WO2017169438A1 - Composition de résine de polyacétal - Google Patents

Composition de résine de polyacétal Download PDF

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Publication number
WO2017169438A1
WO2017169438A1 PCT/JP2017/007480 JP2017007480W WO2017169438A1 WO 2017169438 A1 WO2017169438 A1 WO 2017169438A1 JP 2017007480 W JP2017007480 W JP 2017007480W WO 2017169438 A1 WO2017169438 A1 WO 2017169438A1
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WIPO (PCT)
Prior art keywords
mass
polyacetal resin
glass
parts
inorganic filler
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PCT/JP2017/007480
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English (en)
Japanese (ja)
Inventor
原科　初彦
広和 勝地
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ポリプラスチックス株式会社
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Application filed by ポリプラスチックス株式会社 filed Critical ポリプラスチックス株式会社
Priority to CN201780011242.2A priority Critical patent/CN108603007B/zh
Priority to JP2017547013A priority patent/JP6231728B1/ja
Publication of WO2017169438A1 publication Critical patent/WO2017169438A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to a polyacetal resin composition.
  • Polyacetal resin has excellent properties in mechanical properties, thermal properties, electrical properties, slidability, moldability, impact resistance, dimensional stability of molded products, etc. Widely used in automotive parts, precision machine parts, etc. It is known that a reinforcing material such as a glass-based inorganic filler is blended in order to improve the mechanical properties of the polyacetal resin, such as strength and rigidity.
  • polyacetal resin has poor activity
  • glass-based inorganic fillers also have poor activity. Therefore, simply blending glass-based inorganic filler with polyacetal resin and melt-kneading will result in insufficient adhesion between the two. In many cases, the mechanical properties cannot be improved as much as possible. Therefore, various methods for improving the mechanical properties by improving the adhesion between the polyacetal resin and the glass-based inorganic filler have been proposed.
  • the present invention has been made to solve the above-described problems, and its purpose is excellent in mechanical properties such as tensile strength, tensile elongation, bending strength, bending elastic modulus, impact resistance, and the like. Another object is to provide a polyacetal resin having excellent hot water resistance.
  • the present inventors have intensively studied.
  • the polyacetal resin has a high mechanical property by using a specific glass-based inorganic filler and a small amount of boric acid.
  • the inventors have found that the hot water resistance can be improved while maintaining the above, and have completed the present invention.
  • the present invention provides the following.
  • the present invention relates to (A) 100 parts by mass of a polyacetal resin, (B) at least one isocyanate compound selected from blocked isocyanate compounds and polyurethane resins, an aminosilane coupling agent, magnesium halide, and 1 to 100 parts by weight of a glass-based inorganic filler surface-treated with at least one halide selected from ammonium halides, and (C) 0.001 to 1.0 parts by weight of boric acid
  • a polyacetal resin composition containing:
  • this invention is a polyacetal resin composition as described in (1) which contains 0.002 mass part or more and 10 mass parts or less of the triazine derivative which has (D) nitrogen-containing functional group further.
  • the present invention also provides the polyacetal resin composition according to (1) to (2), wherein (C) boric acid is orthoboric acid.
  • the present invention provides the polyacetal resin composition according to any one of (1) to (3), wherein the glass-based inorganic filler (B) is a glass fiber.
  • a polyacetal resin that is excellent in mechanical properties such as tensile strength, tensile elongation, bending strength, flexural modulus, and impact resistance, and also excellent in hot water resistance.
  • the polyacetal resin composition of the present embodiment comprises (B) at least one isocyanate compound selected from a blocked isocyanate compound and a polyurethane resin, an aminosilane coupling agent, and a halogen with respect to 100 parts by mass of (A) polyacetal resin. 1 to 100 parts by mass of a glass-based inorganic filler surface-treated with at least one halide selected from magnesium halide and ammonium halide, and (C) 0.001 to 1 part by mass of boric acid. 0 parts by mass or less.
  • each component will be described.
  • a polyacetal resin is a high molecular compound having an oxymethylene group (—CH 2 O—) as a main structural unit, a polyoxymethylene homopolymer, or an oxymethylene group as a main repeating unit.
  • the copolymer may be a copolymer, terpolymer or block polymer containing a small amount of a comonomer unit such as ethylene oxide, 1,3-dioxolane, 1,4-butanediol formal and the like.
  • the polyacetal resin may have a branched or crosslinked structure as well as a linear molecule, or may be a known modified polyoxymethylene having other organic groups introduced.
