WO2023171228A1 - フレーク状基材及び樹脂組成物 - Google Patents

フレーク状基材及び樹脂組成物 Download PDF

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Publication number
WO2023171228A1
WO2023171228A1 PCT/JP2023/004467 JP2023004467W WO2023171228A1 WO 2023171228 A1 WO2023171228 A1 WO 2023171228A1 JP 2023004467 W JP2023004467 W JP 2023004467W WO 2023171228 A1 WO2023171228 A1 WO 2023171228A1
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Prior art keywords
particle size
base material
resin composition
flaky base
flaky
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2023/004467
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English (en)
French (fr)
Japanese (ja)
Inventor
伸一 加藤
隆 若宮
伸路 三上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
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Nippon Sheet Glass Co Ltd
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 Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to EP23766408.1A priority Critical patent/EP4491591A4/en
Priority to CN202380022580.1A priority patent/CN118715185A/zh
Priority to JP2024505973A priority patent/JPWO2023171228A1/ja
Priority to US18/845,054 priority patent/US20250188251A1/en
Publication of WO2023171228A1 publication Critical patent/WO2023171228A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/005—Manufacture of flakes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3072—Treatment with macro-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
    • 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
    • C01B33/20—Silicates
    • C01B33/22—Magnesium silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • 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
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/29—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K3/346—Clay
    • 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
    • C08K3/40—Glass
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the present invention relates to a flaky base material and a resin composition.
  • glass fiber, carbon fiber, etc., glass beads, and flaky base materials such as glass flakes, mica, and talc are used to reduce warpage and deformation and/or improve mechanical strength. It is generally known that it is blended into matrix resin as a filler.
  • a glass flake has an average particle size of 0.1 to 15 ⁇ m and an average thickness of 0.1 to 2 ⁇ m, and the volume accumulation from the smaller particle size side in the particle size distribution is
  • a glass flake has been proposed in which the particle size is reduced by limiting the particle size D99, which corresponds to 99%, to 45 ⁇ m or less and the maximum particle size (D100) to 62 ⁇ m or less.
  • a flaky base material having an average particle size of 0.1 to 11 ⁇ m and an average thickness of 0.1 to 1.0 ⁇ m In the particle size distribution of the flaky base material, the particle size corresponding to a volume accumulation of 10% from the smaller particle size side is D10, and the particle size corresponding to a volume accumulation of 50% from the smaller particle size side is D50.
  • D90 is the particle size that corresponds to 90% of the volume accumulation from the small particle side
  • D99 is the particle size that corresponds to 99% of the volume accumulation from the small particle side
  • D99 is the particle size that corresponds to 99% of the volume accumulation from the small particle side.
  • a resin composition comprising a flaky base material and a matrix resin,
  • the flaky base material contained in the resin composition is The average particle size is 0.1 to 11 ⁇ m, the average thickness is 0.1 to 1.0 ⁇ m,
  • D10 is the particle size that corresponds to 10% volume accumulation from the small particle side
  • D50 is the particle size that corresponds to 50% volume accumulation from the small particle side
  • D50 is the particle size that corresponds to 50% volume accumulation from the small particle side
  • D90 is the particle size that corresponds to 90% volume accumulation from the smaller particle size side
  • D99 is the particle size that corresponds to 99% volume accumulation from the smaller particle size side
  • D99 is the particle size that corresponds to 100% volume accumulation from the smaller particle size side.
  • a flaky base material suitable for use as a filler for reinforcing a resin molded product it is possible to provide a flaky base material suitable for use as a filler for reinforcing a resin molded product, and further improve the impact resistance of the resin molded product reinforced with the flaky base material. Can be done.
  • FIG. 1 is a schematic diagram illustrating an example of an apparatus for producing glass flakes. It is a schematic diagram explaining another example of a manufacturing apparatus of flaky glass.
  • D90/D10 may be a predetermined value or more.
  • the flaky base material of this embodiment has an average particle size of 0.1 to 11 ⁇ m and an average thickness of 0.1 to 1.0 ⁇ m. Furthermore, in the particle size distribution of the flaky base material of this embodiment, the particle size corresponding to 10% of the volume accumulation from the smaller particle size side is D10, and the particle size corresponding to 50% of the volume accumulation from the smaller particle size side. D50 is the particle size that corresponds to 90% of the volume accumulation from the small particle size side, D99 is the particle size that corresponds to 99% of the volume accumulation from the small particle size side, and D99 is the particle size that corresponds to 99% of the volume accumulation from the small particle size side.
