WO2022249652A1 - Composition de résine, et article moulé - Google Patents

Composition de résine, et article moulé Download PDF

Info

Publication number
WO2022249652A1
WO2022249652A1 PCT/JP2022/011223 JP2022011223W WO2022249652A1 WO 2022249652 A1 WO2022249652 A1 WO 2022249652A1 JP 2022011223 W JP2022011223 W JP 2022011223W WO 2022249652 A1 WO2022249652 A1 WO 2022249652A1
Authority
WO
WIPO (PCT)
Prior art keywords
calcium carbonate
resin composition
resin
mass
phosphate
Prior art date
Application number
PCT/JP2022/011223
Other languages
English (en)
Japanese (ja)
Inventor
剛紀 笹川
Original Assignee
株式会社Tbm
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 株式会社Tbm filed Critical 株式会社Tbm
Publication of WO2022249652A1 publication Critical patent/WO2022249652A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to resin compositions and molded articles. More specifically, in the present invention, although the thermoplastic resin is highly filled with calcium carbonate, the amount of elution under acidic conditions is small, the moldability is good, and physical properties such as mechanical strength are excellent.
  • the present invention relates to resin compositions and molded articles made of such resin compositions, particularly food packaging containers and tableware.
  • the inorganic substance powder falls off during use, and the inorganic substance powder falls off into the food, especially liquid food such as strongly acidic beverages. It has been a problem that there is a risk that calcium carbonate used as a elution.
  • a resin container used for food with a pH of 5 or less is required to have a small amount of elution in warm acetic acid, but a resin composition containing a large amount of calcium carbonate tends to have a large amount of elution.
  • Patent Literature 2 discloses a sheet-like laminate in which outer layers of a thermoplastic resin are laminated on both sides of an inner layer containing more than 50% by mass of an inorganic filler.
  • Patent Document 2 also describes a technique of treating the surface of calcium carbonate particles with a silane coupling agent or a metallic soap.
  • the surface treatment technique itself is known, and for example, non-patent document 1, patent documents 3 and 4 describe calcium carbonate surface-treated with resin acid, silane, phosphate ester, etc., in addition to fatty acid.
  • a laminate such as that described in Patent Document 2 requires a lamination process during manufacturing, which poses a problem in terms of productivity. Since it is also difficult to provide a surface layer on the edge of a container or the like, good evaluation results may not be obtained in the acetic acid elution test. The cost of the resin laminate tends to be high, and it is difficult to contribute to environmental protection by reducing the consumption of synthetic resin. A technique for suppressing elution from an inorganic substance powder-filled resin composition without laminating a resin layer is desired.
  • Patent Document 2 also states that surface treatment with calcium stearate or the like can suppress the formation of voids at the interface between the calcium carbonate particles and the thermoplastic resin, and improve the moldability of the laminate. However, as shown in the examples below, if the surface treatment agent is inappropriately selected, the moldability and mechanical properties of the resin composition may rather deteriorate.
  • Non-Patent Document 1 Many of the conventional surface treatment methods, such as Non-Patent Document 1, have been studied in systems with a smaller amount of calcium carbonate compounded compared to thermoplastic resins and the like.
  • US Pat. No. 5,400,005 polymer compositions containing up to 95% by weight of surface-treated inorganic substances are also described.
  • Patent Document 4 describes an electric wire sheath layer based on a composition filled with a large amount of silane-treated calcium carbonate or the like, its physical properties such as mechanical strength are not evaluated.
  • resin compositions filled with a large amount of inorganic substance powder, especially resin compositions for food the relationship between the surface treatment method and the moldability and mechanical properties has not been studied at present. .
  • An object of the present invention is to provide a resin composition which is excellent in physical properties such as physical strength and particularly suitable for food packaging containers and tableware, and a molded article made of such a resin composition.
  • a surface treatment agent containing a phosphate ester particularly a surface treatment agent mainly composed of a phosphate ester having a specific structure, is used to produce carbonic acid.
  • the inventors have found that by treating the surface of calcium, the moldability can be improved without deteriorating the physical properties of the resin composition, and the amount of elution into acetic acid and the like can be reduced, leading to the present invention.
  • the present invention for solving the above problems is a resin composition containing a thermoplastic resin and an inorganic substance powder at a mass ratio of 50:50 to 10:90, wherein the inorganic substance powder contains a phosphate ester.
  • a resin composition characterized by being calcium carbonate surface-treated with a surface-treating agent.
  • the phosphate is polyoxyethylene lauryl ether phosphate.
  • the average particle diameter of the calcium carbonate particles calculated from the measurement results of the specific surface area by an air permeation method according to JIS M-8511 is 0.7 ⁇ m or more and 6.0 ⁇ m or less. A resin composition is shown.
  • the calcium carbonate is ground calcium carbonate.
  • the thermoplastic resin is a polyolefin resin.
  • the polyolefin-based resin is a resin composition comprising a polyethylene-based resin and/or a polypropylene-based resin.
  • a food packaging container made of any one of the resin compositions described above is shown.
  • the resin composition has a small amount of elution under acidic conditions, good moldability, and excellent physical properties such as mechanical strength, even though the thermoplastic resin is highly filled with calcium carbonate. goods are provided. Molded articles based on the resin composition of the present invention are particularly suitable for food packaging containers and tableware.
  • the resin composition of the present invention contains a thermoplastic resin and calcium carbonate surface-treated with a surface-treating agent containing a phosphate ester in a mass ratio of 50:50 to 10:90. These components in the resin composition are described below.