  • the polyacetal resin is not particularly limited with respect to the degree of polymerization, and has a melt molding processability (for example, a melt flow value (MFR) at 190 ° C. under a load of 2160 g is 1.0 g / 10 min or more and 100 g / min. 10 minutes or less).
  • MFR melt flow value
  • the glass-based inorganic filler comprises at least one isocyanate compound selected from blocked isocyanate compounds and polyurethane resins, an aminosilane coupling agent, and at least one halide selected from magnesium halide and ammonium halide. It is sufficient that the surface treatment is performed, and the timing of the surface treatment is not limited. That is, the glass-based inorganic filler may be surface-treated with a blocked isocyanate compound and then surface-treated with other components, or may be surface-treated with an aminosilane coupling agent and then other components. The surface treatment may be performed.
  • the surface treatment may be performed with other components after the surface treatment with a halide.
  • the glass-based inorganic filler may be a surface treated with at least one isocyanate compound selected from a blocked isocyanate compound and a polyurethane resin, an aminosilane coupling agent, and a halide at the same time.
  • the glass-based inorganic filler is surface-treated with at least one isocyanate compound selected from blocked isocyanate compounds and polyurethane resins, an aminosilane coupling agent, and a halide is determined as polyacetal.
  • the glass-based inorganic filler can be extracted from the resin composition by solvent extraction and the components can be analyzed.
  • the surface treatment agent does not contain the isocyanate compound, aminosilane coupling agent and halide, the isocyanate compound, aminosilane cup Compared with the surface treatment with a ring agent and a halide, not only mechanical properties such as tensile strength are inferior, but also hot water resistance is inferior, which is not preferable.
  • Glass-based inorganic filler examples include fibrous (glass fiber), granular (glass bead), granular (milled glass fiber), plate (glass flake), and hollow filler. It is not limited. In terms of handling, chopped strands that are glass fibers and cut to about 2 to 8 mm are preferable. The diameter of the glass fiber is usually 5 to 15 ⁇ m, preferably 7 to 13 ⁇ m.
  • any polyfunctional isocyanate compound having two or more isocyanate groups in one molecule can be used without particular limitation.
  • aliphatic (including linear, branched, and alicyclic) and aromatic isocyanate compounds can be mentioned, and in particular, from the viewpoint of compatibility and compatibility with polyacetal resins, aliphatic isocyanate compounds are preferable.
  • bifunctional aliphatic or alicyclic diisocyanates, and polyisocyanates obtained by multiplying these diisocyanates are preferable.
  • linear or branched aliphatic diisocyanate those having 4 to 30 carbon atoms are preferable, and those having 5 to 10 carbon atoms are more preferable.
  • Specific examples include tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene-1,6-diisocyanate, and lysine diisocyanate. Can do.
  • alicyclic diisocyanate those having 8 to 15 carbon atoms are preferable, and those having 10 to 18 carbon atoms are more preferable. Specific examples include isophorone diisocyanate, 1,3-bis (isocyanate methyl) -cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, and the like.
  • aromatic diisocyanate examples include xylylene diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate.
  • Polyisocyanates include compounds having at least two isocyanate groups per molecule, for example, various aromatic diisocyanates such as tolylene diisocyanate or diphenylmethane diisocyanate; m-xylylene diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ Various aralkyl diisocyanates such as' -tetramethyl-m-xylylene diisocyanate; addition reaction of aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate or isophorone diisocyanate with polyhydric alcohols Prepolymers having an isocyanurate ring, obtained by cyclization and trimerization of the above-mentioned various diisocyanates, such as the obtained isocyanate group-containing prepolymers And Ma acids, or the various diisocyanates, such as those obtained by reacting a water adduct having a bi
  • hexamethylene diisocyanate, hexamethylene diisocyanate biuret, or hexamethylene diisocyanate cyclic trimer is preferable from the viewpoint of impact resistance and durability of the resulting composition and industrial availability.
  • Two or more of the above compounds can be used in combination. Furthermore, it may be a mixture of two or more of the above compounds.
