, etc. are mixed and kneaded by a roll mill or the like.
- the obtained resin composition is applied to a substrate and cured by heat, ultraviolet rays, or the like.
- the method for producing a powder of the present invention includes a first step of spray-drying an aqueous alkali silicate solution in a hot air stream to prepare particles, a second step of removing the alkali contained in the prepared particles, and a second step of removing the alkali. and a third step of firing the particles, and a step of classifying the particles to remove fine particles of less than 2.0 ⁇ m (classifying step) is provided between the first step and the third step.
- other processes such as a drying process may be provided between each process. Through such a process, the powder described above can be obtained.
- the classification treatment is intentionally performed before firing. If the sintering process is performed without classifying, the particles are sintered while the fine particles to be removed are present, and the fine particles are sintered with other particles. Therefore, the fine particles cannot be removed even if the classification treatment is performed afterward. Fine particles can be reliably reduced by performing the classification treatment before firing. As a result, a low dielectric constant and a low dielectric loss tangent of the particles can be achieved more reliably, and particles suitable for high-speed data communication can be obtained. In addition, you may perform a classification process again after baking. Each step will be described in detail below.
- Step 1 the alkali silicate aqueous solution is spray-dried in a hot air stream to granulate silica-based particles.
- this step is performed to obtain hollow particles, it is difficult to make all the particles hollow particles, and the granulated silica-based particles eventually contain solid particles.
- solid particles are also contained in the powder obtained through the steps described below. However, if the powder has the properties described above, the expected effect can be obtained even if the powder contains solid particles.
- the molar ratio (SiO 2 /M 2 O) of SiO 2 and M 2 O (M is an alkali metal) in the alkali silicate is preferably 1-5, more preferably 2-4. If this molar ratio is less than 1, the amount of alkali is too large, and it is difficult to sufficiently remove it even if acid washing is carried out in the alkali removing step. Furthermore, the deliquescence of the spray-dried product increases, making it difficult to obtain desired hollow particles. If this molar ratio exceeds 5, the alkali silicate becomes less soluble, making it difficult to prepare an aqueous solution. Even if an aqueous solution can be prepared, it may not be possible to form hollow particles by spray drying.
- the concentration of SiO 2 in the alkali silicate aqueous solution is preferably 1 to 30% by mass, more preferably 5 to 28% by mass. Production is possible even if the content is less than 1% by mass, but the productivity is remarkably lowered. If it exceeds 30% by mass, the stability of the alkali silicate aqueous solution is remarkably lowered and the viscosity becomes high, and spray drying may not be possible. Even if the particles can be spray-dried, the particle size distribution, outer shell thickness, etc. become extremely non-uniform, and the applications of the obtained particles may be limited.
- As the alkali silicate water-soluble sodium silicate and potassium silicate can be used. Sodium silicate is preferred.
- spray-drying method for example, conventionally known methods such as a rotating disk method, a pressurized nozzle method, and a two-fluid nozzle method can be adopted.
- a two-fluid nozzle method is preferred here.
- the inlet temperature of the spray dryer is preferably 300-600°C, more preferably 350-550°C.
- the outlet temperature is preferably 120-300°C, more preferably 130-250°C. Hollow particles can be stably obtained by such temperature setting.
- the alkali contained in the particles granulated in the first step is removed.
- a method of removing by adding an acid for neutralization is suitable.
- a treatment in which the particles are immersed in an acid solution is preferred.
- the molar ratio (Ma/Msp) between the number of moles of M 2 O (Msp) and the number of moles of acid (Ma) in the particles is preferably 0.6 to 4.7, more preferably 1 to 4.5. preferable. If this molar ratio is less than 0.6, the amount of acid relative to M2O is too low.
- the particles are immersed in an acid aqueous solution so that the concentration of the particles is 1 to 30% by mass as SiO 2 . If the amount is less than 1% by mass, there is no problem in alkali removal and cleaning properties, but the production efficiency is lowered. If it exceeds 30% by mass, the concentration may be too high and the alkali removal and cleaning efficiency may be lowered. 5 to 25% by mass is more preferable.
