CN108219356B - Method for producing polyacetal resin composition - Google Patents
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- CN108219356B CN108219356B CN201711285305.1A CN201711285305A CN108219356B CN 108219356 B CN108219356 B CN 108219356B CN 201711285305 A CN201711285305 A CN 201711285305A CN 108219356 B CN108219356 B CN 108219356B
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/166—Magnesium halide, e.g. magnesium chloride
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Abstract
The present invention relates to a method for producing a polyacetal resin composition. [ problem ] to provide a method for producing a polyacetal resin composition having excellent mechanical properties such as tensile strength, tensile elongation, flexural strength, and impact resistance, and particularly excellent creep properties. [ solution ] A method for producing a polyacetal resin composition, wherein (B) 1 to 100 parts by mass of a glass-based inorganic filler obtained by surface treatment with a silane coupling agent, (C) 0.0001 to 0.5 parts by mass of at least one halide selected from magnesium halides and ammonium halides, and (D) 0.002 to 10 parts by mass of a triazine derivative having a nitrogen-containing functional group are melt-kneaded with respect to 100 parts by mass of (A) a polyacetal resin.
Description
Technical Field
The present invention relates to a method for producing a polyacetal resin composition.
Background
Polyacetal resins have excellent properties in mechanical properties, thermal properties, electrical properties, slidability, moldability, impact resistance, dimensional stability of molded articles, and the like, and are widely used as structural materials and mechanical parts for electric devices, automobile parts, precision machine parts, and the like. In addition, it is known to blend a reinforcing material such as a glass-based inorganic filler in order to improve mechanical properties, for example, strength and rigidity, of the polyacetal resin.
However, since the polyacetal resin is poor in activity and the glass-based inorganic filler is poor in activity, merely mixing the glass-based inorganic filler with the polyacetal resin and melting and kneading the mixture results in insufficient adhesion between the two, and the mechanical properties cannot be improved as expected in many cases. Therefore, various methods have been proposed for improving the adhesion between the polyacetal resin and the glass-based inorganic filler to improve the mechanical properties.
For example, known are: a method in which a glass-based inorganic filler and a boric acid compound are added to a polyacetal resin, and the glass-based inorganic filler is subjected to a surface treatment with a specific silane compound (see patent document 1); a polyacetal resin is added with glass fibers obtained by surface treatment with a blocked isocyanate or a urethane resin, and further with phosphorous acid to adjust pH (see patent documents 2 and 3).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. H09-151298
Patent document 2: japanese laid-open patent publication No. H03-79631
Patent document 3: japanese patent laid-open No. 2000-335942
Disclosure of Invention
Problems to be solved by the invention
However, these methods all improve the chemical activity of the glass-based inorganic filler and obtain mechanical properties such as tensile strength, tensile elongation, and flexural strength. In recent years, there has been a demand for providing a polyacetal resin exhibiting impact resistance, durability, and particularly creep characteristics in addition to these mechanical characteristics, and there is room for further improvement in the durability such as creep characteristics of conventional polyacetal resins.
The present invention has been made to solve the above-described problems, and an object thereof is to provide: a process for producing a polyacetal resin having excellent mechanical properties such as tensile strength, tensile elongation, flexural strength and impact resistance, particularly excellent creep properties.
Means for solving the problems
The present inventors have made extensive studies to solve the above problems, and as a result, have found that: the present inventors have completed the present invention by providing a composition which can maintain high mechanical properties and improve creep properties by melt-kneading a specific glass-based inorganic filler with a small amount of a specific halide and a specific triazine derivative with respect to a polyacetal resin. Specifically, the present invention is as follows.
(1) A process for producing a polyacetal resin composition, which comprises (A) 100 parts by mass of a polyacetal resin,
1 to 100 parts by mass of a glass-based inorganic filler (B) obtained by surface treatment with a silane coupling agent,
(C) 0.0001 to 0.5 parts by mass of at least one halide selected from magnesium halide and ammonium halide, and
(D) the triazine derivative having a nitrogen-containing functional group is produced by melt-kneading 0.002 to 10 parts by mass of the triazine derivative.
(2) The method for producing a polyacetal resin composition according to the item (1), wherein the glass-based inorganic filler (B) is obtained by further surface-treating with at least one compound selected from a blocked isocyanate compound and a urethane resin.
(3) The method for producing a polyacetal resin composition according to the above (1) or (2), wherein the halide (C) is one selected from the group consisting of magnesium chloride, magnesium bromide, ammonium chloride and ammonium bromide.
