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WO2025057822A1 - Mélange de pastilles, mélange-maître et procédé de production d'une composition de résine - Google Patents

Mélange de pastilles, mélange-maître et procédé de production d'une composition de résine Download PDF

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Publication number
WO2025057822A1
WO2025057822A1 PCT/JP2024/031628 JP2024031628W WO2025057822A1 WO 2025057822 A1 WO2025057822 A1 WO 2025057822A1 JP 2024031628 W JP2024031628 W JP 2024031628W WO 2025057822 A1 WO2025057822 A1 WO 2025057822A1
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Prior art keywords
mass
parts
polyacetal resin
master batch
group
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English (en)
Japanese (ja)
Inventor
大輔 須長
かりん 福原
大介 小林
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Global Polyacetal Co Ltd
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Global Polyacetal Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals

Definitions

  • the present invention relates to a method for producing a pellet blend, a masterbatch, and a resin composition.
  • Polyacetal resin has high mechanical strength and rigidity, excellent resistance to oil and organic solvents, is well-balanced over a wide temperature range, and is easy to process. Therefore, polyacetal resin is a representative engineering plastic and is widely used in office equipment, digital home appliances, automobile parts, and other industrial parts.
  • Patent Document 1 Patent Document 2
  • a formaldehyde scavenger is blended into a polyacetal resin.
  • a formaldehyde scavenger is blended into a high-viscosity polyacetal resin and melt-kneaded, shear heat generation in an extruder becomes significant. As a result, a large amount of the formaldehyde scavenger is consumed during melt-kneading.
  • a molded product formed from such a resin composition has a problem in that it cannot sufficiently capture formaldehyde. It is possible to increase the blending amount of the formaldehyde scavenger, but this would cause mold contamination during molding.
  • the present invention aims to solve the above problems, and to provide a pellet blend containing a high-viscosity polyacetal resin and a formaldehyde scavenger, which has a high formaldehyde scavenging effect and is less likely to cause mold contamination, as well as a master batch and a method for producing a resin composition using the pellet blend.
  • the present inventors have conducted research and have found that the above-mentioned problems can be solved by compounding a formaldehyde scavenger with a relatively low-viscosity polyacetal resin, forming the resulting pellets, and further blending the pellets with pellets containing a high-viscosity polyacetal resin. Specifically, the above problems were solved by the following means.
  • the pellets (2) contain a polyacetal resin (C) having a melt volume rate (MVR) of 0.1 to 4 cm3/10 min or less, measured at 190°C and a load of 2.16 kg in accordance with ISO 1133.
  • Pellet blend. ⁇ 2> The pellet blend according to ⁇ 1>, containing 3 to 25 parts by mass of the master batch (1) per 100 parts by mass of the pellets (2).
  • the formaldehyde scavenger (B) includes at least one selected from the group consisting of hydrazide compounds, hydrazones of hydrazine compounds, guanamine compounds, and urea compounds.
  • a masterbatch comprising 100 parts by mass of a polyacetal resin (A) having a melt volume rate (MVR) of 5 to 50 cm3/10 min measured in accordance with ISO 1133 at 190°C under a load of 2.16 kg, and 0.5 to 3.0 parts by mass of a formaldehyde scavenger (B).
  • the formaldehyde scavenger (B) includes at least one selected from the group consisting of hydrazide compounds, hydrazones of hydrazine compounds, guanamine compounds, and urea compounds.
  • the method includes melt-kneading a polyacetal resin (C) having a melt volume rate (MVR) of 0.1 to 4 cm3/10 min or less, measured in accordance with ISO 1133 at 190°C and a load of 2.16 kg, with a master batch (1);
  • the master batch (1) contains 100 parts by mass of a polyacetal resin (A) having a melt volume rate (MVR) of 5 to 50 cm3/10 min measured at 190°C under a load of 2.16 kg in accordance with ISO1133, and 0.5 to 3.0 parts by mass of a formaldehyde scavenger (B).
  • the present invention makes it possible to provide a pellet blend containing a high-viscosity polyacetal resin and a formaldehyde scavenger, which has a high formaldehyde scavenging effect and is less likely to cause mold contamination, a master batch, and a method for producing a resin composition.