- the conditions for immersion in the acid aqueous solution are not particularly limited as long as the desired amount of alkali can be removed, and the treatment temperature is usually 5 to 100° C. and the treatment time is 0.5 to 24 hours. After that, it is preferable to wash by a conventionally known method. For example, it is filtered and washed with pure water. The acid treatment and washing may be repeated as necessary.
- the residual amount (mass ratio) of alkali (M) after alkali removal is preferably 300 ppm or less, more preferably 200 ppm or less, and even more preferably 100 ppm or less.
- the alkali content of the final product is also preferably within the range described above, and is usually equivalent to the alkali content after the alkali removal step.
- the amount of residual alkali can be measured using an atomic absorption photometer, using a sample of powder dissolved in acid. Na is measured when sodium silicate is used, and K is measured when potassium silicate is used. Specifically, it will be described in Examples.
- acids used in this step mineral acids (hydrochloric acid, nitric acid, sulfuric acid, etc.) and organic acids (acetic acid, tartaric acid, malic acid, etc.) can be used.
- Mineral acids are preferably used, and sulfuric acid having a high valence is particularly preferred.
- the firing temperature is preferably 600-1200°C, more preferably 900-1100°C.
- the firing temperature is lower than 600° C.
- the amount of remaining SiOH groups is large and the dielectric loss tangent of the particles is high. Therefore, it is difficult to obtain the effect of reducing the dielectric loss tangent even if it is added to the resin.
- the firing temperature exceeds 1200° C., the particles are likely to be sintered together, so irregularly shaped particles and coarse particles are likely to be generated. This causes deterioration in filterability and injectability of the resin composition-forming liquid.
- Fine particles smaller than 2.0 ⁇ m are removed by performing a classification treatment between the first step and the third step.
- the classification treatment is performed before removing the alkali, it is necessary to perform the classification treatment immediately after granulation in order to prevent the hollow particles from absorbing moisture (deliquescence) and aggregating and coalescing. Further, when the classification treatment is performed before firing, the classification treatment may be performed following the alkali removal treatment.
- the amount of fine particles with a particle size of less than 2.0 ⁇ m is reduced to 20% by volume or less.
- the content is preferably 15% by volume or less, more preferably 10% by volume or less, even more preferably 5% by volume or less, and most preferably 3% by volume or less.
- the ratio of suspended particles present in the powder can be controlled within a predetermined range.
- the content of fine particles and coarse particles in the final product does not change significantly from the content after the classification step.
- the classification process in this classification process means particle size classification that separates powders by particle size with the aim of aligning the particle size of the powder.
- Fluid classification can be mentioned as an operation of this particle size classification.
- Fluid classification can be classified into dry classification and wet classification. Wet classification is carried out while particles are suspended in water. As a result, SiOH groups are generated on the particle surface, which may adversely affect the dielectric properties. Dry classification is therefore preferred.
- classifiers used for dry classification can be broadly classified into gravity classifiers, inertial classifiers, and centrifugal classifiers. More precise classification is possible by using an inertial classifier or a centrifugal classifier.
- Classifiers that can accurately classify even light particles such as the present invention include Elbow Jet manufactured by Nittetsu Mining Co., Ltd., SG Separator manufactured by 3M Japan, Aerofine Classifier manufactured by Nisshin Engineering, and Microspin manufactured by Nippon Pneumatic Industry. can be mentioned. Among these, an elbow jet and an aerofine classifier are preferable.
- a drying treatment step may be provided as appropriate during the manufacturing process.
- the drying treatment can be provided between the alkali removal treatment and the classification treatment, between the classification treatment and the firing, or both, or between the alkali removal treatment and the firing. It may be provided multiple times as required.
- the drying treatment may be performed before firing, and the classification treatment may be performed between the drying treatment and firing.
- Heat drying is suitable as the drying treatment.
- the drying temperature is preferably 50 to 400°C, more preferably 50 to 200°C. Specific examples include a method of drying at a low temperature of about 50 to 200°C over a long period of time, a method of gradually increasing the temperature, and a method of changing the temperature in several stages for drying. can.