(4) The method for producing a polyacetal resin composition according to any one of (1) to (3), further comprising (E) 0.001 parts by mass or more and 1.0 parts by mass or less of a boric acid compound.
(5) The method for producing a polyacetal resin composition according to any one of (1) to (4), wherein the glass-based inorganic filler (B) is a glass fiber.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a polyacetal resin excellent in mechanical properties such as tensile strength, tensile elongation, flexural strength and impact resistance, and particularly excellent in creep property.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all.
< polyacetal resin composition >
The method for producing a polyacetal resin composition of the present invention is characterized by melt-kneading 1 part by mass or more and 100 parts by mass or less of (B) a glass-based inorganic filler surface-treated with a silane coupling agent, (C) 0.0001 part by mass or more and 0.5 part by mass or less of at least one halide selected from magnesium halides and ammonium halides, and (D) 0.002 part by mass or more and 10 parts by mass or less of a triazine derivative having a nitrogen-containing functional group, relative to 100 parts by mass of (a) a polyacetal resin.
(A) polyacetal resin
The polyacetal resin (A) of the present invention is a polyacetal resin comprising oxymethylene group (-CH)2The polymer compound having O-) as a main constituent unit may be a polyoxymethylene homopolymer, or a copolymer, terpolymer or block copolymer containing oxymethylene as a main repeating unit and a small amount of other constituent units in addition to the oxymethylene unit, for example, a comonomer unit such as ethylene oxide, 1, 3-dioxolan or 1, 4-butanediol formal.
The polyacetal resin may be a resin having a branched or crosslinked structure in which the molecule is linear and glycidyl ether or the like is copolymerized, a known modified polyoxymethylene into which another organic group is introduced, or a mixture of a linear resin and a resin having a branched or crosslinked structure.
The polymerization degree of the polyacetal resin is not particularly limited, and may be any polymerization degree that has melt-moldability (for example, a Melt Flow Rate (MFR) at 190 ℃ under a load of 2160g is 0.1g/10 min or more and 100g/10 min or less).
(B) glass-based inorganic Filler obtained by surface treatment with silane coupling agent
The glass-based inorganic filler (B) of the present invention is obtained by surface treatment with a silane coupling agent. The silane coupling agent is preferably an aminosilane coupling agent as long as it has a functional group (e.g., a vinylalkoxysilane, an epoxyalkoxysilane, a mercaptoalkoxysilane, an allylalkoxysilane, an aminosilane, etc.) to exert the effects of the present invention. The aminosilane coupling agent is a compound containing a silicon atom to which an alkoxy group is bonded in one molecule and a functional group containing a nitrogen atom.
Specific examples of the aminosilane coupling agent include gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, n, N ' -bis [ 3- (trimethoxysilyl) propyl ] ethylenediamine, N ' -bis [ 3- (triethoxysilyl) propyl ] ethylenediamine, N ' -bis [ 3- (methyldimethoxysilyl) propyl ] ethylenediamine, N ' -bis [ 3- (trimethoxysilyl) propyl ] hexamethylenediamine, N ' -bis [ 3- (triethoxysilyl) propyl ] hexamethylenediamine, and the like.
Among the above aminosilane coupling agents, preferred are γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, γ -aminopropylmethyldimethoxysilane, γ -aminopropylmethyldiethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltriethoxysilane and N-phenyl- γ -aminopropyltrimethoxysilane, and more preferred are γ -aminopropyltrimethoxysilane and γ -aminopropyltriethoxysilane.
These silane coupling agents may be used alone or in combination of two or more.
The glass-based inorganic filler (B) of the present invention includes, but is not particularly limited to, fibrous (glass fibers), granular (glass beads), granular (ground glass fibers), plate-like (glass flakes), and hollow fillers. In operation, glass fibers are suitable and chopped into 2-8 mm chopped strands. The diameter of the glass fiber is preferably 5 to 15 μm, preferably 7 to 13 μm.
Blocked isocyanate Compound
The isocyanate compound used as a raw material of the blocked isocyanate compound of the present invention is not particularly limited as long as it is a polyfunctional isocyanate compound having 2 or more isocyanate groups in one molecule.
Examples thereof include aliphatic, alicyclic (hereinafter also referred to as "alicyclic") and aromatic isocyanate compounds, and aliphatic and alicyclic isocyanate compounds are particularly preferable from the viewpoint of compatibility and suitability with the polyacetal resin. Particularly preferred are 2-functional aliphatic or alicyclic diisocyanates and polyisocyanates obtained by polymerizing these diisocyanates.