  • the flaky base material having the above characteristics is suitable for improving the impact resistance of the resulting resin molded product when used as a filler for reinforcing the resin molded product. Furthermore, the appearance and surface smoothness of the resulting resin molded product can be improved.
  • the flaky base material of this embodiment may be an inorganic base material formed of an inorganic material, or may be an organic base material formed of an organic material.
  • the inorganic base material include base materials made of carbon such as glass, mica, talc, wallasnite, kaolin, calcium carbonate, montmorillonite, silica, clay, bentonite, hydrotalcite, and graphite.
  • the organic base material include base materials made of aramid, polyamide, polyester, polyethylene, polypropylene, acrylic, or rayon. Further, as other organic base materials, base materials formed into flakes of cotton, linen, silk, etc. can also be used.
  • the flaky base material of this embodiment may be made of at least one selected from the group consisting of glass, mica, and talc.
  • the flaky base material of this embodiment may be flaky glass.
  • the average particle diameter of the flaky base material of this embodiment is within the range of 0.1 to 11 ⁇ m as described above.
  • the average particle size may be 0.5 ⁇ m or more, 1.0 ⁇ m or more, 2.2 ⁇ m or more, or even 2.4 ⁇ m or more.
  • the average particle size may be within the range of 2.4 to 11 ⁇ m, for example.
  • the average particle size may be 5 ⁇ m or less.
  • the average particle size of a flaky base material is the particle size distribution of a flaky base material measured based on a laser diffraction/scattering method, and the volume accumulation from the small particle size side is 50%.
  • the particle size (D50) corresponds to According to this embodiment, it is possible to obtain a flaky base material suitable for improving the impact strength of a resin molded product without restricting the overall particle size to a small value and reducing the average particle size (D50).
  • a flaky base material having a large average particle size is generally advantageous in that the degree of scattering during handling is suppressed.
  • the average thickness of the flaky base material of this embodiment is within the range of 0.1 to 1.0 ⁇ m.
  • the average thickness may be 0.2 ⁇ m or more, and further 0.3 ⁇ m or more.
  • the average thickness may be 0.9 ⁇ m or less, 0.8 ⁇ m or less, or even 0.7 ⁇ m or less.
  • the average thickness of a flake-like base material is, for example, the thickness of 100 or more flake-like base materials measured using a scanning electron microscope (SEM). It can be calculated as the total thickness divided by the number of sheets measured.
  • the width of the particle size distribution of the flaky base material can be expressed using D90/D10 as an index.
  • D90/D10 the wider the width of the particle size distribution, and the smaller the value of D90/D10, the narrower the width of the particle size distribution.
  • (D90 ⁇ D99 ⁇ D100)/D50 is an index indicating the content of coarse particles in the particle size distribution. The larger the value of (D90 ⁇ D99 ⁇ D100)/D50, the higher the content of coarse particles, and the smaller the value of (D90 ⁇ D99 ⁇ D100)/D50, the lower the content of coarse particles.
  • the flaky base material used as a glittering pigment generally has a narrow particle size distribution (that is, the content of fine particles and coarse particles is small).
  • Japanese Patent No. 4,652,445 discloses flaky particles (flake-like glass) that are applied to glitter pigments and have a D90/D10 value of 2.0 or more and 3.0 or less.
  • flaky base materials used as fillers for reinforcing resin molded articles do not need to have a narrow particle size distribution.
  • the fact that (D90 ⁇ D99 ⁇ D100)/D50 ⁇ 3200 and 3 ⁇ D90/D10 are satisfied at the same time greatly reduces the content of coarse particles.
  • the (D90 ⁇ D99 ⁇ D100)/D50 of the flaky base material of this embodiment is preferably 2,800 or less ((D90 ⁇ D99 ⁇ D100)/D50 ⁇ 2,800), particularly 2,700 or less.
  • the lower limit of (D90 ⁇ D99 ⁇ D100)/D50 is preferably 300 or more (300 ⁇ D90 ⁇ D99 ⁇ D100).
  • the lower limit particle size for pulverization of flaky base material is determined by the method and conditions, but the lower limit of (D90 x D99 x D100)/D50 of 300 or more means that pulverization can be carried out at an appropriate level with good manufacturing efficiency. In other words, this means that the content of coarse particles is not reduced too much.
  • the lower limit value of (D90 ⁇ D99 ⁇ D100)/D50 of the flaky base material of this embodiment may be 700 or more (700 ⁇ D90 ⁇ D99 ⁇ D100).
  • the upper limit value of D90/D10 of the flaky base material of this embodiment is not particularly limited, but is, for example, 13 or less (D90/D10 ⁇ 13).