  • thermoplastic resin In the resin composition of the present invention, the type of thermoplastic resin is not particularly limited. Examples include polyethylene resins, polypropylene resins, polymethyl-1-pentene, polyolefin resins such as ethylene-cyclic olefin copolymers; ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid Copolymer, metal salt of ethylene-(meth)acrylic acid copolymer (ionomer), ethylene-alkyl acrylate copolymer, ethylene-alkyl methacrylate copolymer, maleic acid-modified polyethylene, maleic acid-modified polypropylene functional group-containing polyolefin resins such as; nylon-6, nylon-6,6, nylon-6,10, nylon-6,12 and other polyamide resins; polyethylene terephthalate and its copolymers, polyethylene naphthalate, polybutylene Aromatic polyester resins such as
  • thermoplastic resins can also be used in combination. It also contains elastomer components such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-ethylene copolymer, styrene-isoprene-ethylene copolymer, acrylonitrile-butadiene copolymer, fluorine-based elastomer, etc. It's okay to be
  • thermoplastic resins polyolefin resins are preferred in terms of moldability, performance, and economy.
  • the polyolefin-based resin is a polyolefin-based resin having olefin component units as a main component. Cyclic olefin copolymers and the like, and mixtures of two or more thereof are also included.
  • the above-mentioned "mainly composed” means that the olefin component unit is contained in the polyolefin resin in an amount of 50% by mass or more, and the content is preferably 75% by mass or more, more preferably 85% by mass. % or more, more preferably 90 mass % or more.
  • homopolymers (homopolymers) of polyolefins are preferred.
  • the method for producing the polyolefin resin used in the present invention is not particularly limited, and can be obtained by any method using a Ziegler-Natta catalyst, a metallocene catalyst, a radical initiator such as oxygen or a peroxide, or the like. It may be something else.
  • the resin composition of the present invention preferably contains a polyethylene-based resin and/or a polypropylene-based resin as these polyolefin-based resins. More preferably, the thermoplastic resin consists essentially of polyethylene-based resin and/or polypropylene-based resin. These resins are particularly excellent in the balance of physical properties, moldability, and cost, and are suitable as the thermoplastic resin component in the resin composition of the present invention. In particular, polypropylene-based resins are preferably used because they are particularly excellent in the balance between mechanical strength and heat resistance.
  • polypropylene-based resin examples include resins having a propylene component unit of 50% by mass or more, such as propylene homopolymers and copolymers of propylene and other copolymerizable monomers.
  • Propylene homopolymers include isotactic, syndiotactic, atactic, hemiisotactic, and linear or branched polypropylenes exhibiting various stereoregularities.
  • the above copolymer may be a random copolymer or a block copolymer, and may be a terpolymer as well as a binary copolymer.
  • Copolymerization components include ethylene, 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3,4-dimethyl-1-butene, 1-heptene, ⁇ -olefins having 4 to 10 carbon atoms such as 3-methyl-1-hexene; furthermore, tetrafluoroethylene, vinyl acetate and the like, but are not limited thereto.
  • propylene homopolymers as a result of polymerization, there are cases where a structure as if an ⁇ -olefin such as hexene is copolymerized is partly included, but in the present invention, such a polymer is also included. , is broadly included as a propylene homopolymer (propylene homopolymer). These polypropylene-based resins can be used alone or in combination of two or more.
  • polyethylene-based resin examples include resins having an ethylene component unit of 50% by mass or more.
  • examples include high-density polyethylene (HDPE), low-density polyethylene (LDPE), medium-density polyethylene, linear low-density polyethylene ( LLDPE), ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-butene 1 copolymer, ethylene-butene 1 copolymer, ethylene-hexene 1 copolymer, ethylene-4 methylpentene 1 Copolymers, ethylene-octene 1 copolymers, etc., and mixtures of two or more thereof are also included.
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • ethylene-vinyl acetate copolymer ethylene-propylene copolymer
  • the inorganic powder contained in the resin composition of the present invention is calcium carbonate surface-treated with a surface-treating agent containing a phosphate ester.
  • Calcium carbonate includes those prepared by a synthetic method (so-called light calcium carbonate) and those obtained by mechanically pulverizing and classifying natural raw materials containing CaCO3 as a main component such as limestone (so-called heavy calcium carbonate). Any of them may be used, and these may be used in combination.
  • the shape thereof is not particularly limited, and may be in the form of particles, flakes, granules, fibers, or the like. As for the particulate form, it may be spherical as generally obtained by a synthetic method, or irregularly shaped as obtained by pulverizing collected natural minerals. .
  • the average particle size of the inorganic substance powder such as calcium carbonate described in this specification refers to a value calculated from the measurement result of the specific surface area by the air permeation method according to JIS M-8511.
  • a specific surface area measuring device SS-100 manufactured by Shimadzu Corporation can be preferably used.
  • the average particle size is larger than 6.0 ⁇ m, for example, when a sheet-like molded product is formed, the inorganic powder protrudes from the surface of the molded product and falls off, depending on the layer thickness of the molded product. Otherwise, the surface properties, mechanical strength, etc. may be impaired.
  • the particle size distribution does not contain particles having a particle size of 45 ⁇ m or more.
  • the particles are too fine, the viscosity will increase significantly when kneaded with the above-mentioned resin, which may make it difficult to produce molded articles. Such a problem can be prevented by setting the average particle size of the inorganic powder to 0.7 ⁇ m or more, particularly 0.8 ⁇ m or more and 6.0 ⁇ m or less.