The aliphatic diisocyanate is preferably a substance having 4 to 30 carbon atoms, and more preferably a substance having 5 to 10 carbon atoms. Specific examples thereof include tetramethylene-1, 4-diisocyanate, pentamethylene-1, 5-diisocyanate, hexamethylene diisocyanate, 2, 4-trimethyl-hexamethylene-1, 6-diisocyanate, and lysine diisocyanate.
The alicyclic diisocyanate is preferably a substance having 8 to 15 carbon atoms, and more preferably a substance having 10 to 18 carbon atoms. Specific examples thereof include isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) -cyclohexane, and 4, 4' -dicyclohexylmethane diisocyanate. Further, examples of the aromatic diisocyanate include xylylene diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate.
Further, examples of the polyisocyanate include compounds having at least 2 isocyanate groups per molecule, for example, various aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; various aralkyl diisocyanates such as m-xylylene diisocyanate and α, α, α ', α' -tetramethyl-m-xylylene diisocyanate; and polyisocyanates having a biuret structure obtained by reacting the various diisocyanates with water, and the like.
Among them, hexamethylene diisocyanate, a cyclic dimer of hexamethylene diisocyanate, or a cyclic trimer of hexamethylene diisocyanate is preferable from the viewpoint of impact resistance, durability, and industrial availability of the obtained composition. In addition, 2 or more of the above-mentioned compounds may be used in combination.
The blocked isocyanate compound of the present invention is not particularly limited, and a compound obtained by blocking a reactive group of the isocyanate compound with a known blocking agent by a conventional method can be used.
Specific examples of the blocking agent include oxime-based blocking agents such as methyl ethyl ketoxime, acetone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; phenol-based blocking agents such as m-cresol and xylenol; alcohol-based blocking agents such as methanol, ethanol, butanol, 2-ethylhexanol, cyclohexanol, and ethylene glycol monoethyl ether; lactam-based blocking agents such as epsilon-caprolactam; diketone systems such as diethyl malonate and acetoacetate; thiol-based blocking agents such as thiophenol; urea-based blocking agents such as thiourea; pyrazole-based blocking agents such as dimethylpyrazole; an imidazole-based capping agent; a carbamic acid-based blocking agent; bisulfite, etc., but is not particularly limited thereto. Among them, lactam-based blocking agents, oxime-based blocking agents, and diketone-based blocking agents are preferably used.
The blocked isocyanate of the present invention is used in an amount of 0.1 to 5 parts by mass, preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the glass-based inorganic filler.
Polyurethane resin
The polyurethane resin of the present invention is particularly preferably a polyurethane resin obtained from a polyisocyanate component mainly composed of xylene diisocyanate and a polyol component mainly composed of polyester polyol in view of bundling property and the like. Examples of the xylylene diisocyanate include o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, and a mixture thereof, and among them, m-xylylene diisocyanate is preferable.
On the other hand, examples of the polyester polyol include a condensation-type polyester polyol obtained by dehydration condensation of a polyhydric alcohol and a polycarboxylic acid, a lactone-type polyester polyol obtained by ring-opening polymerization of a lactone based on a polyhydric alcohol, an ester-modified polyol obtained by ester-modifying an end of a polyether polyol with a lactone, and a copolyester polyol thereof.
Examples of the polyhydric alcohol used in the condensation polyester polyol include ethylene glycol, propylene glycol, 1, 3-propanediol, butanediol, 1, 4-butanediol, 1, 5-pentanediol, hexanediol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, and examples of the polycarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1, 3-cyclopentanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1, 4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and trimellitic acid.
Examples of the lactone polyester polyol include poly (. epsilon. -caprolactone) polyol. These polyester polyols suitably 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 a GPC method and converted to standard polystyrene.
In the production of the polyurethane resin, for example, the following steps can be performed: xylene diisocyanate and polyester polyol are heated at a temperature of 30 ℃ to 130 ℃ or lower in the absence of a solvent or in the presence of a small amount of an organic solvent.
When the heating reaction is carried out, the polyol exemplified in the description of the polyester polyol may be suitably allowed to coexist as a chain extender. When an organic solvent is used, the organic solvent is not particularly limited as long as it does not react with isocyanate and is miscible with water, and for example, acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformamide and the like can be used.
The urethane resin of the present invention is used in an amount of 0.1 to 5 parts by mass, preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the glass-based inorganic filler.