  • the upper limit value of D90/D10 may be 11 or less (D90/D10 ⁇ 11).
  • D10 of the flaky base material of this embodiment may be 10 ⁇ m or less (D10 ⁇ 10 ⁇ m), and further may be 6.0 ⁇ m or less (D10 ⁇ 6.0 ⁇ m). D10 is preferably 2.0 ⁇ m or less (D10 ⁇ 2.0 ⁇ m). The lower limit of D10 is not particularly limited, but is, for example, 0.5 ⁇ m or more (0.5 ⁇ m ⁇ D10).
  • D50 of the flaky base material of this embodiment is as described above as the average particle diameter.
  • D90 of the flaky base material of this embodiment may be 25 ⁇ m or less (D90 ⁇ 25 ⁇ m), and further may be 20 ⁇ m or less (D90 ⁇ 20 ⁇ m). D90 is preferably 11 ⁇ m or less (D90 ⁇ 11 ⁇ m).
  • the lower limit of D90 is not particularly limited, but is, for example, 5.0 ⁇ m or more (5.0 ⁇ m ⁇ D90).
  • D99 of the flaky base material of this embodiment is preferably 21 ⁇ m or less (D99 ⁇ 21 ⁇ m).
  • the lower limit of D99 is not particularly limited, but is, for example, 10 ⁇ m or more (10 ⁇ m ⁇ D99).
  • D100 of the flaky base material of this embodiment is preferably 32 ⁇ m or less (D100 ⁇ 32 ⁇ m).
  • the lower limit of D100 is not particularly limited, but is, for example, 18 ⁇ m or more (18 ⁇ m ⁇ D100).
  • the values of D10, D50, D90, D99, and D100 in the particle size distribution of the flaky base material of this embodiment are values measured by dispersing it in water.
  • Flake glass can be suitably used as the flake base material of this embodiment.
  • the composition of the glass flakes commonly known glass compositions can be used. Specifically, a glass containing a small amount of alkali metal oxide such as E-glass, for example a glass in which the total content of Na 2 O and K 2 O is 2% or less on a mass basis, can be suitably used.
  • a typical composition of E-glass is shown below. The units of the following compositions are mass %.
  • the glass having this glass composition will be referred to as "TA-1 glass.”
  • substantially not contained means that it is not intentionally contained, unless it is unavoidably mixed, for example, by industrial raw materials.
  • the content of each of B 2 O 3 , F, ZnO, BaO, SrO and ZrO 2 is less than 0.1% by mass (preferably less than 0.05% by mass, more preferably 0.03% by mass). less than).
  • glass composition is disclosed by the applicant in WO 2010/024283. Hereinafter, the glass having this glass composition will be referred to as "TA-2 glass.”
  • the composition of the glass flakes is not limited to the glass compositions of E glass, TA-1 glass, and TA-2 glass shown above.
  • glass compositions of C glass, A glass, ECR glass, and S glass can also be used.
  • Low dielectric glasses disclosed by the present applicant for example, Patent No. 6505950, Patent No. 6775159, International Publication No. 2020/255396, International Publication No. 2020/256142, International Publication No. 2020/256143, International Publication 2021/049581
  • Patent No. 6505950, Patent No. 6775159, International Publication No. 2020/255396, International Publication No. 2020/256142, International Publication No. 2020/256143, International Publication 2021/049581 can also be used.
  • the flaky glass of this embodiment can be produced by, for example, the so-called blow method disclosed in Japanese Patent Publications No. 41-17148 and Japanese Patent Publication No. 45-3541, Japanese Patent Application Laid-open No. 59-21533 and Japanese Patent Application Publication No. It can be produced by the so-called rotary method disclosed in Japanese Patent No. 503669.
  • the glass manufacturing apparatus shown in FIG. 1 can be used.
  • This glass manufacturing apparatus includes a fireproof kiln tank 12, a blow nozzle 15, and a pressure roll 17.
  • the glass base 11 melted in the refractory kiln tank 12 (melting tank) is blown up into a balloon shape by the gas sent into the blow nozzle 15, and becomes a hollow glass film 16.
  • the hollow glass membrane 16 is crushed by a press roll 17 to obtain glass flakes 1.
  • the thickness of the glass flakes 1 can be controlled by adjusting the pulling speed of the hollow glass membrane 16, the flow rate of the gas sent from the blow nozzle 15, and the like.
  • the glass manufacturing apparatus shown in FIG. 2 can be used.
  • This glass manufacturing apparatus includes a pipe 21, a rotary cup 22, a set of annular plates 23, and an annular cyclone collector 24.