  • calcium carbonate is a first calcium carbonate having an average particle size of 0.7 ⁇ m or more and less than 2.0 ⁇ m, particularly 0.8 ⁇ m or more and less than 2.0 ⁇ m, as measured by an air permeation method according to JIS M-8511; It may also contain a second calcium carbonate having an average particle size of 2.0 ⁇ m or more and 6.0 ⁇ m or less, particularly 2.0 ⁇ m or more and 5.0 ⁇ m or less, as measured by an air permeation method using M-8511. As a result, it is possible to improve the physical properties such as the surface properties of the molded product and the printability and blocking property.
  • the average particle size of the first calcium carbonate is a and the average particle size of the second calcium carbonate is b
  • the a/b ratio is 0.85 or less, more preferably. is roughly 0.10 to 0.70, more preferably 0.10 to 0.50. This is because a particularly excellent effect can be expected by jointly using particles having such a clear difference in average particle size to some extent.
  • each of the first calcium carbonate and the second calcium carbonate preferably has a coefficient of variation (Cv) of the distribution of particle diameters ( ⁇ m) of about 0.01 to 0.10, particularly 0.03. It is desirable to be about 0.08. If the variation in particle size defined by the coefficient of variation (Cv) is this level, it is considered that each powder group can provide more complementary effects.
  • the mass ratio of the first calcium carbonate to the second calcium carbonate is preferably about 90:10 to 98:2, more preferably about 92:8 to 95:5. Three or more calcium carbonate groups having different average particle size distributions may be used.
  • calcium carbonate preferably contains ground calcium carbonate.
  • the inorganic substance powder in the resin composition of the present invention is composed of heavy calcium carbonate and its unavoidable impurities.
  • heavy calcium carbonate is obtained by mechanically pulverizing and processing natural limestone or the like, and is clearly distinguished from synthetic calcium carbonate produced by chemical precipitation reaction or the like.
  • the pulverization method includes a dry method and a wet method, and the dry method is preferred.
  • ground calcium carbonate is characterized by surface irregularities and a large specific surface area due to the fact that particles are formed by a pulverization process. Since ground calcium carbonate has such an irregular shape and a large specific surface area, when blended in a thermoplastic resin, ground calcium carbonate has a larger contact interface with the thermoplastic resin. , is effective for uniform dispersion.
  • the specific surface area of the calcium carbonate is desirably about 3,000 cm 2 /g or more and 35,000 cm 2 /g or less, though it depends on the average particle size. .
  • the specific surface area referred to here is obtained by the air permeation method. When the specific surface area is within this range, there is a tendency to suppress deterioration in processability of the obtained molded article.
  • the irregularity of the calcium carbonate particles can be represented by a low degree of spheroidization of the particle shape, and is not particularly limited. 0.95 or less, more preferably 0.55 or more and 0.93 or less, and still more preferably 0.60 or more and 0.90 or less. If the circularity of the calcium carbonate particles is within this range, the strength and molding processability of the molded article will be moderate.
  • the circularity can be expressed by (the projected area of the grain)/(the area of the circle having the same circumferential length as the projected circumferential length of the grain).
  • the method for measuring the roundness is not particularly limited, and for example, the projected area and the projected peripheral length of the grain may be measured from a micrograph, or image analysis software that is generally commercially available may be used.
  • the above calcium carbonate is at least partly surface-treated with a surface-treating agent containing a phosphate ester.
  • a surface-treating agent containing a phosphate ester By such surface treatment (surface modification), the dispersibility and reactivity of calcium carbonate can be enhanced, and the physical properties and moldability of the resin composition can be improved.
  • surface treatment surface modification
  • the dispersibility and reactivity of calcium carbonate can be enhanced, and the physical properties and moldability of the resin composition can be improved.
  • unlike calcium carbonate that has been modified with general-purpose surface treatment agents such as fatty acids even when it is highly filled in a thermoplastic resin, it has excellent physical properties such as mechanical properties and elution under acidic conditions in a well-balanced manner.
  • a resin composition suitable for packaging containers and tableware is provided.
  • a surface treatment agent containing a phosphoric acid ester includes all surface treatment agents containing a phosphoric acid-based ester.
  • phosphoric acid-based esters include monoesters, diesters and triesters of phosphoric acid and alcohols; monoesters, diesters and triesters of phosphoric acid and phenols; monoesters, diesters and triesters of phosphoric acid and alkylphenols.
  • phosphoric acid esters having a structure in which an alkyloxy group, an alkyloxyalkyleneoxy group, and a hydroxy group are bonded to a phosphorus atom; and salts thereof, such as sodium salts, potassium salts, ammonium salts, etc., but are not limited thereto.
  • salts thereof such as sodium salts, potassium salts, ammonium salts, etc., but are not limited thereto.
  • a plurality of types of these phosphate esters can also be used in combination.
  • surface treatment agents containing fatty acids, resin acids, fatty acid anhydride-modified resins, etc., together with these phosphate esters may be used.
  • the phosphate ester is preferably a monoester, a diester, a salt thereof, or a mixture of two or more thereof.
  • surface treatment agents containing monoesters and diesters are effective in modifying the surface of calcium carbonate.
  • the longer the aliphatic hydrocarbon chain length the more excellent the compatibility with the thermoplastic resin tends to be, and the effect of the present invention is particularly remarkable.
  • phosphoric acid esters having long-chain aliphatic hydrocarbon groups in the molecule such as monoesters, diesters and triesters of phosphoric acid and long-chain alcohols; monoesters, diesters and triesters of phosphoric acid and long-chain alkylphenols. monoesters, diesters, triesters of phosphoric acid, long-chain alcohols and alkylene oxides; and salts thereof. More preferably, it is one or more phosphoric acid esters selected from monoesters and diesters of phosphoric acid and long-chain alcohols, monoesters and diesters of phosphoric acid, long-chain alcohols and alkylene oxide, and salts thereof. .