In the present invention, the synergistic effect of the combination of the aminosilane coupling agent and the blocked isocyanate compound and/or the urethane resin is easily obtained, and the adhesion between the polyacetal resin and the glass-based inorganic filler can be improved.
When at least one isocyanate compound selected from blocked isocyanate compounds and urethane resins is used in combination with the glass fibers, the glass fibers may be surface-treated with an aminosilane coupling agent, regardless of the timing of the surface treatment.
That is, the glass fiber may be one obtained by surface-treating with a blocked isocyanate compound and then with other components, or may be one obtained by surface-treating with an aminosilane coupling agent and then with other components.
When the glass fiber of the present invention is surface-treated, it is preferable to use at least one isocyanate compound selected from a blocked isocyanate compound and a urethane resin and an aminosilane coupling agent dissolved or dispersed in an organic solvent or dispersed in water. In particular, as a method for producing an aqueous emulsion containing a polyurethane resin, a self-emulsifying method and a method using an emulsifier are known, and these can be appropriately combined.
< halides >
The halide of the present invention is a magnesium halide or an ammonium halide, and as the halogen element, bromine or chlorine is preferable. Particularly, one selected from the group consisting of magnesium chloride, magnesium bromide, ammonium chloride and ammonium bromide is preferable.
In the present invention, the halide includes anhydrous salts or hydrous salts (e.g., dihydrate salts, tetrahydrate salts, hexahydrate salts, octahydrate salts, and dodecahydrate salts).
The halide of the present invention is also known as a glass sizing agent, for example, as disclosed in Japanese patent application laid-open No. 2003-112952.
The halide of the present invention is 0.0001 to 0.5 parts by mass, and preferably 0.001 to 0.05 parts by mass in terms of creep characteristics.
< (D) triazine derivatives with nitrogen-containing functional groups
In the present invention, (D) a triazine derivative having a nitrogen-containing functional group is preferably compounded. As the triazine derivative (D) having a nitrogen-containing functional group used in the present invention, specifically, there are: guanamine, melamine, N-butylmelamine, N-phenylmelamine, N-diphenylmelamine, N-diallylmelamine, N', N-triphenylmelamine, benzoguanamine, acetoguanamine, 2, 4-diamino-6-butyl-s-triazine, ammeline, 2, 4-diamino-6-benzyloxy-s-triazine, 2, 4-diamino-6-butoxy-s-triazine, 2, 4-diamino-6-cyclohexyl-s-triazine, 2, 4-diamino-6-chloro-s-triazine, 2, 4-diamino-6-mercapto-s-triazine, 6-amino-2, 4-dihydroxy-s-triazine (otherwise known as (ammelide)), 1-bis (3, 5-diamino-2, 4, 6-triazinyl) methane, 1, 2-bis (3, 5-diamino-2, 4, 6-triazinyl) ethane (otherwise known as (succinoguanylamine)), 1, 3-bis (3, 5-diamino-2, 4, 6-triazinyl) propane, 1, 4-bis (3, 5-diamino-2, 4, 6-triazinyl) butane, methyleneated melamine, ethylenebis (melamine), triguanamine, melamine cyanurate, ethylenebis (melamine) cyanurate, triguanamine cyanurate, and the like.
These triazine derivatives can be used in a single kind, or in combination of 2 or more kinds. Guanamine and melamine are preferable, and melamine is particularly preferable.
In the present invention, when the triazine derivative (D) having a nitrogen-containing functional group is blended, the blending amount thereof is preferably 0.002 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 2 parts by mass or less, and particularly preferably 0.03 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the polyacetal resin.
When 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 when the content is 10 parts by mass or less, the problem of bleeding out from the polyacetal resin does not occur, which is preferable.
(C) boric acid
In the present invention, boric acid is preferably compounded. The type is not particularly limited, and examples thereof include orthoboric acid, metaboric acid, and tetraboric acid. Among them, orthoboric acid is preferable. (C) The amount of boric acid added is 0.001 to 1.0 part by mass, and preferably 0.005 to 0.2 part by mass from the viewpoint of mechanical properties.
< other various stabilizers and additives >
The polyacetal resin composition of the present invention may further contain various known stabilizers and additives. Examples of the stabilizer include one or 2 or more kinds of hindered phenol compounds, nitrogen-containing basic compounds, hydroxides, inorganic salts, and carboxylates of alkali or alkaline earth metals.