  • the molten glass base 11 is poured into the rotating cup 22 from the pipe 21, flows out radially from the upper edge of the rotating cup 22 due to centrifugal force, passes between the annular plates 23, is sucked by the air flow, and is passed through the annular cyclone type trap. It is introduced into the collector 24. While passing through the annular plate 23, the glass cools and solidifies in the form of a thin film, and is further crushed into minute pieces, thereby obtaining the glass flakes 1.
  • the thickness of the glass flakes 1 can be controlled by adjusting the spacing between the annular plates 23, the speed of the air flow, and the like.
  • the flaky base material of this embodiment can realize a resin molded article with improved impact resistance even if at least a portion of its surface is not covered with a surface treatment agent.
  • the surface treatment agent includes, for example, at least one selected from the group consisting of a binder component and a silane coupling agent.
  • the binder component contained in the surface treatment agent is not particularly limited, and any known binder component used for surface treatment of flaky base materials can be used as appropriate.
  • organic binder components include methylcellulose, carboxymethylcellulose, starch, carboxymethylstarch, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, acrylic resin, epoxy resin, epoxy-modified polyolefin resin, phenolic resin, vinyl acetate, and urethane resin. etc.
  • examples of the inorganic binder component include water glass, colloidal silica, and colloidal alumina.
  • the epoxy-modified polyolefin resin when used as a binder component, may include a polyolefin-glycidyl methacrylate copolymer, a polyolefin-allyl glycidyl ether copolymer, and/or a polyolefin containing glycidyl methacrylate or allyl glycidyl.
  • a preferred embodiment is a copolymer in which an ether is graft-bonded by the action of an organic peroxide, and an ethylene-glycidyl methacrylate copolymer (especially an ethylene-glycidyl methacrylate graft copolymer) containing ethylene and glycidyl methacrylate as essential components is a preferred embodiment.
  • Polymer is preferably used.
  • the invention is not limited to these, and includes, for example, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-ethyl acrylate ester-glycidyl methacrylate copolymer, ethylene - Acrylic acid butyl ester-glycidyl methacrylate copolymer, ethylene-acrylic acid-acrylic acid ester-glycidyl methacrylate copolymer, ethylene-methacrylic acid ester-glycidyl methacrylate copolymer, ethylene-methacrylic acid-methacrylic acid ester copolymer - glycidyl methacrylate copolymer, ethylene-polypropylene copolymer-glycidyl methacrylate graft copolymer, ethylene-vinyl acetate copolymer-glycidyl methacryl
  • examples of the epoxy resin include bisphenol A type epoxy resin, phenol novolac type epoxy resin, O-cresol novolac type epoxy resin, bisphenol F type epoxy resin.
  • examples include epoxy resins, biphenyl-type epoxy resins, alicyclic epoxy resins, and hydrogenated bisphenol A-type epoxy resins.
  • Epoxy resins may be used alone or in combination.
  • silane coupling agent examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -ureidopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, ⁇ - Examples include methacryloxypropyltrimethoxysilane. Among these, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane and ⁇ -ureidopropyltriethoxysilane are preferably used.
  • a titanium-based coupling agent, an aluminum-based coupling agent, a zirconia-based coupling agent, etc. can also be used.
  • the surface treatment agent may contain other components as necessary.
  • the surface treatment agent may further contain a crosslinking agent.
  • the surface treatment agent may further contain other components such as a urethane resin, a surfactant, and/or an antifoaming agent, if necessary.
  • the method of coating the surface of the flaky base material with the surface treatment agent is not particularly limited, and any known method can be used. For example, by adding a solution of the surface treatment agent to the flaky base material, stirring and drying, it is possible to form a flake base material in which at least a portion of the surface is coated with the surface treatment agent. Specific methods for adding, stirring and drying the solution of the surface treatment agent are not particularly limited, but examples thereof will be explained below.
  • a predetermined amount of the binder is added by spraying or the like while the flaky base material is fluidized, and mixed and stirred.
  • the flaky base material is dried while stirring in a mixer, or the flaky base material is taken out from the mixer and dried.
  • a flaky base material can also be produced using a rolling granulation method as described in JP-A-2-124732. That is, the flaky base material may be placed in a horizontal vibration type granulator equipped with stirring blades, and a solution of the surface treatment agent may be sprayed onto the flaky base material to form granules.
  • flaky base materials can be produced by applying known methods generally called agitation granulation, fluidized bed granulation, jet granulation, and rotary granulation.
  • the drying step is performed, for example, by heating the flaky base material to a temperature equal to or higher than the boiling point of the solvent used in the surface treatment agent solution and drying it until the solvent evaporates.