  • the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
  • the use of "to” means that the numerical values before and after it are included as the lower limit and upper limit.
  • various physical properties and characteristic values are those at 23° C. unless otherwise specified. If the measurement methods, etc. described in the standards shown in this specification vary from year to year, they will be based on the standards as of January 1, 2023, unless otherwise specified.
  • the pellet blend of the present embodiment is characterized by comprising a master batch (1) containing 0.5 to 3.0 parts by mass of a formaldehyde scavenger (B) per 100 parts by mass of a polyacetal resin (A) having a melt volume rate (MVR) of 5 to 50 cm3/10 min measured in accordance with ISO 1133 at 190°C under a load of 2.16 kg, and pellets (2) containing a polyacetal resin (C) having a melt volume rate (MVR) of 0.1 to 4 cm3/10 min or less measured in accordance with ISO 1133 at 190°C under a load of 2.16 kg.
  • a master batch (1) containing 0.5 to 3.0 parts by mass of a formaldehyde scavenger (B) per 100 parts by mass of a polyacetal resin (A) having a melt volume rate (MVR) of 5 to 50 cm3/10 min measured in accordance with ISO 1133 at 190°C under a load of 2.16 kg
  • a formaldehyde scavenger (B) is blended in advance with a polyacetal resin (A) having an MVR of 5 to 50 cm3/10 min, melt-kneaded to form a master batch, and then blended with pellets of a polyacetal resin (C) having an MVR of 0.1 to 4 cm3/10 min or less.
  • the formaldehyde scavenger (B) can be blended with the polyacetal resin without excessive shear heat being generated during compounding (when making pellets).
  • the heating step for the formaldehyde scavenger (B) can be limited to the molding step, and unnecessary consumption of the formaldehyde scavenger (B) can be avoided.
  • a pellet blend was obtained in which the formaldehyde scavenger effect of the resulting molded product was sufficiently high and mold contamination was suppressed, despite the use of a high-viscosity polyacetal resin and the blending of a formaldehyde scavenger. The details of this embodiment will be described below.
  • the master batch (1) of the present embodiment contains 0.5 to 3.0 parts by mass of a formaldehyde scavenger (B) based on 100 parts by mass of a polyacetal resin (A) having a melt volume rate (MVR) of 5 to 50 cm3/10 min measured in accordance with ISO 1133 under conditions of 190°C and a load of 2.16 kg.
  • MVR melt volume rate
  • the master batch (1) contains a polyacetal resin (A) having a melt volume rate (MVR) of 5 to 50 cm3/10 min, measured in accordance with ISO1133 at 190°C under a load of 2.16 kg.
  • MVR melt volume rate
  • the melt volume rate (MVR) of the polyacetal resin (A) measured according to ISO1133 at 190°C and a load of 2.16 kg is preferably 7 cm3/10 min or more, more preferably 10 cm3/10 min or more, even more preferably 15 cm3/10 min or more, even more preferably 20 cm3/10 min or more, even more preferably 25 cm3/10 min or more, and preferably 45 cm3/10 min or less, more preferably 40 cm3/10 min or less, even more preferably 35 cm3/10 min or less, and even more preferably 30 cm3/10 min or less.
  • the master batch (1) of the present embodiment may contain only one type of polyacetal resin (A) or may contain two or more types. When two or more types are contained, the MVR of the mixture is preferably in the above range.
  • the polyacetal resin (A) is not particularly limited in terms of its type, etc., so long as it satisfies the above MVR, and may be a homopolymer containing only divalent oxymethylene groups as constituent units, or a copolymer containing divalent oxymethylene groups and divalent oxyalkylene groups having two or more carbon atoms as constituent units.
  • the oxyalkylene group having two or more carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • the proportion of oxyalkylene groups having 2 or more carbon atoms in the total number of moles of oxymethylene groups and oxyalkylene groups having 2 or more carbon atoms is not particularly limited, and may be, for example, 0.5 to 10 mol %.
  • the number of carbon atoms in the oxyalkylene groups may be 2 or more, but is preferably 6 or less, and more preferably 4 or less.
  • trioxane is usually used as the main raw material.
  • a cyclic formal or a cyclic ether can be used.
  • cyclic formals include 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepane, 1,3-dioxocane, 1,3,5-trioxepane, and 1,3,6-trioxocane.