  • blocking agents include, for example, oxime blocking agents such as methyl ethyl ketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime; phenol blocking agents such as m-cresol, xylenol; methanol, ethanol, butanol Alcohol blocking agents such as 2-ethylhexanol, cyclohexanol and ethylene glycol monoethyl ether; lactam blocking agents such as ⁇ -caprolactam; diketone blocking agents such as diethyl malonate and acetoacetate; thiophenol Mercaptan blocking agents such as thiourea, urea blocking agents such as thiourea, imidazole blocking agents, pyrazo
  • the blocked isocyanate of the present invention is used in an amount of 0.01 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the glass-based inorganic filler. ⁇ Polyurethane resin ⁇
  • the polyurethane resin of the present embodiment those obtained from a polyisocyanate component mainly composed of xylylene diisocyanate and a polyol component mainly composed of polyester polyol are preferable from the viewpoint of sizing properties and the like.
  • examples of the xylylene diisocyanate include o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, and mixtures thereof. Among these, m-xylylene diisocyanate is preferable.
  • polyester polyol examples include a condensed polyester polyol obtained by dehydration condensation of a polyhydric alcohol and a polycarboxylic acid, a lactone polyester polyol obtained by ring-opening polymerization of a lactone based on a polyhydric alcohol, Examples thereof include ester-modified polyols obtained by ester-modifying the ends of ether polyols with lactones and copolymerized polyester polyols thereof.
  • Examples of the polyhydric alcohol used in the condensed polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, butylene glycol, 1,4-butanediol, 1,5-pentanediol, hexylene glycol, Examples include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, etc.
  • Examples of polyvalent carboxylic acids include succinic acid, adipic acid, and azelain.
  • Acid sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, iso Tal acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, trimellitic acid and the like.
  • lactone polyester polyol examples include poly ( ⁇ -caprolactone) polyol. These polyester polyols preferably have a weight average molecular weight in the range of 500 or more and 4000 or less.
  • the weight average molecular weight of the resin in the present specification is a value measured by GPC method and converted to standard polystyrene.
  • the polyurethane resin can be produced, for example, by heating xylylene diisocyanate and polyester polyol at about 30 ° C. to 130 ° C. in the absence of a solvent or in the presence of a small amount of an organic solvent.
  • the organic solvent is not particularly limited as long as it does not react with isocyanate and is miscible with water.
  • acetone, methyl ethyl ketone, tetrahydrofuran, dimethyl Formamide or the like can be used.
  • the polyurethane resin of the present invention is used in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the glass-based inorganic filler.
  • aminosilane coupling agent is used for the surface treatment of the glass-based inorganic filler of the present embodiment.
  • the aminosilane coupling agent means a compound containing a silicon atom having an alkoxy group bonded in one molecule and a functional group containing a nitrogen atom.
  • Specific aminosilane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltriethoxysilane, N, N'-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N'- Bis- [3- (triethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (trimethoxysilyl) propyl] Hexam
  • aminosilane coupling agents among them, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, N- ( ⁇ -aminoethyl) ) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltriethoxysilane and N-phenyl- ⁇ -aminopropyltrimethoxysilane are preferred, and ⁇ -aminopropyltrimethoxysilane And ⁇ -aminopropyltriethoxysilane are more preferable.
  • aminosilane coupling agents According to these aminosilane coupling agents, a synergistic effect by the combination with the blocked isocyanate compound can be easily obtained, and the adhesion between the polyacetal resin and the glass-based inorganic filler can be improved.
  • the surface treatment with the aminosilane coupling agent of the present invention is performed at 0.01 to 3 parts by mass, preferably 0.03 to 1 part by mass, with respect to 100 parts by mass of the glass-based inorganic filler.
  • halide selected from magnesium halide and ammonium halide is used for the surface treatment of the glass-based inorganic filler of the present embodiment.
  • the halide of the present invention is magnesium halide or ammonium halide, and bromine and chlorine are preferable as the halogen element.
  • one selected from magnesium chloride, magnesium bromide, ammonium chloride and ammonium bromide is preferable.
  • the halide includes an anhydrous salt or a hydrated salt (dihydrate, tetrahydrate, hexahydrate, octahydrate, dodecahydrate, etc.).
  • the halide of the present invention is 0.00001 parts by mass or more and 0.5 parts by mass or less, and preferably 0.0001 parts by mass or more and 0.05 parts by mass or less with respect to 100 parts by mass of the glass-based inorganic filler. Since the halide of the present invention has water solubility, the halide may be used in a state of being dissolved in water in the surface treatment of the glass-based inorganic filler of the present embodiment.
  • the halide used for the surface treatment of the glass-based inorganic filler of this embodiment greatly contributes to the improvement of the tensile strength, bending strength, bending elastic modulus, impact resistance and hot water resistance of the polyacetal resin. It is done.