  • the content ratio of the surface treatment agent in the flaky base material can be controlled by adjusting the concentration of the surface treatment agent in the surface treatment agent solution to be added or sprayed. That is, by adding or spraying a predetermined amount of surface treatment agent solution to a predetermined amount of flaky base material so that the surface treatment agent becomes a predetermined amount, the content ratio of the coating film made of the surface treatment agent can be adjusted.
  • a flaky base material having a predetermined value can be manufactured.
  • the content of the coating film made of the surface treatment agent is, for example, 0.05 to 2% by mass, preferably 0.2 to 1.5% by mass, and More preferably, the content is .3 to 1% by mass.
  • the content ratio of the coating film is 0.05% by mass or more, the flaky base material can be sufficiently coated with the surface treatment agent, so the occurrence of a decrease in the strength of the resin molded product due to insufficient coverage is suppressed.
  • the content of the coating film is 2% by mass or less, gas is generated during extrusion molding, and problems such as contamination of the mold and discoloration of the resin molded product are suppressed.
  • the content of the coating film is 2% by mass or less, the bonding force between the flaky base materials will become too strong, and if the kneading of the resin molding is insufficient, the flaky base materials will form aggregates. Remaining in the resin molded product is unlikely to cause a decrease in the strength of the resin molded product.
  • the content of the coating film is 2% by mass or less, the excessive components of the coating film will adversely affect the adhesion between the base material and the matrix resin, making it impossible to obtain good molded product properties. There is nothing like that.
  • the resin composition of this embodiment includes the flaky base material of this embodiment described above and a matrix resin.
  • the flaky base material contained in the resin composition of this embodiment has an average particle size of 0.1 to 11 ⁇ m, an average thickness of 0.1 to 1.0 ⁇ m, D99 ⁇ 35 ⁇ m, D100 ⁇ 45 ⁇ m, 3 ⁇ D90/D10 and (D90 ⁇ D99 ⁇ D100)/D50 ⁇ 3200 are satisfied.
  • the resin composition of this embodiment can provide a resin molded article with improved impact resistance.
  • the resin composition of this embodiment can also improve the appearance and surface smoothness of the resulting resin molded product by including the flaky base material of this embodiment having the above characteristics as a filler. .
  • the values of D10, D50, D90, D99, and D100 in the particle size distribution of the flaky base material included in the resin composition of this embodiment are the values of D10, D50, and It satisfies the same numerical range as the values of D90, D99, and D100.
  • the particle size distribution of the flaky base material is affected by the dispersion into the resin composition, specifically, the effect of extrusion molding and/or molding of the resin composition to obtain a resin composition containing the flaky base material. It may be affected by injection molding to obtain resin molded products. That is, the particle size distribution of the flaky base material in the resin composition is not necessarily the same as the particle size distribution of the flaky base material before being dispersed in the resin composition. However, from the viewpoint of further improving the impact strength, it is desirable that the particle size distribution of the flaky base material in the resin composition also satisfy the conditions described above for the flaky base material.
  • the upper limit of the flaky base material contained in the resin composition of this embodiment may be 2800 ((D90 ⁇ D99 ⁇ D100)/D50 ⁇ 2800).
  • the flaky base material contained in the resin composition may have a particle size distribution satisfying 300 ⁇ (D90 ⁇ D99 ⁇ D100)/D50, and further, D90/D10 ⁇ 13.
  • the values of D10, D50, D90, D99, and D100 in the particle size distribution of the flaky base material contained in the resin composition of this embodiment are determined by heating the resin composition in an atmosphere of 625°C, This is a value measured by dispersing a flaky base material taken out by removing components in water.
  • the matrix resin may be, for example, a thermoplastic resin.
  • Thermoplastic resins include polypropylene, polyethylene, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polystyrene resin, styrene-acrylonitrile copolymer resin, polyacrylate, styrene-butadiene-acrylonitrile copolymer resin, polyarylene sulfide, polyphenylene sulfide, polyacetal, It may be at least one selected from the group consisting of polyamide, polyamideimide, liquid crystal polymer, polyetheretherketone, and polyetherimide.
  • the flaky base material of the present embodiment described above can achieve a high reinforcing effect on resin molded products, especially when polyolefin is used as the matrix resin, and even higher effects can be achieved when polypropylene is used, especially among polyolefins. Further, the flaky base material of the present embodiment described above can achieve a high reinforcing effect on resin molded products even when polybutylene terephthalate or polycarbonate is used as the matrix resin.