  • cyclic ethers include ethylene oxide, propylene oxide, and butylene oxide.
  • 1,3-dioxolane can be used, to introduce an oxypropylene group, 1,3-dioxane can be used, and to introduce an oxybutylene group, 1,3-dioxepane can be used.
  • polyacetal resin (A) it is preferable that the amount of hemiformal end groups, formyl end groups, and end groups that are unstable to heat, acid, or base is small.
  • a hemiformal end group is represented by -OCH2OH
  • a formyl end group is represented by -CHO.
  • the content of the polyacetal resin (A) in the master batch (1) of this embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 97% by mass or more, and still more preferably 98% by mass or more.
  • the upper limit of the content of the polyacetal resin (A) is an amount at which all components other than the formaldehyde scavenger (B) are polyacetal resin (A).
  • the master batch (1) of the present embodiment may contain only one type of polyacetal resin (A), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the master batch (1) of the present embodiment contains the formaldehyde scavenger (B) in a ratio of 0.5 to 3.0 parts by mass per 100 parts by mass of the polyacetal resin (A).
  • the formaldehyde scavenger (B) used in this embodiment is not particularly limited in terms of type, etc., and a wide variety of compounds that are used as formaldehyde scavengers for polyacetal resins can be used.
  • the formaldehyde scavenger (B) is preferably a compound containing a nitrogen atom, more preferably at least one selected from the group consisting of hydrazide compounds, hydrazones of hydrazine compounds, guanamine compounds, and urea compounds, and even more preferably at least one selected from the group consisting of hydrazide compounds and urea compounds.
  • the hydrazide compound is preferably a hydrazide compound having two or more hydrazide groups.
  • Examples of the dihydrazide compound include an aliphatic dihydrazide compound and an aromatic dihydrazide compound.
  • Aliphatic dihydrazide compounds include carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide (1,12-dodecanedicarbohydrazide), 1,18-octadecanedicarbohydrazide, stearic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, and 7,11-octadecadiene-1,18-dicarbohydrazide.
  • Aromatic dihydrazide compounds include isophthalic acid dihydrazide, terephthalic acid dihydrazide, 1,5-naphthalenedicarbohydrazide, 1,8-naphthalenedicarbohydrazide, 2,6-naphthalenedicarbohydrazide, 4,4'-oxybisbenzenesulfonylhydrazide, and 1,5-diphenylcarbonohydrazide.
  • the hydrazide compound used in the present embodiment is preferably represented by the following formula (1).
  • Formula (1) (In formula (1), R11 represents an aliphatic hydrocarbon group having 2 to 18 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms; R12 to R15 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R12 and R13, and R14 and R15 may be bonded to each other to form a ring.)
  • R11 represents an aliphatic hydrocarbon group having 2 to 18 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and is preferably an aliphatic hydrocarbon group having 2 to 18 carbon atoms.
  • the number of carbon atoms in the aliphatic hydrocarbon group having 2 to 18 carbon atoms is preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less.
  • the aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched.
  • aliphatic hydrocarbon group examples include alkylene groups such as butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, and nonadecylene.
  • alkylene groups such as butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, and nonadecylene.
  • the alicyclic hydrocarbon group may be saturated or unsaturated.
  • Examples of the alicyclic hydrocarbon group include a cycloalkylene group having 6 to 10 carbon atoms.
  • Examples of the cycloalkylene group include a cyclohexylene group.
  • the aromatic hydrocarbon group includes arylene groups such as a phenylene group and a naphthylene group. At least some of the carbon atoms of the aromatic hydrocarbon group may be bonded with a substituent, such as a halogen group, a nitro group, or an alkyl group having 1 to 20 carbon atoms.
  • R12 to R15 are each preferably independently a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.
  • Specific examples of compounds represented by formula (1) include adipic acid dihydrazide and 1,12-dodecanedioic acid dihydrazide.
  • the hydrazone derivative of a hydrazine compound is preferably at least one hydrazone derivative selected from the group consisting of compounds represented by the following formula (2) and compounds represented by the following formula (3).