  • the glass-based inorganic filler of this embodiment is more preferably a glass-based inorganic filler surface-treated with a blocked isocyanate compound, a polyurethane resin, an aminosilane coupling agent, and a halide.
  • the glass-based inorganic filler only needs to be surface-treated with an isocyanate compound, an aminosilane coupling agent, and a halide, and the timing of the surface treatment does not matter. That is, when surface-treating the glass-based inorganic filler, a plurality of surface treatment agents may be used sequentially, or a plurality of surface treatment agents may be used simultaneously.
  • At least one isocyanate compound selected from a blocked isocyanate compound and a polyurethane resin, an aminosilane coupling agent, and a halide are contained in an organic solvent. It is preferable to dissolve or disperse in water, or disperse in water.
  • a method for producing an aqueous emulsion containing a polyurethane resin there are a self-emulsification method and a method using an emulsifier, but these may be combined appropriately.
  • Hydrophilicity by introducing an ionic group (sulfonic acid group, amino group, carboxyl group, etc.) or nonionic hydrophilic group (polyethylene glycol, polyoxyalkylene glycol, etc.) into the side chain or terminal of the polyurethane resin. And then dispersing or dissolving in water by self-emulsification.
  • an ionic group sulfonic acid group, amino group, carboxyl group, etc.
  • nonionic hydrophilic group polyethylene glycol, polyoxyalkylene glycol, etc.
  • a polyurethane resin emulsion having a higher molecular weight can be produced by adding a chain extender to a polyurethane resin having an isocyanate group at the time of emulsification or after emulsification.
  • a chain extender known ones such as ethylene glycol, diethylene glycol, propylene glycol, hydrazine, N, N-dimethylhydrazine can be used.
  • the compounding quantity of a glass-type inorganic filler is 1 to 100 mass parts with respect to 100 mass parts of polyacetal resin, Preferably it is 5 to 55 mass parts, Most preferably, it is 10 mass. Part to 40 parts by weight.
  • the content of the glass-based inorganic filler is less than 1 part by mass, the mechanical properties and hot water resistance of the molded product are insufficiently improved, and when the content exceeds 100 parts by mass, the molding process becomes difficult. .
  • the kind of boric acid is not specifically limited, Any of orthoboric acid, metaboric acid, tetraboric acid, etc. may be sufficient. Of these, orthoboric acid is preferred.
  • the blending amount of boric acid is 0.001 part by mass or more and 1.0 part by mass or less, preferably 0.003 part by mass or more and 0.5 part by mass or less with respect to 100 parts by mass of the polyacetal resin. If it is less than 0.001 part by mass, the mechanical effect and hot water resistance are poor and the desired effect cannot be obtained, and if it exceeds 1.0 part by mass, the mechanical effect and hot water resistance are similarly poor and the desired effect cannot be obtained.
  • the effect of the present invention cannot be obtained if the acid is a general inorganic acid or organic acid. Even if hydrochloric acid or phosphoric acid is used as the inorganic acid and formic acid or acetic acid is used as the organic acid, the mechanical properties and hot water resistance do not reach the level of the effect of boric acid.
  • This embodiment has improved both the mechanical properties and hot water resistance of the polyacetal resin by using (B) a glass-based inorganic filler subjected to a specific surface treatment and (C) boric acid in combination. It is characterized by. (B) Although the cause of the improvement of the mechanical properties and hot water resistance of the polyacetal resin by the glass-based inorganic filler subjected to a specific surface treatment and (C) boric acid is unknown, It is thought to be due to a synergistic effect due to interaction.
  • a polyacetal resin (C When no boric acid is contained or (C) an acid other than boric acid is contained, the polyacetal resin cannot have sufficient mechanical properties and hot water resistance.
  • the polyacetal resin composition of the present embodiment may further contain a glass-based inorganic filler surface-treated with a known coupling agent other than an aminosilane coupling agent.
  • the coupling agent is used to improve the wettability and adhesiveness of the glass-based inorganic filler with the polyacetal resin.
  • silane coupling agent examples include vinyl alkoxy silane, epoxy alkoxy silane, mercapto alkoxy silane, and allyl alkoxy silane.
  • vinylalkoxysilane examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, and the like.
  • Examples of the epoxyalkoxysilane include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and ⁇ -glycidoxypropyltriethoxysilane.
  • Examples of mercaptoalkoxysilanes include ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane.
  • allylalkoxysilanes include ⁇ -diallylaminopropyltrimethoxysilane, ⁇ -allylaminopropyltrimethoxysilane, and ⁇ -allylthiopropyltrimethoxysilane.