  • the content of the flaky base material in the resin composition is preferably 3 to 70% by mass. By setting the content to 3% by mass or more, the flaky base material can fully exhibit its function as a reinforcing material. On the other hand, by setting the content to 70% by mass or less, the flaky base material can be uniformly dispersed in the resin composition. In order to keep the molding shrinkage rate lower, it is more preferable that the content of the flaky base material is 10% by mass or more and 50% by mass or less.
  • the resin composition may contain components other than the matrix resin and flaky base material.
  • other components include fillers such as carbon black and thermoplastic elastomers.
  • Thermoplastic elastomers include olefin elastomers, styrene elastomers, hydrogenated polymer elastomers, and the like.
  • olefin elastomers include ethylene/ ⁇ -olefin copolymer elastomers (ethylene/propylene copolymer elastomer (EPR), ethylene/butene copolymer elastomer (EBR), and ethylene/hexene copolymer elastomer (EHR)).
  • thermoplastic elastomers Two or more types of thermoplastic elastomers can also be used in combination.
  • the resin molded product produced using the resin composition of this embodiment can obtain improved impact resistance due to the reinforcing effect of the flaky base material. Furthermore, improved appearance and surface smoothness can also be obtained.
  • Glass flakes 1 to 3 were produced by the blowing method described with reference to FIG. 1 using E glass, TA-1 glass, and TA-2 glass having the compositions shown in Tables 1A, 1B, and 1C, respectively. Specifically, each glass was placed in a melting tank heated to 1200° C. or higher and melted. Thin glass was prepared by blowing air through a nozzle, and this thin glass was continuously pulled out with a roller. Glass flakes 1 to 3 were obtained by adjusting the amount of air blown and the number of rotations of the roller so as to obtain the target thickness.
  • the average thickness and average particle diameter (D50) of glass flakes 1 to 3 are shown in Table 2.
  • the average thickness of the glass flakes was calculated by measuring the thickness of 100 pieces of glass flakes using an SEM, dividing the total thickness by the number of pieces measured, and rounding off the value to the second decimal place.
  • D50 of glass flakes 1 to 3 was measured by dispersing each glass flake in water using a laser diffraction particle size distribution measuring device (manufactured by Microtrac Bell, model: MT3300EX, measurement mode: HRA).
  • the average particle diameters (D50) of glass flakes a to f are shown in Table 2. Note that since glass flakes do not break in the thickness direction, that is, in the vertical direction, there was no difference in the average thickness of the glass before and after crushing. The D50 of glass flakes a to f was measured in the same manner as for glass flakes 1 to 3.
  • a rolling ball mill (pot mill, tube mill, conical mill, etc.), vibrating ball mill (circular vibrating vibrating mill, orbiting vibrating mill, centrifugal mill, etc.), planetary mill, etc. can be used.
  • pulverization was performed using a ball mill, but the pulverization method is not limited to this, and pulverization may be performed by other pulverization methods, whether wet or dry.
  • pulverization methods include impact crusher, gyratory crusher, cone crusher, jaw crusher, roll crusher, cutter mill, autogenous crusher, stamp mill, stone mill, mill, ring mill, roller mill, jet mill, hammer mill, pin mill, rotary mill.
  • a mill, vibratory mill, planetary mill, attritor, or bead mill can be used alone. These methods may be used in combination as appropriate.
  • the amount of decrease in the total mass of glass flakes due to classification relative to the total mass of glass flakes before classification is defined as the cut rate.
  • the cut rate is at least 5% or more, preferably 10% or more, more preferably 15% or more, and still more preferably 30% or more.
  • the cut rate is too large, the accuracy of classification will decrease and the expected effect may not be obtained.
  • the cutting rate is too large, the yield will also decrease, leading to an increase in manufacturing costs. Therefore, it is desirable that the cut rate is in the range of 15 to 45%.
  • the sieving and classification may be performed not only once but also in multiple times.
  • classification was performed by starting with a coarse sieve and decreasing the sieve opening size until the target cut rate was achieved.
  • a dry vibrating sieve can be used for sieving and classification. For example, use a sieve with a predetermined opening size or more to remove particularly large particles (for example, D100 and D99), then use a sieve with a predetermined opening size or less to remove By further removing particles with a large particle size (for example, D90) and thereby reducing the content of coarse particles, glass flakes having the particle size distribution in this embodiment can be obtained.
  • the opening size of the sieve used here may be appropriately selected depending on the particle size of the particles before sieving, the value of D50, D90, D99, D100, or D90/D10 of the desired glass flakes.