  • Equation (2) (In formula (2), R1 represents an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • R2 to R5 each independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, at least one of R2 and R3 represents an alkyl group having 1 or 2 carbon atoms, and at least one of R4 and R5 represents an alkyl group having 1 or 2 carbon atoms.
  • R1 represents an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • the aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched.
  • aliphatic hydrocarbon group examples include alkylene groups such as butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, and icosylene.
  • the aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 6 to 12 carbon atoms.
  • the alicyclic hydrocarbon group may be saturated or unsaturated.
  • Examples of the alicyclic hydrocarbon group include a cycloalkylene group having 6 to 10 carbon atoms.
  • Examples of the cycloalkylene group include a cyclohexylene group.
  • the aromatic hydrocarbon group includes arylene groups such as a phenylene group and a naphthylene group.
  • R2 to R5 each independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms
  • at least one of R2 and R3 represents an alkyl group having 1 or 2 carbon atoms
  • at least one of R4 and R5 represents an alkyl group having 1 or 2 carbon atoms.
  • R3 and R5 are hydrogen atoms
  • R2 and R4 are methyl groups
  • R3 and R5 are hydrogen atoms or methyl groups.
  • the reactivity of the hydrazone of the hydrazine compound with formaldehyde becomes higher, and the generation of formaldehyde is more effectively suppressed.
  • Specific examples of the compound represented by the above formula (2) include 1,12-bis[2-(1-methylethylidene)hydrazino]]-1,12-dodecanedione, 1,12-bis(2-ethylidenehydrazino)-1,12-dodecanedione, 1,12-bis(2-propylidenehydrazino)-1,12-dodecanedione, 1,12-bis[2-(1-methylpropylidene)hydrazino]-1,12-dodecanedione, 1,12-bis[2-(1-ethylpropylidene)hydrazino]-1,12-dodecanedione, 1,10-bis[2-(1-methylethylidene)hydrazino]]-1,10-decanedione, 1,10-bis(2-propylidenehydrazino)-1,10-decanedione, 1,10-bis(2-propylidenehydrazino
  • Equation (3) (In formula (3), R8 represents an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. R6 and R7 each independently represent an alicyclic hydrocarbon group having 3 to 12 carbon atoms.)
  • R8 is the same as R1, and the preferred range is also the same.
  • R6 and R7 each independently represent an alicyclic hydrocarbon group having 3 to 12 carbon atoms.
  • Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include a cyclohexylene group.
  • Specific examples of the compound represented by the above formula (3) include 1,12-bis(2-cyclohexylidenehydrazino)-1,12-dodecanedione, 1,10-bis(2-cyclohexylidenehydrazino)-1,10-decanedione, and 1,6-bis(2-cyclohexylidenehydrazino)-1,6-hexanedione.
  • guanamine compounds examples include benzoguanamine and N-methylol benzoguanamine.
  • the urea compound include urea, ethylene urea, allantoin, biurea, dimethylethylene urea, propylene urea, and tetrabutyl urea, and it is preferable that the urea compound contains ethylene urea and/or allantoin, and it is more preferable that the urea compound contains ethylene urea.
  • the molecular weight of the formaldehyde scavenger (B) used in this embodiment is preferably 60 or more, and more preferably 86 or more.
  • the upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less.
  • the content of the master batch (1) in this embodiment is 0.5 parts by mass or more, more preferably 1 part by mass or more, and also 3.0 parts by mass or less, preferably 2.5 parts by mass or less, based on 100 parts by mass of the polyacetal resin (A).
  • the master batch (1) of the present embodiment may contain only one type of formaldehyde scavenger (B), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
  • the master batch (1) of the present embodiment may or may not contain components other than the polyacetal resin (A) and the formaldehyde scavenger (B).
  • components other than the polyacetal resin (A) and the formaldehyde scavenger (B) include functional group-containing compounds (e.g., melamine compounds), heat stabilizers, antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, release agents, lubricants, crystal nucleating agents, antistatic agents, antibacterial agents, colorants (pigments, dyes), etc. These can be used alone or in combination of two or more.
  • the content of these other components is preferably less than 5% by mass of the masterbatch (1), more preferably less than 3% by mass, even more preferably less than 1% by mass, even more preferably less than 0.5% by mass, and even more preferably less than 0.1% by mass.