  • titanate-based surface treatment agent examples include titanium-i-propoxyoctylene glycolate, tetra-n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, and the like. These coupling agents may be used alone or in combination of two or more.
  • the polyacetal resin composition of the present embodiment may further contain various known stabilizers / additives.
  • the stabilizer include one or more of hindered phenol compounds, nitrogen-containing basic compounds, alkali or alkaline earth metal hydroxides, inorganic salts, carboxylates, and the like.
  • general additives for thermoplastic resins for example, coloring agents such as dyes and pigments, lubricants, nucleating agents, mold release agents, antistatic agents, and surfactants are used alone or in combination. Can be mentioned.
  • the nitrogen-containing basic compound is used for enhancing the heat resistance stability of the polyacetal resin composition.
  • the kind of nitrogen-containing basic compound is not particularly limited, an example is (D) a triazine derivative having a nitrogen-containing functional group.
  • Triazine derivative having nitrogen-containing functional group It is particularly preferable to blend a triazine derivative having a nitrogen-containing functional group from the viewpoint of further improving mechanical properties.
  • Specific examples of the triazine derivative (D) having a nitrogen-containing functional group used in this embodiment include guanamine, melamine, N-butylmelamine, N-phenylmelamine, N, N′-diphenylmelamine, N, N '-Diallylmelamine, N, N', N ''-triphenylmelamine, benzoguanamine, acetoguanamine, 2,4-diamino-6-butyl-sym-triazine, ammeline, 2,4-diamino-6-benzyloxy- sym-triazine, 2,4-diamino-6-butoxy-sym-triazine, 2,4-diamino-6-cyclohexyl-sym-triazine
  • triazine derivatives may be used alone or in combination of two or more.
  • Preferred are guanamine and melamine, with melamine being particularly preferred.
  • the blending amount is preferably 0.002 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyacetal resin. Preferably they are 0.01 mass part or more and 2 mass parts or less, Most preferably, they are 0.03 mass part or more and 1 mass part or less.
  • the content of the triazine derivative (D) is 0.002 parts by mass or more, the thermal stability of the polyacetal resin can be improved, and if it is 10 parts by mass or less, problems such as bleeding from the polyacetal resin. This is preferable.
  • inorganic, organic, and metallic fibers other than glass-based inorganic fillers, plates, powders, etc. It is also possible to mix one type or two or more types of fillers such as granules. Examples of such fillers include talc, mica, wollastonite, carbon fiber, etc., but are not limited to these.
  • the polyacetal resin composition of this embodiment is easily prepared by a known method generally used as a conventional resin composition preparation method. For example, after mixing each component, kneading and extruding with a single or twin screw extruder to prepare pellets, then forming, pellets with different compositions (master batch) once prepared, the pellets Any of a method of mixing (diluting) a predetermined amount for use in molding and obtaining a molded product of the desired composition after molding can be used. Further, in the preparation of the acetal composition, it is preferable to extrude after part or all of the polyacetal resin as a substrate is mixed and mixed with other components to improve the dispersibility of the additive. Is the method.
  • (B4) Hexamethylene diisocyanate blocked with methyl ethyl ketoxime 1.0 mass% blocked isocyanate, 0.02 mass% aminosilane coupling agent ( ⁇ -aminopropyltriethoxysilane), 0.001 mass% magnesium chloride surface Treated chopped strand with a diameter of 10 ⁇ m.
  • (B5) A chopped strand having a diameter of 10 ⁇ m and surface-treated with 1.2% by mass of a polyurethane resin, 0.02% by mass of an aminosilane coupling agent ( ⁇ -aminopropyltriethoxysilane) and 0.001% by mass of magnesium chloride.
  • a glass-based inorganic filler, boric acid and a triazine derivative having a nitrogen-containing functional group are blended in 100 parts by mass of a polyacetal resin in the amounts shown in Tables 1 to 4, and melt-kneaded with an extruder having a cylinder temperature of 200 ° C.
  • Pellet-shaped polyacetal resin compositions according to examples and comparative examples were prepared.
  • Test pieces were molded from the pellet-shaped compositions according to the examples and comparative examples using an injection molding machine. Then, the tensile strength / tensile elongation according to ISO527-1 and 2, the bending strength / flexural modulus according to ISO178, and the Charpy impact strength (notched, 23 ° C.) according to ISO179 / 1eA were measured. . The results are shown in Tables 1 to 4.