- particle agglomerate refers to, for example, particles having a particle size exceeding 50 ⁇ m, and a sieve having an opening (mesh number) capable of removing such a particle agglomerate is appropriately used.
- Example 1 Using 30000 g of water glass aqueous solution (SiO 2 /Na 2 O molar ratio 3.2, SiO 2 concentration 24% by mass), one of the two-fluid nozzles is supplied with a flow rate of 0.62 kg / hr, and the other nozzle is supplied with air at 31800 L / Hollow particles were granulated by spraying with hot air having an inlet temperature of 400° C. at a flow rate of hr (empty/liquid volume ratio of 63,600). Here, the outlet temperature was 150° C. (first step). A small amount of solid particles may also be granulated in the first step, but it is not necessary to remove the solid particles to proceed to the next step.
- a powder containing hollow particles was obtained by heat-treating the collected particles at 1000°C for 10 hours (third step). After the baking, particle lumps (foreign matters) were removed with a sieve with an opening of 150 ⁇ m.
- the resulting powder was mixed with a liquid acid anhydride "Likacid MH700 manufactured by Shin Nippon Rika Co., Ltd.”, an imidazole-based epoxy resin curing agent “2PHZ-PW manufactured by Shikoku Kasei Co., Ltd.”, and a liquid epoxy resin "ZX manufactured by Nippon Steel Chemical & Materials Co., Ltd.” -1059".
- a liquid acid anhydride "Likacid MH700 manufactured by Shin Nippon Rika Co., Ltd.”
- an imidazole-based epoxy resin curing agent “2PHZ-PW manufactured by Shikoku Kasei Co., Ltd.”
- a liquid epoxy resin "ZX manufactured by Nippon Steel Chemical & Materials Co., Ltd.” -1059.
- the proportion of "ZX-1059” is 100 parts by mass
- "Rikacid MH700” is 86 parts by mass
- “2PHZ-PW” is 1 part by mass
- the proportion of powder in the formulation (paste) is 35% by volume.
- This compound was preliminarily kneaded in a planetary mill and then kneaded in a triple roll to obtain a paste (resin composition).
- This paste was cured by heating at 170° C. for 2 hours to obtain a plate-shaped resin molding (resin product) of 50 mm ⁇ 50 mm ⁇ 1 mm.
- Average particle size (D50), maximum particle size (D100), and amount of fine particles Using a particle size analyzer (Laser Micronsizer LMS-3000 manufactured by Seishin Enterprise Co., Ltd.), the particle size distribution of the powder was measured in a dry manner. . Average particle size (D50) and maximum particle size (D100) were obtained from the measurement results. Further, the particle size distribution was analyzed to calculate the volume ratio of particles less than 2.0 ⁇ m, which was defined as the amount of fine particles.
- Dielectric constant (Dk) and dielectric loss tangent (Df) of resin molding Dielectric constant (Dk) and dielectric loss tangent (Df) of a plate-shaped molding (resin molding) of 50 mm ⁇ 50 mm ⁇ 1 mm were measured at 9.4 GHz using a network analyzer (manufactured by Anritsu, MS46122B) and a coaxial resonator. It was measured. It was compared with a resin molding containing no powder (filler) according to the following formula and evaluated according to the following criteria.
- Dielectric constant (Dk) reduction rate (%) (dielectric constant without powder blending - dielectric constant with powder blending)/dielectric constant without powder blending x 100
- Dielectric loss tangent (Df) reduction rate (%) (Dielectric loss tangent without powder blending - Dielectric loss tangent with powder blended) / Dielectric loss tangent without powder blended x 100
- ⁇ Reduction rate of 50% or more
- ⁇ Reduction rate of 30% or more and less than 50%
- ⁇ Reduction rate of 20% or more and less than 30%
- ⁇ Reduction rate of less than 20%
- Example 2 In the classification process, a dry inertia classification process was performed using an elbow jet (EJ-15) manufactured by Nittetsu Mining Co., Ltd. This device can classify powder into three types: F powder (fine powder), M powder (fine powder), and G powder (coarse powder). At this time, the F edge distance was adjusted so that the fine particles of less than 2.0 ⁇ m contained in the M powder (fine powder) were 2% by volume or less. M powder was collected and the subsequent steps were performed. A powder and a resin molding were prepared in the same manner as in Example 1 except for this.