  • the removed coarse particles can be reused by re-pulverizing and re-classifying. By doing so, the final yield can be improved and costs can be reduced.
  • pulverization was performed using a sieve, but the classification method is not limited to this.
  • the target cut rate may be achieved by other classification methods, whether wet or dry.
  • horizontal flow and vertical upward flow wet type, hollow tube type, fluidized bed type, multi-stage bending type
  • inertial force field classification method a linear type, a curved type (impactor type), and an inclined type (louver type, Coanda effect utilization type) can be used.
  • the centrifugal force field classification method natural vortex type and forced vortex type can be used.
  • the cut rate and average particle diameter (D50) in the classification of flaky glasses A to M are shown in Table 2.
  • the measurement of D50 of glass flakes A to M was carried out in the same manner as for glass flakes 1 to 3.
  • the surface treatment agent solution is prepared by using water as a solvent and adding an emulsion of ethylene-glycidyl methacrylate copolymer as a binder component and a hydrolyzed solution of ⁇ -aminopropyltriethoxysilane as a silane coupling agent. Created. Thereafter, the undried glass flakes were taken out from the mixer and dried in a dryer at 125° C. for 8 hours to obtain glass flakes with at least a portion of the surface covered with the surface treatment agent.
  • the calculated proportion of the binder component in the flaky glass after drying is 50% by mass (50% by mass includes about 10% of emulsion-derived surfactant), and the proportion of the silane coupling agent is 50% by mass. there were.
  • the adhesion rate of the surface treatment agent was evaluated by the ignition loss method.
  • the adhesion rate of the surface treatment agent is the content rate of the coating film made of the surface treatment agent in the glass flakes. Specifically, after drying an appropriate amount of glass flakes at 110°C, it is heated in an atmosphere of 625°C to remove the surface treatment agent from the surface of the glass flakes, and the mass of the glass flakes before heating and the heating The adhesion rate of the surface treatment agent on the glass flakes was calculated from the difference from the mass of the subsequent glass flakes.
  • Examples 1 to 4, Comparative Examples 1 to 12 The glass flakes of Examples 1 to 4 and Comparative Examples 1 to 12 are indicated by alphabetical symbols in the column of glass flakes in Tables 3A to 3C. Symbols A to M correspond to glass flakes A to M in Table 2. Symbols a to f correspond to glass flakes a to f in Table 2. Symbol 1 corresponds to glass flake 1 in Table 2. The same applies to Examples and Comparative Examples described later. Incidentally, the glass flakes H and I were obtained only by classifying the glass flakes 1 without crushing them. No surface treatment was applied to the glass flakes of Examples 1 to 4 and Comparative Examples 1 to 12.
  • Examples 5 to 9, Comparative Examples 13 to 20 The glass flakes of Examples 5 to 9 and Comparative Examples 13 to 20 are indicated by alphabetical symbols in the column of glass flakes in Tables 4A to 4B. The glass flakes of Examples 5 to 9 and Comparative Examples 13 to 20 were subjected to surface treatment P.
  • Examples 10 to 15, Comparative Examples 21 to 23 The glass flakes of Examples 10 to 15 and Comparative Examples 21 to 23 are indicated by alphabetical symbols in the column of glass flakes in Tables 5A to 5B. The glass flakes of Examples 10 to 12 and Comparative Example 21 were not subjected to surface treatment. The glass flakes of Examples 13 to 15 and Comparative Examples 22 to 23 were subjected to surface treatment Q.
  • Examples 16-18, Comparative Examples 24-25 The glass flakes of Examples 16 to 18 and Comparative Examples 24 to 25 are indicated by alphabetical symbols in the column of glass flakes in Table 6. The glass flakes of Examples 16 to 18 and Comparative Examples 24 to 25 were subjected to surface treatment Q.
  • Resin molded product Resin molded articles of Examples 1 to 9 and Comparative Examples 1 to 20 were molded by the following method. Glass flakes, polypropylene (Novatec BC06C, manufactured by Nippon Polypro Co., Ltd.), thermoplastic elastomer (ethylene-octene copolymer elastomer, Engage 8200, manufactured by Dow Chemical Company), and carbon black fine powder were each mixed at 20% by mass and 58% by mass. They were uniformly mixed so that the concentrations were 20% by mass, 20% by mass, and 2% by mass.
  • the resulting mixture was kneaded using an extrusion molding machine (KZW15-30MG, manufactured by Technovel Co., Ltd., molding temperature: approximately 210 to 220°C), and the resulting mixture contained polypropylene as a matrix resin and glass flakes as a reinforcing filler.
  • a resin composition was obtained.