  • the aliphatic hydrocarbon group in the phosphate ester is not particularly limited, and includes all saturated or unsaturated linear, branched, or cyclic aliphatic hydrocarbon groups. It may be substituted with a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, or the like. Examples include isopropyl group, butyl group, hexyl group, n-octyl group, isooctyl group, decyl group, dodecyl group (lauryl group), pentadecyl group (myristyl group), tetradecyl group (myristyl group), hexadecyl group (palmityl group).
  • octadecyl group (stearyl group), hexadecenyl group (palmitoleyl group), octadecenyl group (oleyl group), octadecadienyl group (linoleyl group, elaidolinolenyl group), octadecatrienyl group (linolenyl group), hydroxy octadecenyl group (linoleyl group) and the like, but not limited thereto.
  • the number of carbon atoms in the aliphatic hydrocarbon group is also not particularly limited, and may be, for example, an aliphatic hydrocarbon group having 3 to 20 carbon atoms, especially 8 to 18 carbon atoms, especially 10 to 14 carbon atoms.
  • the phosphoric acid ester is particularly preferably monoester, diester and/or salt thereof of phosphoric acid, alcohol and alkylene oxide.
  • the hydrocarbon group (corresponding to C x H 2x+1 ) of the phosphate ester may have, for example, an unsaturated bond or a cyclic structure, and the number of hydrogen atoms may be 2x-1 or less.
  • the surface of calcium carbonate can be particularly effectively modified, the amount of elution under acidic conditions is small, and it is possible to obtain a resin composition having good physical properties such as mechanical strength.
  • a resin composition having good physical properties such as mechanical strength.
  • having an alkylene oxide unit in the molecule causes the aliphatic hydrocarbon group to spread more widely from the phosphate ester on the calcium carbonate surface, resulting in the surface It is considered that the compatibility between the treated calcium carbonate and the thermoplastic resin is good.
  • the number of alkylene oxide units (z in Formula 1) is also not particularly limited. For example, 1 to 12 alkylene oxide units, particularly 1 to 4 Individual ones are preferred. More preferably, polyoxyethylene (1-4) lauryl ether phosphate and/or salts thereof, particularly preferably monopolyoxyethylene (2) lauryl ether phosphate, dipolyoxyethylene (2) lauryl ether phosphate, and salts thereof.
  • ⁇ Surface treatment method> There is no particular limitation on the surface treatment method of calcium carbonate with the phosphate ester as described above, and various known surface treatment methods can be employed. For example, a method of adding a phosphoric acid ester to a slurry of calcium carbonate and stirring (wet method), a method of adding calcium carbonate and a phosphoric acid ester to a grinder or a mixer, and optionally heating and stirring (dry method), Furthermore, a method of stirring a hydrous cake of calcium carbonate and a phosphoric acid ester while heating them in a mixer may be used, but the methods are not limited to these. Depending on the type of phosphate ester used as the surface treatment agent, it is generally preferable to carry out the surface treatment of light calcium carbonate by a wet method and the surface treatment of heavy calcium carbonate by a dry method.
  • the amount ratio of phosphate ester to calcium carbonate during surface treatment is not particular limitation.
  • the amount of the phosphate ester is 0.2 to 10 parts by mass, particularly 0.5 to 5 parts by mass, more preferably about 1 to 3 parts by mass, based on 100 parts by mass of calcium carbonate.
  • the amount of phosphate on the surface of calcium carbonate can be quantified by a known analysis method such as solvent extraction or pyrolysis GC/MS.
  • the aqueous slurry has a calcium carbonate concentration of 10 to 300 g/L, particularly 25 to 200 g/L. With such a concentration, the productivity of surface treatment is enhanced, and the workability is not lowered due to an increase in viscosity.
  • the slurry temperature in the wet method is preferably 20 to 98°C, more preferably 40 to 90°C, still more preferably 60 to 80°C.
  • the surface treatment agent can be uniformly adsorbed and bonded onto the calcium carbonate, and the surface can be treated uniformly.
  • the slurry temperature is 98° C. or lower, there is no risk of bumping or the like, and a pressure-resistant device is not required.
  • the slurry may contain a surfactant.
  • the surface treatment by the dry method can be performed by kneading calcium carbonate and phosphate ester in a kneader such as a Henschel mixer, kneader, or extrusion kneader.
  • a kneader such as a Henschel mixer, kneader, or extrusion kneader.
  • a desired phosphoric acid ester can be added to the grinder, and surface treatment can be performed at the same time as adjusting the particle size of the calcium carbonate.
  • the temperature during the surface treatment can be arbitrarily set according to the type of phosphate ester used, but is generally about 20 to 150°C, particularly 40 to 130°C, and further about 60 to 120°C. is preferred. By carrying out the surface treatment at 20° C.
  • the surface treatment agent can be uniformly adsorbed and bonded onto the calcium carbonate, and the surface can be treated uniformly.
  • the treatment temperature is about 150° C. or lower, the risk of thermal deterioration and deterioration of the surface treatment agent can be reduced. More preferably, the temperature is higher than the melting point of the phosphate used. This allows the surface treatment agent to more uniformly adsorb and bind onto the calcium carbonate.
  • polyoxyethylene lauryl ether phosphate or the like is liquid at room temperature, the surface treatment can be performed at room temperature. When polyoxyethylene stearyl ether phosphate or the like is used, it may be kneaded at a temperature of about 50 to 150°C.
  • a small amount of solvent can be used in combination even in the dry method.
  • an aqueous solution of a phosphoric acid ester, particularly a salt-type phosphoric acid ester may be added to calcium carbonate and kneaded or pulverized as described above.
  • the temperature during treatment is preferably 20 to 150°C, particularly about 40 to 98°C. This makes it possible to reduce the risk of non-uniform adsorption and bumping of the surface treatment agent.