  • Example 1 containing the glass fiber (B1) of this embodiment surface-treated with a blocked isocyanate compound, polyurethane resin, aminosilane coupling agent and magnesium chloride, blocked isocyanate compound, aminosilane coupling agent and chloride
  • Example 4 containing the glass-based inorganic filler (B4) of this embodiment surface-treated with magnesium, or the glass-based inorganic filler of this embodiment surface-treated with a polyurethane resin, an aminosilane coupling agent and magnesium chloride
  • Example 5 containing the material (B5)
  • Example 1 is most excellent in terms of impact strength.
  • a glass-based inorganic filler surface-treated with a blocked isocyanate compound, an aminosilane coupling agent, a polyurethane resin, and magnesium chloride is more preferable in terms of improving the impact strength of the polyacetal resin composition. It was.
  • the polyacetal resin composition molded article of Example 7 containing the glass-based inorganic filler (B3) and the triazine derivative according to this embodiment is different only in that it does not contain a triazine derivative. Since it shows mechanical properties such as higher impact strength than the molded product, it was confirmed that the triazine derivative enhances the effect of the glass-based inorganic filler subjected to the surface treatment of the present invention.
  • Comparative Examples 1 to 5 and 7 to 9 containing no boric acid are inferior in mechanical properties such as initial tensile strength and impact resistance. Further, Comparative Examples 6, 10 and 11 using the glass inorganic filler not subjected to the surface treatment of the present invention are also inferior in mechanical properties such as initial tensile strength and impact resistance.
  • Comparative Examples 7 and 8 containing an acid that is not boric acid are greatly inferior to the examples of the present invention in mechanical properties.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention décrit une résine de polyacétal qui fait preuve d'excellentes propriétés mécaniques et résistance à l'eau chaude. Cette composition de résine de polyacétal contient : (A) 100 parties en masse d'une résine de polyacétal ; (B) de 1 à 100 parties en masse, comprenant un matériau de charge de verre inorganique soumis à un traitement de surface en utilisant au moins un type de composé isocyanate sélectionné parmi un composé isocyanate bloqué et une résine de polyuréthane, un agent de couplage aminosilane, et au moins un type d'halogénure sélectionné parmi l'halogénure de magnésium et l'halogénure d'ammonium ; et (C) de 0,001 à 1,0 partie en masse, comprenant de l'acide borique. De plus, il est préférable que le constituant (C) soit de l'acide orthoborique. En outre, il est préférable que la composition de résine de polyacétal contienne également (D) de 0,002 à 10 parties en masse, comprenant un dérivé triazine qui possède un groupe fonctionnel contenant de l'azote.
PCT/JP2017/007480 2016-03-31 2017-02-27 Composition de résine de polyacétal WO2017169438A1 (fr)

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JP2021036017A (ja) * 2019-08-30 2021-03-04 ポリプラスチックス株式会社 ポリアセタール樹脂組成物とその製造方法

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JP2006037267A (ja) * 2004-07-26 2006-02-09 Asahi Fiber Glass Co Ltd チョップドストランド及び繊維強化ポリアセタール樹脂成形材料
JP2006070196A (ja) * 2004-09-03 2006-03-16 Polyplastics Co ポリアセタール樹脂組成物
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Publication number Priority date Publication date Assignee Title
JPH09151298A (ja) * 1995-09-29 1997-06-10 Polyplastics Co ポリアセタール樹脂組成物
JP2003112952A (ja) * 2001-10-03 2003-04-18 Nitto Boseki Co Ltd 塩化マグネシウムを含有するガラス繊維用集束剤
JP2009167426A (ja) * 2002-03-05 2009-07-30 Ticona Gmbh ポリオキシメチレン成形用化合物及びそれらから製造した成形品
JP2006037267A (ja) * 2004-07-26 2006-02-09 Asahi Fiber Glass Co Ltd チョップドストランド及び繊維強化ポリアセタール樹脂成形材料
JP2006070196A (ja) * 2004-09-03 2006-03-16 Polyplastics Co ポリアセタール樹脂組成物
JP2008044995A (ja) * 2006-08-11 2008-02-28 Polyplastics Co ポリアセタール樹脂組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021036017A (ja) * 2019-08-30 2021-03-04 ポリプラスチックス株式会社 ポリアセタール樹脂組成物とその製造方法
JP7339812B2 (ja) 2019-08-30 2023-09-06 ポリプラスチックス株式会社 ポリアセタール樹脂組成物とその製造方法

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