- EJ-15 elbow jet manufactured by Nittetsu Mining Co., Ltd. This device can classify powder into three types: F powder (fine powder), M powder (fine powder), and G powder (coarse powder). At this time, the F edge distance was adjusted so that the fine particles of less than 2.0 ⁇ m contained in the M powder (fine powder) were 2% by volume or less. M powder was collected and the subsequent steps were performed. A powder and
- Example 3 In the classification process, a dry centrifugal (semi-free vortex) classification treatment was performed using an Aerofine Classifier manufactured by Nisshin Engineering. The angle of the blades and the like were adjusted and classified so that the fine particles of less than 2.0 ⁇ m contained in the recovered powder were 20% by volume or less. A powder and a resin molding were prepared in the same manner as in Example 1 except for this.
- Example 4 The angles of the blades and the like were adjusted so that the fine particles of less than 2.0 ⁇ m contained in the collected particles were 10% by volume or less. A powder and a resin molding were prepared in the same manner as in Example 3 except for this.
- Example 1 A powder and a resin molding were prepared in the same manner as in Example 1, except that the classification treatment (classification process) was not performed.
- Example 2 In the first step, the inlet temperature of the spray dryer was changed to 250°C, and in the second step, the immersion stirring time was changed to 1.5 hours. Furthermore, no classification step was performed. A powder and a resin molding were prepared in the same manner as in Example 1 except for this.
- Example 3 In the first step, the inlet temperature of the spray dryer was changed to 420°C, and no classification treatment (classification step) was performed. A powder and a resin molding were prepared in the same manner as in Example 1 except for this.
- the powders according to the examples and the resin moldings containing the powders have low dielectric constants and low dielectric loss tangents.
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Abstract
Description
上述した粉体と樹脂材料を配合することにより、樹脂組成物が調製される。このような樹脂組成物は、半導体等の電子材料の絶縁材料、具体的には、プリント配線板(リジッド基板及びフレキシブル基板を含む)を形成するための銅張積層板、プリプレグ、ビルドアップフィルム等に用いることができる。また、モールド樹脂、モールドアンダーフィル、アンダーフィル等の半導体パッケージ関連材料や、フレキシブル基板用接着剤等に用いることができる。 [Resin composition]
A resin composition is prepared by blending the powder and the resin material described above. Such a resin composition is an insulating material for electronic materials such as semiconductors, and more specifically, copper-clad laminates, prepregs, build-up films, etc. for forming printed wiring boards (including rigid boards and flexible boards). can be used for It can also be used for semiconductor package-related materials such as mold resins, mold underfills, and underfills, adhesives for flexible substrates, and the like.
本発明の粉体の製造方法は、珪酸アルカリ水溶液を熱風気流中で噴霧乾燥して粒子を調製する第一工程と、調製された粒子に含まれるアルカリを除去する第二工程と、アルカリ除去された粒子を焼成する第三工程とを有し、第一工程と第三工程の間に、粒子を分級して2.0μm未満の微小粒子を除去する工程(分級工程)が設けられている。なお、各工程の間に、乾燥工程等の他の工程を設けてもよい。このような工程により、上述の粉体を得ることができる。 [Method for producing powder]
The method for producing a powder of the present invention includes a first step of spray-drying an aqueous alkali silicate solution in a hot air stream to prepare particles, a second step of removing the alkali contained in the prepared particles, and a second step of removing the alkali. and a third step of firing the particles, and a step of classifying the particles to remove fine particles of less than 2.0 μm (classifying step) is provided between the first step and the third step. In addition, other processes such as a drying process may be provided between each process. Through such a process, the powder described above can be obtained.