  • the lower limit is 0% by mass.
  • the pellets (2) contain a polyacetal resin (C) having a melt volume rate (MVR) of 0.1 to 4 cm3/10 min measured in accordance with ISO1133 at 190°C under a load of 2.16 kg.
  • MVR melt volume rate
  • the formaldehyde scavenger (B) can be preliminarily made into a master batch using the low-viscosity polyacetal resin (A)
  • the high-viscosity polyacetal resin (C) can be preferably used as a constituent component of the pellet blend.
  • the MVR is preferably 3.5 cm3/10 min or less, more preferably 0.5 cm3/10 min or more, more preferably 1 cm3/10 min or more, even more preferably 1.5 cm3/10 min or more, even more preferably 2 cm3/10 min or more, and even more preferably 2.5 cm3/10 min or more.
  • the pellet (2) in the present embodiment may contain only one type of polyacetal resin (C) or may contain two or more types. When two or more types are contained, it is preferable that the MVR of the mixture is in the above range.
  • the polyacetal resin (C) is not particularly limited in terms of its type, etc., so long as it satisfies the above MVR, and may be a homopolymer containing only divalent oxymethylene groups as constituent units, or a copolymer containing divalent oxymethylene groups and divalent oxyalkylene groups having two or more carbon atoms as constituent units.
  • the oxyalkylene group having two or more carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • the proportion of oxyalkylene groups having 2 or more carbon atoms in the total number of moles of oxymethylene groups and oxyalkylene groups having 2 or more carbon atoms is not particularly limited, and may be, for example, 0.5 to 10 mol %.
  • the number of carbon atoms in the oxyalkylene groups may be 2 or more, but is preferably 6 or less, and more preferably 4 or less.
  • trioxane is usually used as the main raw material.
  • a cyclic formal or a cyclic ether can be used.
  • cyclic formals include 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepane, 1,3-dioxocane, 1,3,5-trioxepane, and 1,3,6-trioxocane.
  • cyclic ethers include ethylene oxide, propylene oxide, and butylene oxide.
  • 1,3-dioxolane can be used, to introduce an oxypropylene group, 1,3-dioxane can be used, and to introduce an oxybutylene group, 1,3-dioxepane can be used.
  • polyacetal resin (C) it is preferable that the amount of hemiformal end groups, formyl end groups, and end groups that are unstable to heat, acid, or base are small.
  • a hemiformal end group is represented by -OCH2OH
  • a formyl end group is represented by -CHO.
  • the content of the polyacetal resin (C) in the pellet (2) in this embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 97% by mass or more, and still more preferably 99% by mass or more, and may be 100% by mass or less.
  • the pellet (2) in the present embodiment may contain only one type of polyacetal resin (C), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the pellet (2) in this embodiment may or may not contain components other than the polyacetal resin (C).
  • components other than the polyacetal resin (C) include functional group-containing compounds (e.g., melamine compounds), heat stabilizers, antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, release agents, lubricants, crystal nucleating agents, antistatic agents, antibacterial agents, colorants (pigments, dyes), etc. These can be used alone or in combination of two or more.
  • the content of these other components is preferably less than 5% by mass of the pellets (2), more preferably less than 3% by mass, even more preferably less than 1% by mass, even more preferably less than 0.5% by mass, and even more preferably less than 0.1% by mass.
  • the lower limit is 0% by mass.
  • the pellets (2) in this embodiment may contain a formaldehyde scavenger (B), but it is preferable that they are substantially free of the formaldehyde scavenger (B).
  • substantially free of the formaldehyde scavenger (B) it is preferable that the content of the formaldehyde scavenger (B) in the pellets (2) in this embodiment is less than 0.5% by mass, more preferably less than 0.3% by mass, even more preferably less than 0.1% by mass, even more preferably less than 0.05% by mass, even more preferably less than 0.01% by mass, and particularly preferably less than 0.001% by mass.
  • the lower limit is 0% by mass.
  • the pellet blend of the present embodiment contains 3 to 25 parts by mass of the master batch (1) per 100 parts by mass of the pellets (2).