  • the inorganic substance powder is calcium carbonate surface-treated with a surface treatment agent containing a phosphate ester as described above, but may further contain inorganic substance powders other than these.
  • examples include powdery carbonates, sulfates, silicates, phosphates, borates, oxides, or hydrates thereof of calcium, magnesium, aluminum, titanium, iron, zinc, etc.
  • non-surface-treated calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, silica, alumina, clay, talc, kaolin, aluminum hydroxide, magnesium hydroxide, aluminum silicate, magnesium silicate, silicic acid Calcium, aluminum sulfate, magnesium sulfate, calcium sulfate, magnesium phosphate, barium sulfate, silica sand, carbon black, zeolite, molybdenum, diatomaceous earth, sericite, shirasu, calcium sulfite, sodium sulfate, potassium titanate, bentonite, wollastonite, Dolomite, graphite and the like can be mentioned.
  • the inorganic substance powder in the resin composition of the present invention is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 95% by mass or more. is substantially entirely composed of the above-mentioned surface-treated calcium carbonate powder, excluding unavoidable impurities.
  • the resin composition of the present invention contains the thermoplastic resin and the inorganic powder in a mass ratio of 50:50 to 10:90. If the content of the inorganic substance powder is too small, it is difficult to obtain physical properties such as texture and strength of the resin composition.
  • the ratio of the inorganic substance powder to the total mass of the thermoplastic resin and the inorganic substance powder is preferably 52% by mass or more, more preferably 55% by mass or more.
  • the upper limit of the ratio is preferably 80% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass or less.
  • the resin composition according to the present invention may optionally contain other additives as auxiliary agents.
  • Other additives include, for example, colorants, lubricants, coupling agents, fluidity modifiers (fluidity modifiers), cross-linking agents, dispersants, antioxidants, ultraviolet absorbers, flame retardants, stabilizers, and electrifying agents. Inhibitors, foaming agents, plasticizers, etc. may be blended. These additives may be used alone or in combination of two or more. Moreover, these may be blended in the kneading step described later, or may be blended in the raw material components in advance before the kneading step.
  • the amount of these other additives added is not particularly limited as long as it does not impede the desired physical properties and processability, but the mass of the entire resin composition is 100%.
  • each of these other additives is blended in a ratio of about 0 to 10% by mass, particularly about 0.04 to 5% by mass, and the total amount of the other additives is 10% by mass or less. is desired.
  • 10 to 45% by mass, especially 20 to 25% by mass of thermoplastic resin; 90 to 45% by mass, especially 75 to 55% by mass of surface-modified calcium carbonate; 0 to 10% by weight, in particular 0.04 to 5% by weight of the above additives may be contained.
  • plasticizers include triethyl citrate, acetyl-triethyl citrate, dibutyl phthalate, diaryl phthalate, dimethyl phthalate, diethyl phthalate, di-2-methoxyethyl phthalate, dibutyl tartrate, and o-benzoylbenzoic acid. Ester, diacetin, epoxidized soybean oil and the like. These plasticizers are usually blended in an amount of about several percent by mass with respect to the thermoplastic resin, but the amount is not limited to these ranges, and depending on the application of the resin composition, epoxidized soybean oil or the like is added in an amount of about 20 to 50 parts by mass. Blending is also possible. However, in the resin composition of the present invention, the blending amount is preferably about 0.5 to 10 parts by weight, particularly about 1 to 5 parts by weight, per 100 parts by weight of the thermoplastic resin.
  • organic pigments such as azo-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, diosazine-based, perinone-based, quinophthalone-based, and perylene-based pigments, ultramarine blue, titanium oxide, titanium yellow, and iron oxide. (Rouge), chromium oxide, zinc white, carbon black and other inorganic pigments.
  • lubricants include fatty acid-based lubricants such as stearic acid, hydroxystearic acid, complex stearic acid, and oleic acid; fatty alcohol-based lubricants; stearamide, oxystearamide, oleylamide, erucylamide, ricinolamide, behenamide, and methylol.
  • Aliphatic amide-based lubricants such as amides, methylenebisstearamide, methylenebisstearobehenamide, higher fatty acid bisamic acids, complex amides; n-butyl stearate, methyl hydroxystearate, polyhydric alcohol fatty acid esters, Fatty acid ester-based lubricants such as saturated fatty acid esters and ester-based waxes; and fatty acid metal soap-based lubricants such as zinc stearate and magnesium stearate.
  • antioxidants phosphorus-based antioxidants, phenol-based antioxidants, and pentaerythritol-based antioxidants can be used.
  • Phosphorus-based antioxidants more specifically phosphorus-based antioxidants such as phosphites and phosphates, are preferably used.
  • phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, and other phosphorous acid triesters, diesters, and monoesters. is mentioned.
  • Phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate, and the like. These phosphorus-based antioxidants may be used alone, or two or more of them may be used in combination.
  • Phenolic antioxidants include ⁇ -tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2- t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-t-butyl-4-(N,N-dimethyl aminomethyl)phenol, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, and tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]methane etc., and these can be used alone or in combination of two or more.
  • the flame retardant is not particularly limited, but for example, halogen flame retardants or non-phosphorus halogen flame retardants such as phosphorus flame retardants and metal hydrates can be used.
  • halogen flame retardants include halogenated bisphenol compounds such as halogenated bisphenylalkanes, halogenated bisphenyl ethers, halogenated bisphenylthioethers, and halogenated bisphenylsulfones, brominated bisphenol A, bromine Bisphenol-bis(alkyl ether) compounds such as bisphenol S, chlorinated bisphenol A, and chlorinated bisphenol S, and phosphorus-based flame retardants such as aluminum tris(diethylphosphinate) and bisphenol A bis(diphenyl phosphate).