本工程では、珪酸アルカリ水溶液を熱風気流中で噴霧乾燥してシリカ系粒子を造粒する。なお、本工程は、中空粒子を得るために行われるが、全ての粒子を中空粒子にすることは困難であり、造粒されたシリカ系粒子には、結果的に中実粒子も含まれている可能性がある。この場合、後述の工程を経て得られる粉体に中実粒子も含まれている。しかし、粉体が上述の特性を備えていれば、中実粒子が含まれていても、期待する効果が得られる。 (First step)
In this step, the alkali silicate aqueous solution is spray-dried in a hot air stream to granulate silica-based particles. Although this step is performed to obtain hollow particles, it is difficult to make all the particles hollow particles, and the granulated silica-based particles eventually contain solid particles. There may be In this case, solid particles are also contained in the powder obtained through the steps described below. However, if the powder has the properties described above, the expected effect can be obtained even if the powder contains solid particles.
次に、第一工程で造粒された粒子に含まれるアルカリを除去する。酸を加えて中和することにより除去する方法が適している。粒子を酸の溶液に浸漬する処理が好ましい。このとき、粒子中のM2Oモル数(Msp)と酸のモル数(Ma)とのモル比(Ma/Msp)は、0.6~4.7が好ましく、1~4.5がさらに好ましい。このモル比が0.6未満の場合は、M2Oに対して酸の量が少なすぎる。そのため、アルカリの除去とともに起きると考えられるケイ酸のシリカ骨格化が進行せず、粒子が部分的に溶解したり、溶解した珪酸アルカリがゲル化する場合がある。モル比が4.7を超えてもさらにシリカ骨格化が進むことはなく、酸が過剰であり経済的でない。 (Second step)
Next, the alkali contained in the particles granulated in the first step is removed. A method of removing by adding an acid for neutralization is suitable. A treatment in which the particles are immersed in an acid solution is preferred. At this time, the molar ratio (Ma/Msp) between the number of moles of M 2 O (Msp) and the number of moles of acid (Ma) in the particles is preferably 0.6 to 4.7, more preferably 1 to 4.5. preferable. If this molar ratio is less than 0.6, the amount of acid relative to M2O is too low. Therefore, the formation of a silica skeleton of silicic acid, which is thought to occur with the removal of alkali, does not proceed, and the particles may partially dissolve or the dissolved alkali silicate may gel. Even if the molar ratio exceeds 4.7, the formation of the silica skeleton does not proceed further, and the acid is excessive, which is not economical.
次に、アルカリ除去処理後の粒子を焼成する。焼成温度は、600~1200℃が好ましく、900~1100℃がより好ましい。焼成温度が600℃未満の場合は、SiOH基の残存量が多く、粒子の誘電正接が高くなる。そのため、樹脂に配合しても、誘電正接低減効果が得られにくい。焼成温度が1200℃を超える場合は、粒子同士が焼結しやすいので、異形状の粒子や、粗大粒子が生成しやすい。これは、樹脂組成物形成用液の濾過性や、注入性が低下する原因となる。 (Third step)
Next, the particles after the alkali removal treatment are calcined. The firing temperature is preferably 600-1200°C, more preferably 900-1100°C. When the firing temperature is lower than 600° C., the amount of remaining SiOH groups is large and the dielectric loss tangent of the particles is high. Therefore, it is difficult to obtain the effect of reducing the dielectric loss tangent even if it is added to the resin. When the firing temperature exceeds 1200° C., the particles are likely to be sintered together, so irregularly shaped particles and coarse particles are likely to be generated. This causes deterioration in filterability and injectability of the resin composition-forming liquid.
第一工程と第三工程の間に分級処理を行うことにより、2.0μm未満の微小粒子を除去する。アルカリ除去の前に分級処理を行う場合には、中空粒子が吸湿(潮解)して凝集・合着することを防止するために、造粒後直ちに分級処理をする必要がある。また、焼成前に分級処理を行う場合、アルカリ除去処理に続けて分級処理を行ってもよい。 (Classification process)
Fine particles smaller than 2.0 μm are removed by performing a classification treatment between the first step and the third step. When the classification treatment is performed before removing the alkali, it is necessary to perform the classification treatment immediately after granulation in order to prevent the hollow particles from absorbing moisture (deliquescence) and aggregating and coalescing. Further, when the classification treatment is performed before firing, the classification treatment may be performed following the alkali removal treatment.