  • the content of the master batch (1) in the pellet blend of this embodiment is preferably 4 parts by mass or more, more preferably 6 parts by mass or more, even more preferably 8 parts by mass or more, even more preferably 11 parts by mass or more, even more preferably 15 parts by mass or more, and preferably 22 parts by mass or less, relative to 100 parts by mass of the pellet (2).
  • the pellet blend of this embodiment may contain only one type of master batch (1) and/or pellet (2), or may contain two or more types. When the pellet blend of this embodiment contains two or more types of master batch (1) and/or pellet (2), the total amount is preferably within the above range.
  • the pellet blend of the present embodiment can usually be produced by dry blending the master batch (1) and the pellets (2).
  • the pellet blend of the present embodiment may further contain a second master batch.
  • the second master batch include a master batch of a resin additive other than the formaldehyde scavenger, such as a pigment or a flame retardant.
  • the pellet blend of this embodiment may also be substantially composed of only the master batch (1) and the pellets (2). "Substantially" means, for example, that the total amount of the master batch (1) and the pellets (2) in the pellet blend is 90% by mass or more of the total amount of the pellet blend, preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 99% by mass or more. The upper limit is 100% by mass.
  • the method for producing a resin composition of the present embodiment includes melt-kneading a polyacetal resin (C) having a melt volume rate (MVR) of 0.1 to 4 cm3/10 min or less, measured in accordance with ISO 1133 at 190°C under a load of 2.16 kg, with a master batch (1), and the master batch (1) is characterized in that the master batch (1) contains 0.5 to 3.0 parts by mass of a formaldehyde scavenger (B) per 100 parts by mass of a polyacetal resin (A) having a melt volume rate (MVR) of 5 to 50 cm3/10 min, measured in accordance with ISO 1133 at 190°C under a load of 2.16 kg.
  • C polyacetal resin
  • MVR melt volume rate
  • the masterbatch (1) has the same meaning as the masterbatch (1) described above.
  • the above-mentioned pellets (2) are exemplified as the polyacetal resin (C), and the preferred range is also the same.
  • examples of the method include a method in which the master batch (1) and the polyacetal resin (C) are supplied to an extruder and melt-kneaded to obtain a pellet-shaped composition, and a method in which the master batch (1) and the polyacetal resin (C) are molded as they are.
  • the resin composition of the present embodiment includes pellets and molded articles processed by injection molding or the like.
  • the resin composition of the present embodiment can be molded by a known molding method such as injection molding, extrusion molding, compression molding, blow molding, or vacuum molding.
  • the pellet blend, master batch, resin composition, and molded article of the present embodiment can be suitably used in applications where a reduction in the amount of formaldehyde generated is strongly required, such as automobile parts, electric and electronic parts, precision machinery parts, building materials and piping parts, daily necessities, cosmetic parts, and medical device parts.
  • automobile parts include interior parts such as inner handles, fuel trunk openers, seat belt buckles, assist wraps, various switches, knobs, levers, clips, etc.; electrical system parts such as meters and connectors; in-vehicle electric and electronic parts such as audio equipment and car navigation equipment; parts that come into contact with metal such as the carrier plate of a window regulator; door lock actuator parts, mirror parts, wiper motor system parts, fuel system parts, and other mechanical parts.
  • Examples of electric and electronic parts include components or members of equipment with many metal contacts, such as audio equipment such as cassette tape recorders and CD/DVD players, video equipment such as VTRs, 8mm video cameras and digital video cameras, and office automation equipment such as copy machines, facsimiles, word processors and computers.
  • Specific examples of these components or members include chassis, gears, levers, cams, pulleys and bearings.
  • the invention can be applied to optical and magnetic media parts at least partially composed of molded products, such as metal music tape cassettes, digital audio tape cassettes, 8mm video tape cassettes, digital video cassettes, floppy disk cartridges, mini disk cartridges and DVD disk cartridges.
  • the molded product of this embodiment is suitable for use in a wide range of lifestyle-related, cosmetic-related, and medical-related parts, including lighting fixtures, fittings, pipes, cocks, faucets, toilet peripheral parts, and other building materials and piping parts, fasteners, stationery, lip balm and lipstick containers, cleaners, water purifiers, spray nozzles, spray containers, aerosol containers, general containers, and needle holders.