  • triaryl isopropyl phosphate, cresyl di-2,6-xylenyl phosphate, aromatic condensed phosphate esters, etc., and metal hydrates such as aluminum trihydrate, magnesium hydroxide, combinations thereof, etc. can be exemplified, respectively, and these can be used alone or in combination of two or more. It works as a flame retardant assistant, and can improve the flame retardant effect more effectively.
  • antimony oxides such as antimony trioxide and antimony pentoxide, zinc oxide, iron oxide, aluminum oxide, molybdenum oxide, titanium oxide, calcium oxide, magnesium oxide, etc. can be used in combination as flame retardant aids. .
  • the foaming agent is mixed or injected into the resin composition that is in a molten state in the melt kneader and undergoes a phase change from solid to gas, liquid to gas, or gas itself, and the porosity of the resin composition ( foaming ratio).
  • a foaming agent that is liquid at room temperature undergoes a phase change to a gas depending on the resin temperature and dissolves in the molten resin, while a foaming agent that is gas at room temperature does not undergo a phase change and dissolves in the molten resin as it is.
  • the foaming agent dispersed and dissolved in the molten resin expands inside the sheet as the pressure is released when the molten resin is extruded into a sheet from an extrusion die, forming a large number of fine closed cells within the sheet and foaming. A sheet is obtained.
  • the foaming agent secondarily acts as a plasticizer that lowers the melt viscosity of the raw material resin composition, and lowers the temperature for making the raw resin composition plasticized.
  • blowing agents include aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclobutane, cyclopentane and cyclohexane; chlorodifluoromethane, difluoromethane, trifluoromethane, trichlorofluoromethane; Methane, dichloromethane, dichlorofluoromethane, dichlorodifluoromethane, chloromethane, chloroethane, dichlorotrifluoroethane, dichloropentafluoroethane, tetrafluoroethane, difluoroethane, pentafluoroethane, trifluoroethane, dichlorotetrafluoroethane, trichlorotrifluoroethane , tetrachlorodifluoroethane and perfluorocyclobut
  • a carrier resin containing an active ingredient of the foaming agent can be preferably used.
  • carrier resins include crystalline olefin resins. Among these, crystalline polypropylene resins are preferred.
  • hydrogen carbonate etc. are mentioned as an active ingredient. Among these, hydrogen carbonate is preferred.
  • a blowing agent concentrate containing a crystalline polypropylene resin as a carrier resin and a hydrogen carbonate as a thermally decomposable blowing agent is preferred.
  • the content of the foaming agent contained in the foaming agent in the molding process can be appropriately set according to the amounts of the thermoplastic resin and the inorganic substance powder, etc., and is 0.04 to 5.0% relative to the total mass of the resin composition. 00% by mass is preferable.
  • fluidity modifiers can also be used.
  • examples include, but are not limited to, peroxides such as dialkyl peroxides such as 1,4-bis[(t-butylperoxy)isopropyl]benzene and the like.
  • these peroxides may also act as crosslinkers.
  • part of the copolymer is crosslinked by the action of the peroxide, which helps control the physical properties and workability of the thermoplastic resin composition.
  • the amount of the peroxide to be added is not particularly limited, but should be in the range of 0.04 to 2.00% by mass, particularly 0.05 to 0.50% by mass, based on the total mass of the thermoplastic resin composition. is preferred.
  • a method for preparing the resin composition of the present invention a conventional method can be used, and the method can be appropriately set according to the molding method (extrusion molding, injection molding, vacuum molding, etc.).
  • the molding method can be prepared by kneading and melting a thermoplastic resin and an inorganic powder. Melt-kneading is preferably carried out by applying a high shear stress while dispersing each component uniformly.
  • a mixing device various devices such as a general extruder, a kneader, and a Banbury mixer can be used.
  • the prepared resin composition can be made into pellets of desired shape and size, for example, and used to produce various molded articles.
  • a sheet-shaped molded article can be produced by kneading various raw materials with a twin-screw extruder and extruding a sheet-shaped material.
  • the present invention also includes a molded article made of the resin composition described above.
  • the resin composition of the present invention has good moldability and excellent physical properties such as mechanical strength even though the thermoplastic resin is highly filled with calcium carbonate. Therefore, it can be molded into molded articles of various shapes that are useful for various purposes. Also, since the resin composition of the present invention has a small amount of elution under acidic conditions, it can be used for moldings that come into direct contact with food, unlike conventional inorganic powder-filled resin compositions. Moreover, at that time, it is not necessary to form a two-layer or three-layer structure in which resin layers such as polyolefin are laminated. Therefore, the molded article of the present invention is particularly suitable for food packaging containers and tableware.
  • the present invention further includes a food packaging container comprising the above resin composition.
  • the shape and the like of the food packaging container according to the present invention are not particularly limited, and may be of various shapes and sizes, such as lunch boxes, cups, plates, bowls, bowls, spoons, forks, and chopsticks.
  • the container may have a thickness of 40 ⁇ m to 10 mm, more preferably 100 ⁇ m to 5 mm. If the wall thickness is within this range, the calcium carbonate is uniformly dispersed in the thermoplastic resin, so that good moldability and workability can be obtained, and a homogeneous and defect-free container without uneven wall thickness can be obtained. can be formed.
  • the method for producing the molded article of the present invention is not particularly limited as long as it can be molded into a desired shape, and any of conventionally known methods such as extrusion molding, injection molding, vacuum molding, blow molding and calendar molding can be used. Can be molded.
  • the resin composition of the present invention does not need to have a 2- to 3-layer structure with other resin layers when molded into a food packaging container or the like. can do.
  • the resin composition according to the present invention contains a foaming agent and a molded product in the form of a foam is obtained, as long as it can be molded into a desired shape, conventionally known foam molding methods can be used.