水ガラス水溶液(SiO2/Na2Oモル比3.2、SiO2濃度24質量%)30000gを用い、2流体ノズルの一方に0.62kg/hrの流量で、他方のノズルに空気を31800L/hr(空/液体積比63600)の流量で、入口温度400℃の熱風に噴霧して中空粒子を造粒した。ここで、出口温度は150℃であった(第一工程)。第一工程では、少量の中実粒子も造粒される可能性があるが、中実粒子を除去して次工程に進む必要はない。 [Example 1]
Using 30000 g of water glass aqueous solution (SiO 2 /Na 2 O molar ratio 3.2, SiO 2 concentration 24% by mass), one of the two-fluid nozzles is supplied with a flow rate of 0.62 kg / hr, and the other nozzle is supplied with air at 31800 L / Hollow particles were granulated by spraying with hot air having an inlet temperature of 400° C. at a flow rate of hr (empty/liquid volume ratio of 63,600). Here, the outlet temperature was 150° C. (first step). A small amount of solid particles may also be granulated in the first step, but it is not necessary to remove the solid particles to proceed to the next step.
粒度分析計(セイシン企業社製レーザーマイクロンサイザーLMS-3000)を用いて、乾式で粉体の粒度分布を測定した。測定結果から、平均粒子径(D50)、最大粒子径(D100)が得られた。さらに、この粒度分布を分析して、2.0μm未満の粒子の体積比率を算出し、微小粒子量とした。 (1) Average particle size (D50), maximum particle size (D100), and amount of fine particles Using a particle size analyzer (Laser Micronsizer LMS-3000 manufactured by Seishin Enterprise Co., Ltd.), the particle size distribution of the powder was measured in a dry manner. . Average particle size (D50) and maximum particle size (D100) were obtained from the measurement results. Further, the particle size distribution was analyzed to calculate the volume ratio of particles less than 2.0 μm, which was defined as the amount of fine particles.
粉体を硫酸・弗化水素酸で前処理した後、塩酸に溶解させ、原子吸光光度計(日立製Z-2310)を用いて原子吸光分析法によりNa量を測定した。 (2) Amount of residual alkali The powder was pretreated with sulfuric acid/hydrofluoric acid, dissolved in hydrochloric acid, and the amount of Na was measured by atomic absorption spectrometry using an atomic absorption spectrophotometer (Z-2310 manufactured by Hitachi). .
Quantachrome Instruments社製Ultrapyc1200eを用いて、ガスピクノメーター法により粉体に含まれる粒子の密度の平均(粒子密度)を測定した。ガスは窒素ガスを用いた。
この粒子密度から、式「[2.2-(粒子密度)]/2.2×100」により空隙率(%)を算出した。粉体がシリカ粒子で構成されているとして、この式では、シリカの密度2.2g/cm3を用いた。 (3) Particle Density and Porosity Using Ultrapyc1200e manufactured by Quantachrome Instruments, the average density of particles contained in the powder (particle density) was measured by the gas pycnometer method. Nitrogen gas was used as the gas.
From this particle density, the porosity (%) was calculated by the formula “[2.2-(particle density)]/2.2×100”. Assuming that the powder is composed of silica particles, this formula used a silica density of 2.2 g/cm 3 .
ネットワークアナライザー(アンリツ社製、MS46122B)と空洞共振器(1GHz)を用いて空洞共振器摂動法により、誘電率(Dk)と誘電正接(Df)を測定した。ASTMD2520(JIS C2565)に準拠して測定した。 (4) Permittivity (Dk) and dielectric loss tangent (Df) of powder
A dielectric constant (Dk) and a dielectric loss tangent (Df) were measured by a cavity resonator perturbation method using a network analyzer (manufactured by Anritsu, MS46122B) and a cavity resonator (1 GHz). It was measured according to ASTM D2520 (JIS C2565).