  • This resin composition was molded using an injection molding machine (manufactured by Nissei Jushi Kogyo Co., Ltd., HM7) to obtain a resin molded product.
  • the content of flaky glass in the resulting resin molded product was 20% by mass.
  • the resin molded products of Examples 10 to 15 and Comparative Examples 21 to 23 were the same as those of Examples 1 to 9 and Comparative Examples 1 to 20, except that polypropylene was replaced with polybutylene terephthalate (manufactured by Polyplastics, Duranex 2000). Obtained by the same method as .
  • the content of flaky glass in the resulting resin composition was 30% by mass.
  • the resin molded products of Examples 16 to 18 and Comparative Examples 24 to 25 were the same as Examples 1 to 9 and Comparative Examples 1 to 20, except that polypropylene was replaced with polycarbonate (Iupilon S3000F, manufactured by Mitsubishi Engineering Plastics). Obtained by the method. The content of flaky glass in the resulting resin composition was 30% by mass.
  • the content of flaky glass in the resin composition was evaluated by a loss-on-ignition method. Specifically, an appropriate amount of resin molded product is heated in an atmosphere of 625°C to remove components other than glass flakes, and the mass of the resin molded product before heating and the mass of the residue (flake glass) after heating are calculated. The content of flaky glass in the resin composition was calculated from the difference.
  • Measurement of particle size distribution by laser diffraction/scattering method was performed on the residual glass flakes generated when calculating the content of glass flakes in the resin composition. Specifically, each glass flake was dispersed in water and the particle size distribution was measured using a laser diffraction particle size distribution measuring device (manufactured by Microtrac Bell, model: MT3300EX, measurement mode: HRA). From the measurement results, the values of D10, D50, D90, D99, and D100 of the glass flakes in the resin composition were read.
  • D90/D10 and (D90 ⁇ D99 ⁇ D100)/D50 of the glass flakes in the resin composition were calculated.
  • D10 is the particle size that corresponds to 10% volume accumulation from the small particle size side
  • D50 is the particle size that corresponds to 50% volume accumulation from the small particle size side
  • D50 is the particle size that corresponds to 50% volume accumulation from the small particle size side
  • D90 is the particle size that corresponds to 90% volume accumulation from the side
  • D99 is the particle size that corresponds to 99% volume accumulation from the small side
  • D99 corresponds to 100% volume accumulation from the small side.
  • the particle size was determined as D100. The results are shown in Tables 3A-6.
  • the resin molded product was observed under an optical microscope at a magnification of 20 times, and the relative smoothness of the surface of the resin molded product was evaluated on a scale of 10, and a score of 8 or higher was considered to be a pass.
  • the scratch resistance was measured using a scratch hardness meter (manufactured by Eriksen, pencil type scratch hardness meter: model 318, tip diameter 0.75 mm) while applying a constant load (1 to 10 N) to the above flat plate for appearance evaluation.
  • the scratches (degree of whitening) when pulled vertically at a speed of 1 cm per second were evaluated relative to each other on a scale of 10, and a score of 8 or higher was considered to be a pass.
  • the results are shown in Tables 3A-6.
  • the impact resistance, appearance, surface smoothness, and scratch resistance of the resin molded products of the examples are lower than those of the comparative examples. improved compared to resin molded products.
  • the durability of resin molded products using thermoplastic resins such as polypropylene resin as the matrix resin can be improved. It was possible to improve impact resistance, appearance, surface smoothness, and scratch resistance.
  • the Izod impact strength N (with notch) measured according to JIS K 7110 was a good value.
  • the Izod impact strength N (with notch) was 10.0 or more.
  • flaky glass is used as the flaky base material in the above embodiments, similar effects can be expected in the present invention even with materials other than flaky glass, such as mica and talc.
  • the flaky base material of the present invention can effectively improve the impact resistance, appearance, surface smoothness, and scratch resistance of the resin composition, so it can be applied to various uses.
  • the resin composition containing the flaky base material and thermoplastic resin of the present invention has conventionally been used in fields where appearance and surface smoothness are important, and where fibrous filler cannot be used but impact resistance is important.
  • it is suitably used in the interior and exterior fields of automobiles or electronic parts. More specifically, it can be applied to exterior members such as automobile bumpers or interior members such as instrument panels made of polypropylene.

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JPWO2025057938A1 (https=) * 2023-09-15 2025-03-20
JP2025114646A (ja) * 2023-09-15 2025-08-05 日本板硝子株式会社 ガラス粉体
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JP7833593B2 (ja) 2023-09-15 2026-03-19 日本板硝子株式会社 ガラス粉体

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