Examples of the additives include any one or 2 or more of common additives for thermoplastic resins, for example, colorants such as dyes and pigments, lubricants, nucleating agents, mold release agents, antistatic agents, and surfactants.
One or more than 2 known inorganic, organic, and metallic fillers in fibrous, plate, powder and granular form may be compounded and compounded as long as the performance of the target molded article of the present invention is not significantly deteriorated. Examples of such fillers include talc, mica, wollastonite, carbon fiber, and the like, but are not limited thereto at all.
< production of polyacetal resin composition >
The polyacetal resin composition of the present invention can be easily produced by a known method generally used as a conventional method for producing a resin composition. For example, it is possible to use: mixing the components, melting and mixing the components by a single-screw or double-screw extruder, extruding the mixture to prepare granules, and then molding the granules; any method may be used, such as a method of preparing pellets (master batch) having different compositions temporarily, mixing (diluting) the pellets by a predetermined amount, molding the mixture, and obtaining a molded article having a desired composition after molding.
In the production of the polyacetal composition, a preferable method is, for example, a method of pulverizing a part or the whole of the polyacetal resin as the matrix, mixing the pulverized polyacetal resin with other components, and then extruding the mixture, in order to improve the dispersibility of the additive.
The present invention is characterized in that the components (A), (B), (C) and (D) are prepared separately and then melt-kneaded. (C) The halide of the component (a) is known as a glass sizing agent, and therefore, generally, glass fibers are subjected to surface treatment in advance to be adhered and then melt-kneaded with the components (a) and (B), and the present invention has characteristics of respective preparations. This makes it easy to adjust the amount of component (C) to component (a), and eventually makes it possible to increase the variation in the resin composition.
In the present invention, the cause and effect relationship between the improvement of creep characteristics and the addition of a halide separately, a glass-based inorganic filler, and a resin structure is not clear, but it is estimated that: the halide exists as a function other than the interaction of the glass sizing agent.
Examples
The present invention will be further specifically described below with reference to examples, but the present invention is not limited to the following examples. Unless otherwise stated, each evaluation was performed at 23 ℃ under 55% RH.
< production of polyacetal resin composition >
In tables 1 and 2, various materials are as follows.
[ (A) polyacetal resin ]
(A1) Polyacetal resin (polyacetal copolymer (melt index (measured at 190 ℃ C. under a load of 2160 g): 9g/10 min) obtained by copolymerizing trioxane in an amount of 96.7% by mass with 1, 3-dioxolane in an amount of 3.3% by mass
[ (B) glass-based inorganic Filler ]
(B0) Chopped strands of 9 μm diameter glass fibers obtained by surface treatment with 0.02 mass% of an aminosilane coupling agent (γ -aminopropyltriethoxysilane).
(B1) Chopped strands of 9 μm diameter of glass fibers were obtained by surface-treating with 0.02 mass% of an aminosilane coupling agent (γ -aminopropyltriethoxysilane) and 0.6 mass% of a urethane resin.
(B2) Chopped strands of 10 μm diameter glass fibers were obtained by surface-treating 1.2 mass% of blocked isocyanate of hexamethylene diisocyanate blocked with methyl ethyl ketoxime and 0.02 mass% of aminosilane coupling agent (. gamma. -aminopropyltriethoxysilane).
(B3) Chopped strands of glass fiber having a diameter of 13 μm were obtained by surface-treating 1.2% by mass of blocked isocyanate which is a trimer of hexamethylene diisocyanate blocked with methyl ethyl ketoxime and 0.02% by mass of an aminosilane coupling agent (. gamma. -aminopropyltriethoxysilane).
(B4) Chopped strands having a glass fiber diameter of 10 μm were obtained by surface-treating 1.0 mass% of blocked isocyanate of hexamethylene diisocyanate blocked with methyl ethyl ketoxime, 0.02 mass% of aminosilane coupling agent (. gamma. -aminopropyltriethoxysilane), and 0.3 mass% of urethane resin.
(B5) A chopped strand of 10 μm diameter of glass fiber obtained by surface-treating 1.0 mass% of a blocked isocyanate, 0.02 mass% of an aminosilane coupling agent, and 0.3 mass% of a urethane resin, which are described in example 1 of Japanese patent application publication No. 6-27204.