  • the above-mentioned flat test piece was allowed to stand for 24 hours under an atmosphere of 23°C and 50% relative humidity, and then the amount of formaldehyde generated per 1 g of polyacetal resin (unit: ⁇ g/g-POM) was measured for the above-mentioned flat test piece in accordance with the method described in the German Automotive Industry Association standard VDA275 (Automobile interior parts - Quantitative determination of formaldehyde emission by the revised flask method) by the following method. (i) 50 mL of distilled water was placed in a polyethylene container, and the above-mentioned flat test piece was suspended in the air, and the container was closed with the lid closed, and heated at 60° C. for 3 hours.
  • Mold contamination was evaluated as follows. First, the pellets obtained above were continuously molded for 500 shots using a teardrop-shaped mold in a Minimat M8/7A molding machine manufactured by Sumitomo Heavy Industries, Ltd., at a molding temperature of 200°C and a mold temperature of 40°C. After molding was completed, the condition of the inner wall surface of the mold was observed with the naked eye. The criteria for the mold contamination suppression effect were as follows. In addition, five experts also observed with the naked eye and judged by majority vote. A: No mold deposits, good mold contamination suppression effect B: Other than A, e.g., mold deposits, poor mold contamination suppression effect
  • the pellet blend of this embodiment had a high formaldehyde trapping effect and also caused little mold contamination (Examples 1 to 8).
  • a high-viscosity polyacetal resin was used to make a masterbatch (Comparative Example 1)
  • the amount of formaldehyde generated was large, comparable to the amount when no formaldehyde scavenger was mixed (Comparative Example 2).
  • formaldehyde scavenger was mixed directly into the high-viscosity polyacetal resin without being made into a masterbatch (Comparative Examples 3 and 4)
  • formaldehyde could not be captured.
  • Comparative Examples 3 and 4 when the content of the formaldehyde scavenger was increased (Comparative Example 5), the generation of formaldehyde could be suppressed, but there was a lot of mold contamination.

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

Abstract

L'invention concerne un mélange de pastilles, et un procédé de production d'un mélange-maître et une composition de résine comprenant un mélange de pastilles. Ce mélange de pastilles comprend : un mélange-maître (1) contenant 0,5 à 3,0 parties en masse d'un piégeur de formaldéhyde (B) par rapport à 100 parties en masse d'une résine de polyacétal (A) ayant un taux de volume à l'état fondu (MVR) de 5 à 50 cm3/10 min tel que mesuré dans des conditions de 190°C et une charge de 2,16 kg conformément à ISO1133 ; et des pastilles (2) contenant une résine de polyacétal (C) ayant un taux de volume à l'état fondu (MVR) de 0,1 à 4 cm3/10 min ou moins tel que mesuré dans des conditions de 190°C et une charge de 2,16 kg conformément à ISO1133.
PCT/JP2024/031628 2023-09-12 2024-09-03 Mélange de pastilles, mélange-maître et procédé de production d'une composition de résine Pending WO2025057822A1 (fr)

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JP2023147840 2023-09-12

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002501098A (ja) * 1998-01-27 2002-01-15 ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング ポリオキシメチレン成形用組成物を着色するための着色剤濃縮物
JP2005163019A (ja) * 2003-11-10 2005-06-23 Polyplastics Co ポリアセタール樹脂組成物
JP2007084604A (ja) * 2005-09-20 2007-04-05 Asahi Kasei Chemicals Corp ポリオキシメチレン樹脂製ハードディスクランプ
JP2013127081A (ja) * 2009-02-25 2013-06-27 Asahi Kasei Chemicals Corp ポリアセタール樹脂組成物の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002501098A (ja) * 1998-01-27 2002-01-15 ティコナ ゲゼルシャフト ミット ベシュレンクテル ハフツング ポリオキシメチレン成形用組成物を着色するための着色剤濃縮物
JP2005163019A (ja) * 2003-11-10 2005-06-23 Polyplastics Co ポリアセタール樹脂組成物
JP2007084604A (ja) * 2005-09-20 2007-04-05 Asahi Kasei Chemicals Corp ポリオキシメチレン樹脂製ハードディスクランプ
JP2013127081A (ja) * 2009-02-25 2013-06-27 Asahi Kasei Chemicals Corp ポリアセタール樹脂組成物の製造方法

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