  • liquid phase foaming methods such as injection foaming, extrusion foaming and foam blowing, or solid phase foaming methods such as bead foaming, batch foaming, press foaming and normal pressure secondary foaming can be used.
  • solid phase foaming methods such as bead foaming, batch foaming, press foaming and normal pressure secondary foaming
  • an injection foaming method and an extrusion foaming method can be desirably used.
  • the molding temperature in injection molding, extrusion molding, etc. varies to some extent depending on the molding method and the type of thermoplastic resin used, so it cannot be defined unconditionally, but the melting point of the thermoplastic resin component is preferable.
  • the temperature can be about +5 to 100°C, particularly about +10 to 50°C, for example, 180 to 260°C, more preferably 190 to 230°C. At such a temperature, the resin composition according to the present invention has good drawdown properties and spreadability, and can be molded into a predetermined shape without locally modifying the composition.
  • Example 1 100 parts by mass of heavy calcium carbonate (Softon (trade name) 1000 manufactured by Bihoku Funka Kogyo Co., Ltd.) having an average particle size of 2.2 ⁇ m (according to the air permeation method) and a specific surface area of 10,000 cm 2 /g, is mixed with polyoxyethylene. Lauryl ether phosphate (Toho Chemical Industry Co., Ltd.
  • Example 1 The same operation as in Example 1 was performed using untreated SOFTON 1000 as the inorganic powder. Table 1 shows the test results.
  • SOFTON 1000 was dispersed in purified water (concentration 100 g/L) to prepare a slurry.
  • a sodium salt of a phosphoric acid ester having a long unsaturated aliphatic hydrocarbon chain and an ethylene oxide unit (unsaturated EO phosphoric acid ester salt, Phosphanol (registered trademark) RD-720 manufactured by Toho Chemical Industry Co., Ltd.) , Hydrocarbon chain carbon number 18, ethylene oxide unit number 7) is added to 1 L of slurry (3% by mass based on calcium carbonate), stirred at 50 ° C. for 30 minutes, filtered, dried and surface treated. Calcium carbonate was obtained. Using this surface-treated calcium carbonate, a sheet was produced in the same manner as in Example 1, and its physical properties were evaluated. Table 1 shows the test results.
  • Example 2 As the surface-treated calcium carbonate, commercially available fatty acid surface-treated heavy calcium carbonate (average particle size 2.2 ⁇ m; Ryton (registered trademark) S-4 manufactured by Bihoku Funka Kogyo Co., Ltd.) was used, and the same operation as in Example 1 was performed. gone. Table 1 shows the test results.
  • Comparative Example 4 The same operation as in Comparative Example 3 was performed using styrene/maleic acid ester (maleic acid-modified resin; Regit (registered trademark) SM-101 manufactured by Sanyo Chemical Industries, Ltd.) as a surface treatment agent. Table 1 shows the test results.
  • the samples of Examples 1 to 4 containing calcium carbonate surface-treated with a phosphate ester had a small amount of acetic acid elution, and were found to be suitable for food applications.
  • the sample of Example 1 surface-treated with a phosphoric acid ester having an ethylene oxide unit, especially polyoxyethylene lauryl ether phosphoric acid showed a significant reduction in the amount of acetic acid eluted.
  • the resin composition filled with a large amount of calcium carbonate tends to have a large acetic acid elution amount and a low tensile strength.
  • Example 5 Comparative Example 5
  • Example 1 The same operations as in Example 1 and Comparative Example 2 were performed, except that 70 parts by mass of surface-treated calcium carbonate and 30 parts by mass of polypropylene homopolymer were used. Table 2 shows the test results.
  • Example 6 The same operation as in Example 5 was performed except that the amount of phosphate ester during surface treatment was changed to 1 part by mass. Table 2 shows the test results.
  • Comparative Examples 7-8 The same operations as in Comparative Examples 3 and 4 were performed except that 70 parts by mass of surface-treated calcium carbonate and 30 parts by mass of polypropylene homopolymer were used. Table 2 shows the test results.
  • both the samples of Examples 5 and 6 containing calcium carbonate surface-treated with a phosphate ester have a smaller acetic acid elution amount than the sample of Comparative Example 5 containing general-purpose fatty acid-treated calcium carbonate. It was found to be suitable for food applications. Tensile properties were also good. On the other hand, in Comparative Examples 6 to 8, since the calcium carbonate particles were covered with the modified resin, the acetic acid elution amount was rather low, but the tensile properties were remarkably deteriorated. It was shown that the present invention has remarkable effects.
  • thermoplastic resin composition containing calcium carbonate surface-treated with a surface-treating agent containing a phosphate ester according to the present invention can be used under acidic conditions despite being highly filled with inorganic powder. It has been found that the elution amount is small, moldability is good, physical properties such as mechanical strength are excellent, and it is particularly suitable for food packaging containers and tableware.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine, laquelle, sans tenir compte que du carbonate de calcium est fortement chargé dans une résine thermoplastique, présente une faible quantité d'élution dans des conditions acides, présente une bonne aptitude au formage ainsi que d'excellentes propriétés physiques telles que résistance mécanique etc.; et laquelle est particulièrement adaptée à une utilisation dans des contenants pour produits alimentaires et des ustensiles de cuisine. L'invention concerne également un article moulé constitué d'une telle composition de résine.　Cette composition de résine contient une résine thermoplastique et une poudre de substance inorganique dans un rapport de masse compris dans les proportions 50:50 à 10:90, cette composition de résine se caractérisant en ce que la poudre de substance inorganique est un carbonate de calcium traité en surface à l'aide d'un agent de traitement de surface contenant un ester phosphorique. De préférence, cet ester phosphorique est un phosphate de polyoxyéthylène lauryl éther.
PCT/JP2022/011223 2021-05-28 2022-03-14 Composition de résine, et article moulé WO2022249652A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021090053A JP6954705B1 (ja) 2021-05-28 2021-05-28 樹脂組成物及び成形品
JP2021-090053 2021-05-28