まず、5質量%となるように粉体と水を混合し、10分間の超音波処理を行った。得られた分散液を25℃にて24時間静置した後、浮遊粒子、懸濁粒子及び沈降粒子をそれぞれ回収した。続いて、各粒子を105℃で24時間乾燥した後に計量し、その割合を算出した。 (5) Percentage of Floating Particles, Suspended Particles, and Sedimented Particles When Suspended in Water First, powder and water were mixed so as to make 5% by mass, and ultrasonic treatment was performed for 10 minutes. After the resulting dispersion was allowed to stand at 25° C. for 24 hours, suspended particles, suspended particles and settled particles were collected. Subsequently, each particle was dried at 105° C. for 24 hours and then weighed to calculate the ratio.
50mm×50mm×1mmの板状成型体(樹脂成型物)の誘電率(Dk)及び誘電正接(Df)を、ネットワークアナライザー(アンリツ社製、MS46122B)と同軸共振器を用いて、9.4GHzで測定した。粉体(フィラー)を配合していない樹脂成型物と次式で比較し、以下の基準で評価した。 (6) Dielectric constant (Dk) and dielectric loss tangent (Df) of resin molding
Dielectric constant (Dk) and dielectric loss tangent (Df) of a plate-shaped molding (resin molding) of 50 mm × 50 mm × 1 mm were measured at 9.4 GHz using a network analyzer (manufactured by Anritsu, MS46122B) and a coaxial resonator. It was measured. It was compared with a resin molding containing no powder (filler) according to the following formula and evaluated according to the following criteria.
△:低減率=0
×:低減率<0 ○: Reduction rate > 0
△: reduction rate = 0
×: reduction rate < 0
〇:低減率30%以上50%未満
△:低減率20%以上30%未満
×:低減率20%未満 ◎: Reduction rate of 50% or more ○: Reduction rate of 30% or more and less than 50% △: Reduction rate of 20% or more and less than 30% ×: Reduction rate of less than 20%
分級工程で日鉄鉱業社製エルボージェット(EJ-15)を用いて乾式慣性分級処理を行った。この装置では、粉体をF粉(微粉)、M粉(細粉)、G粉(粗粉)の3種類に分級することができる。このとき、M粉(細粉)に含まれる2.0μm未満の微小粒子が2体積%以下となるようにFエッジ距離を調整した。M粉を回収し、以降の工程を行った。これ以外は、実施例1と同様にして粉体と樹脂成型物を調製した。 [Example 2]
In the classification process, a dry inertia classification process was performed using an elbow jet (EJ-15) manufactured by Nittetsu Mining Co., Ltd. This device can classify powder into three types: F powder (fine powder), M powder (fine powder), and G powder (coarse powder). At this time, the F edge distance was adjusted so that the fine particles of less than 2.0 μm contained in the M powder (fine powder) were 2% by volume or less. M powder was collected and the subsequent steps were performed. A powder and a resin molding were prepared in the same manner as in Example 1 except for this.
分級工程で日清エンジニアリング社製エアロファインクラシファイアを用いて乾式遠心(半自由渦)分級処理を行った。回収粉に含まれる2.0μm未満の微小粒子が20体積%以下となるように、羽根の角度等を調整して分級した。これ以外は、実施例1と同様にして粉体と樹脂成型物を調製した。 [Example 3]
In the classification process, a dry centrifugal (semi-free vortex) classification treatment was performed using an Aerofine Classifier manufactured by Nisshin Engineering. The angle of the blades and the like were adjusted and classified so that the fine particles of less than 2.0 μm contained in the recovered powder were 20% by volume or less. A powder and a resin molding were prepared in the same manner as in Example 1 except for this.
回収された粒子に含まれる2.0μm未満の微小粒子が10体積%以下となるように、羽根の角度等を調整した。これ以外は、実施例3と同様にして粉体と樹脂成型物を調製した。 [Example 4]
The angles of the blades and the like were adjusted so that the fine particles of less than 2.0 μm contained in the collected particles were 10% by volume or less. A powder and a resin molding were prepared in the same manner as in Example 3 except for this.
分級処理(分級工程)を行わないこと以外は、実施例1と同様にして粉体と樹脂成型物を調製した。 [Comparative Example 1]
A powder and a resin molding were prepared in the same manner as in Example 1, except that the classification treatment (classification process) was not performed.