[ (C) halide ]
(C1) Magnesium chloride hexahydrate
(C2) Ammonium chloride
(C3) Magnesium bromide hexahydrate
(C4) Ammonium bromide
[ (C') other halides ]
(C' 1) sodium chloride
[ (D) triazine derivatives having Nitrogen-containing functional group ]
(D1) Melamine
[ (E) boric acid Compound ]
(E1) Orthoboric acid
100 parts by mass of a polyacetal resin was compounded with a glass-based inorganic filler, a halide, a triazine derivative having a nitrogen-containing functional group, and a boric acid compound in amounts shown in tables 1 and 2, and melt-kneaded in an extruder having a barrel temperature of 200 ℃.
In the examples using ammonium chloride and ammonium bromide, an aqueous solution in which a predetermined amount of a halide shown in the table was dissolved in 2 parts by weight of water was uniformly mixed with the polyacetal resin in advance with respect to 100 parts by weight of the polyacetal resin, and then the mixture was dried at 120 ℃.
< evaluation of physical Properties >
Test pieces were molded from the pelletized compositions of examples and comparative examples using an injection molding machine. Then, the tensile strength and tensile elongation according to ISO527-1.2, the bending strength according to ISO178, and the Charpy impact strength (notched, 23 ℃) according to ISO179 & 1eA were measured.
< evaluation of creep resistance >
The time until the test piece cracked was measured in a creep testing machine by applying a load of 40MPa at 80 ℃ in the atmosphere as a high-temperature high-load condition using a tensile test piece according to ISO 3167.
The evaluation results are shown in tables 1 and 2.
[ Table 1]
[ Table 2]
As is clear from tables 1 and 2, the polyacetal resin compositions of the present invention are excellent in creep characteristics and also excellent in mechanical characteristics such as tensile strength, tensile elongation, flexural strength and charpy impact strength.
Claims (4)
1. A process for producing a polyacetal resin composition, which comprises (A) 100 parts by mass of a polyacetal resin,
1 to 100 parts by mass of a glass-based inorganic filler obtained by subjecting (B) a glass-based inorganic filler obtained by surface-treating with a silane coupling agent and further subjecting the resultant to surface treatment with at least one compound selected from a blocked isocyanate compound and a urethane resin,
(C) 0.0001 to 0.5 parts by mass of at least one halide selected from magnesium halide and ammonium halide, and
(D) the triazine derivative having a nitrogen-containing functional group is produced by melt-kneading 0.002 to 10 parts by mass of the triazine derivative.
2. The method for producing a polyacetal resin composition according to claim 1, wherein the halide (C) is one selected from the group consisting of magnesium chloride, magnesium bromide, ammonium chloride and ammonium bromide.
3. The method for producing a polyacetal resin composition according to claim 1 or 2, further comprising (E) 0.001 parts by mass or more and 1.0 parts by mass or less of a boric acid compound.
4. The method for producing a polyacetal resin composition according to claim 1 or 2, wherein the glass-based inorganic filler (B) is glass fiber.
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| JP2016247414A JP6832151B2 (en) | 2016-12-21 | 2016-12-21 | Method for producing polyacetal resin composition |
| JP2016-247414 | 2016-12-21 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003112952A (en) * | 2001-10-03 | 2003-04-18 | Nitto Boseki Co Ltd | Sizing agent for glass fiber containing magnesium chloride |
| CN101010380A (en) * | 2004-09-03 | 2007-08-01 | 宝理塑料株式会社 | Polyacetal resin composition |
| CN101121810A (en) * | 2006-08-11 | 2008-02-13 | 宝理塑料株式会社 | Polyacetal resin composition |
| CN104995254A (en) * | 2013-02-04 | 2015-10-21 | 宝理塑料株式会社 | Polyacetal resin composition, and manufacturing method for same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4060831B2 (en) * | 2004-07-26 | 2008-03-12 | オーウェンスコーニング製造株式会社 | Chopped strand and fiber reinforced polyacetal resin molding material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003112952A (en) * | 2001-10-03 | 2003-04-18 | Nitto Boseki Co Ltd | Sizing agent for glass fiber containing magnesium chloride |
| CN101010380A (en) * | 2004-09-03 | 2007-08-01 | 宝理塑料株式会社 | Polyacetal resin composition |
| CN101121810A (en) * | 2006-08-11 | 2008-02-13 | 宝理塑料株式会社 | Polyacetal resin composition |
| CN104995254A (en) * | 2013-02-04 | 2015-10-21 | 宝理塑料株式会社 | Polyacetal resin composition, and manufacturing method for same |
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| JP6832151B2 (en) | 2021-02-24 |
| CN108219356A (en) | 2018-06-29 |
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