Publications (1)

Publication Number Publication Date
WO2022249652A1 true WO2022249652A1 (fr) 2022-12-01

Family

ID=78150264

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/011223 WO2022249652A1 (fr) 2021-05-28 2022-03-14 Composition de résine, et article moulé

Country Status (2)

Country Link
JP (1) JP6954705B1 (fr)
WO (1) WO2022249652A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7195678B1 (ja) 2022-06-24 2022-12-26 株式会社Tbm 積層シート、及び食品包装容器
KR102680604B1 (ko) * 2023-05-30 2024-07-03 마루오 칼슘 가부시키가이샤 표면처리 탄산칼슘 필러, 그것을 사용한 수지 조성물 및 성형품

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57108164A (en) * 1980-12-24 1982-07-06 Shiraishi Chuo Kenkyusho:Kk Inorganic surface-modified filler and thermoplastic resin composition blended therewith
JPS62225556A (ja) * 1986-03-28 1987-10-03 Nippon Soda Co Ltd 不飽和ポリエステル樹脂の充填剤用表面処理剤
JP2001164017A (ja) * 1999-12-07 2001-06-19 Yupo Corp 多孔性樹脂フィルム
JP2002519468A (ja) * 1998-06-30 2002-07-02 オムヤ・エス・アー リン酸エステルによる無機充填剤の処理方法、該処理方法によって得られた充填剤及びその使用
JP2014019784A (ja) * 2012-07-18 2014-02-03 Maruo Calcium Co Ltd 表面処理重質炭酸カルシウム、その製造方法、及び該炭酸カルシウムを含有した樹脂組成物
JP2015083661A (ja) * 2013-09-17 2015-04-30 東レ株式会社 多孔フィルム及びその製造方法
JP2016513159A (ja) * 2013-02-22 2016-05-12 オムヤ インターナショナル アーゲー プラスチックに適用するための白色無機物質の新しい表面処理

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57108164A (en) * 1980-12-24 1982-07-06 Shiraishi Chuo Kenkyusho:Kk Inorganic surface-modified filler and thermoplastic resin composition blended therewith
JPS62225556A (ja) * 1986-03-28 1987-10-03 Nippon Soda Co Ltd 不飽和ポリエステル樹脂の充填剤用表面処理剤
JP2002519468A (ja) * 1998-06-30 2002-07-02 オムヤ・エス・アー リン酸エステルによる無機充填剤の処理方法、該処理方法によって得られた充填剤及びその使用
JP2001164017A (ja) * 1999-12-07 2001-06-19 Yupo Corp 多孔性樹脂フィルム
JP2014019784A (ja) * 2012-07-18 2014-02-03 Maruo Calcium Co Ltd 表面処理重質炭酸カルシウム、その製造方法、及び該炭酸カルシウムを含有した樹脂組成物
JP2016513159A (ja) * 2013-02-22 2016-05-12 オムヤ インターナショナル アーゲー プラスチックに適用するための白色無機物質の新しい表面処理
JP2015083661A (ja) * 2013-09-17 2015-04-30 東レ株式会社 多孔フィルム及びその製造方法

Also Published As

Publication number Publication date
JP6954705B1 (ja) 2021-10-27
JP2022182473A (ja) 2022-12-08

Similar Documents

Publication Publication Date Title
CN113490713B (zh) 含无机物质粉末的热塑性树脂组合物及成形品
WO2022249652A1 (fr) Composition de résine, et article moulé
US20220251332A1 (en) Flame retardant ploymer composition and methods of use
JP7033359B1 (ja) 床材用ポリ塩化ビニル系樹脂シート
WO2021199558A1 (fr) Composition de résine pour la production de feuilles étirées, feuille étirée et procédé de production de feuille étirée
WO2021192427A1 (fr) Composition de résine thermoplastique contenant de la poudre de coquille d'oeuf et article moulé
WO2022196434A1 (fr) Composition de résine chargée de poudre inorganique et produit moulé
JP2006307015A (ja) 耐傷付性樹脂組成物、耐傷付性樹脂組成物の製造方法、及び成形品
JP6933408B1 (ja) 無機物質粉末充填樹脂組成物及び成形品
WO2022249653A1 (fr) Composition de résine, et article moulé
JP7195678B1 (ja) 積層シート、及び食品包装容器
WO2022196436A1 (fr) Composition de résine chargée de poudre de substance inorganique et produit moulé
WO2023095393A1 (fr) Composition de résine chargée d'une poudre de substance inorganique et produit moulé
JP6704151B1 (ja) 無機物質粉末充填樹脂組成物、及び成形体
JP7282404B2 (ja) 高周波誘電体
JP6892185B1 (ja) 無機物質粉末充填樹脂組成物及び成形品
JP7499398B1 (ja) 樹脂組成物およびこれを含む成形品
JP7100933B1 (ja) 積層シート及び食品包装容器
JP2023074203A (ja) 無機物質粉末充填樹脂組成物及び成形品

Legal Events

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

Ref document number: 22810930

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22810930

Country of ref document: EP

Kind code of ref document: A1