第一工程で噴霧乾燥器の入口温度を250℃に、第二工程で浸漬撹拌時間を1.5時間に変更した。さらに、分級工程を行わなかった。これ以外は実施例1と同様にして粉体と樹脂成型物を調製した。 [Comparative Example 2]
In the first step, the inlet temperature of the spray dryer was changed to 250°C, and in the second step, the immersion stirring time was changed to 1.5 hours. Furthermore, no classification step was performed. A powder and a resin molding were prepared in the same manner as in Example 1 except for this.
第一工程で噴霧乾燥機の入口温度を420℃に変更し、分級処理(分級工程)を行わなかった。これ以外は実施例1と同様にして粉体と樹脂成型体を調製した。 [Comparative Example 3]
In the first step, the inlet temperature of the spray dryer was changed to 420°C, and no classification treatment (classification step) was performed. A powder and a resin molding were prepared in the same manner as in Example 1 except for this.
分級処理(分級工程)を焼成後に行った。これ以外は実施例1と同様にして粉体と樹脂成型物を調製した。 [Comparative Example 4]
Classification treatment (classification process) was performed after firing. A powder and a resin molding were prepared in the same manner as in Example 1 except for this.
As shown in Table 1, the powders according to the examples and the resin moldings containing the powders have low dielectric constants and low dielectric loss tangents.
Claims (6)
- 無孔質の外殻の内部に空洞を有する中空粒子を含む粉体であって、
前記粉体の平均粒子径(D50)が2.0~10.0μm、粒子径2.0μm未満の微小粒子の含有量が20体積%以下であり、
前記粉体を水に懸濁した際、浮遊粒子が7.0~25.0質量%、懸濁粒子が0~4.0質量%、沈降粒子が71.0~93.0質量%であることを特徴とする粉体。 A powder comprising hollow particles having a cavity inside a nonporous outer shell,
The average particle diameter (D50) of the powder is 2.0 to 10.0 μm, and the content of fine particles having a particle diameter of less than 2.0 μm is 20% by volume or less,
When the powder is suspended in water, the suspended particles are 7.0 to 25.0% by mass, the suspended particles are 0 to 4.0% by mass, and the sedimented particles are 71.0 to 93.0% by mass. A powder characterized by: - 請求項1記載の粉体を樹脂材料に配合することを特徴とする樹脂組成物の製造方法。 A method for producing a resin composition, which comprises blending the powder according to claim 1 with a resin material.
- 珪酸アルカリ水溶液を熱風気流中で噴霧乾燥して粒子を調製する第一工程と、
前記粒子に含まれるアルカリを除去する第二工程と、
前記アルカリ除去された粒子を焼成する第三工程と、
を有し、
前記第一工程と前記第三工程の間に、粒子径2.0μm未満の微小粒子を除去する分級工程が設けられたことを特徴とする粉体の製造方法。 a first step of preparing particles by spray-drying an aqueous alkali silicate solution in a hot air stream;
a second step of removing the alkali contained in the particles;
a third step of firing the alkali-removed particles;
has
A method for producing powder, wherein a classification step for removing fine particles having a particle size of less than 2.0 μm is provided between the first step and the third step. - 前記第二工程において、粒子に含まれるアルカリ量を300ppm以下に低減することを特徴とする請求項3記載の粉体の製造方法。 The method for producing powder according to claim 3, wherein in the second step, the amount of alkali contained in the particles is reduced to 300 ppm or less.
- 前記第三工程の前に、前記中空粒子を乾燥する乾燥工程が設けられるとともに、
前記乾燥工程と前記第三工程の間に、前記分級工程が設けられたことを特徴とする請求項3又は4記載の粉体の製造方法。 A drying step for drying the hollow particles is provided before the third step,
5. The method for producing powder according to claim 3, wherein the classifying step is provided between the drying step and the third step. - 前記分級工程において、前記微小粒子が乾式分級処理により除去されることを特徴とする請求項3~5のいずれか一項に記載の粉体の製造方法。
6. The method for producing powder according to any one of claims 3 to 5, wherein in the classifying step, the fine particles are removed by a dry classification treatment.
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