CN110003609B - Resin composition - Google Patents
Resin composition Download PDFInfo
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- CN110003609B CN110003609B CN201811624518.7A CN201811624518A CN110003609B CN 110003609 B CN110003609 B CN 110003609B CN 201811624518 A CN201811624518 A CN 201811624518A CN 110003609 B CN110003609 B CN 110003609B
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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
- C08K3/02—Elements
- C08K3/08—Metals
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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
- C08K3/34—Silicon-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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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Abstract
The invention provides a resin composition which can produce a molded article with less formaldehyde generation and excellent metal tone appearance, and can inhibit mold fouling during molding. A resin composition comprising: (A) 100 parts by mass of polyacetal resin, (B) 0.01 to 15 parts by mass of metal particles, and (C) a pearlescent pigment, wherein the volume average particle diameter (D) of the metal particles (B)50) Is 3-100 μm.
Description
Technical Field
The present invention relates to a resin composition.
Background
Crystalline resins have a plurality of useful characteristics such as high mechanical strength and rigidity, and excellent chemical resistance. Since this crystalline resin is easy to process, it has been used in a wide range including mechanical parts and sliding parts in precision instruments, home appliances, office automation equipment, automobiles, industrial materials, daily necessities, and the like.
In addition, in order to impart a characteristic metallic luster called metallic tone (メタリック) to various resins, metallic color pigments including metallic particles typified by aluminum flakes (hereinafter also referred to as "aluminum flakes") are blended. Resin compositions containing the metallic color pigments are used for interior and exterior parts of automobiles, computer cases, and the like.
As such a resin composition, for example, a resin composition described in the following patent documents is known, and for example, an attempt is made to impart design properties by molding a resin containing a bright pigment to express metallic gloss. Specifically, patent documents 1 and 2 disclose molded articles comprising a synthetic resin composition containing a specific metal pigment. Further, patent document 3 proposes a polyacetal resin composition containing a weather-resistant agent, aluminum particles having a specific particle diameter, particle size distribution and particle thickness, and a specific fatty acid, and discloses that the composition is excellent in production stability, mechanical properties, molding appearance, welding performance and lightness. Further, patent document 4 proposes a polyacetal resin composition containing a polyacetal resin, a metallic pigment and a specific liquid additive, and discloses that the composition is excellent in extrusion characteristics, retention stability during molding and appearance characteristics, has a reduced content of an organic solvent, and is imparted with a metallic appearance (metallic appearance). Further, patent document 5 discloses a polymer composition comprising a polyacetal resin, a metallic pigment and an ultraviolet stabilizer, and the metallic pigment and the ultraviolet stabilizer are dispersed in amounts sufficient to make the glossiness of the outer surface of the obtained molded article to be a certain level or more.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 62-020574
Patent document 2: japanese laid-open patent publication No. 61-159453
Patent document 3: japanese laid-open patent publication No. 2010-065210
Patent document 4: japanese patent laid-open publication No. 2009-155418
Patent document 5: international publication No. 2013/49541
Disclosure of Invention
Problems to be solved by the invention
However, when the methods described in patent documents 1 and 2 are applied to a polyacetal resin, there are influences of heat generation during melt mixing and active sites on the metal surface, and sufficient effects are not obtained with respect to suppression of formaldehyde generation amount and improvement of appearance such as gloss of a product.
In addition, with respect to the technique disclosed in patent document 3, no study has been made on the influence on the amount of formaldehyde generated, the influence on the appearance such as the gloss of the product, and the like.
Patent document 4 proposes a technique for the purpose of heat stability of a molded article and suppression of formaldehyde, but discloses only a pigment obtained by dispersing aluminum powder in polyethylene as a metallic pigment, and does not study the influence on the appearance such as glossiness and brightness of the molded article obtained.
Further, patent document 5 is completely silent on the influence of other additives on glossiness and the like. In addition, in the technique disclosed in patent document 5, when a large amount of aluminum pigment is used, there is a possibility that the aluminum pigment comes off at the time of molding or adhesion (mold deposit) of the aluminum pigment on a molding die occurs, and there is a potential problem that the aluminum pigment adheres to a hand only by touching pellets containing the polymer composition.
The present invention has been made in view of the above-mentioned circumstances of the prior art, and an object of the present invention is to provide a resin composition which can produce a molded article having excellent metallic appearance with less formaldehyde emission and which can suppress mold deposit during molding.
Means for solving the problems
The present inventors have conducted extensive studies and as a result, have found that a resin composition which generates little formaldehyde and has an excellent metallic tone appearance and in which a mold is not contaminated with metal particles at the time of molding can be obtained by adding a pearl pigment and a predetermined amount of metal particles having a specific size to a polyacetal resin, and have completed the present invention.
Namely, the present invention is as follows.
[1]
A resin composition comprising:
(A) 100 parts by mass of a polyacetal resin,
(B) 0.01 to 15 parts by mass of metal particles, and
(C) a pearlescent pigment, and
the volume average particle diameter (D) of the metal particles (B)50) Is 3-100 μm.
[2]
The resin composition according to item [1], wherein the resin composition contains more than 1 part by mass and 15 parts by mass or less of the (B) metal particles relative to 100 parts by mass of the (A) polyacetal resin.
[3]
The resin composition according to item [1] or [2], wherein the resin composition contains 0.01 to 10 parts by mass of the (C) pearl pigment per 100 parts by mass of the (A) polyacetal resin.
[4]
Such as item [1]]～[3]The resin composition according to any one of (A) to (B), wherein the volume average particle diameter (D) of the pearlescent pigment (C)50) Is 1-300 μm.
[5]
The resin composition according to any one of items [1] to [4], wherein the (C) pearl pigment contains 40% by mass or more of a synthetic mineral.
[6]
The resin composition according to any one of items [1] to [5], wherein the (C) pearl pigment is mica coated with titanium dioxide or iron oxide.
[7]
The resin composition according to any one of items [1] to [6], which further contains (D) a dispersing aid.
Effects of the invention
According to the present invention, there can be provided a resin composition which can produce a molded article having excellent metallic appearance with little formaldehyde emission and can suppress mold deposit at the time of molding.
Drawings
Fig. 1 is a schematic diagram illustrating an FI value evaluation method in the example.
Detailed Description
Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following description, and various modifications can be made within the scope of the present invention.
The resin composition of the present embodiment is characterized by containing: (A) 100 parts by mass of polyacetal resin, and 0.01 to 15 parts by mass of metal particles (B)Parts by weight, and (C) a pearl pigment, and the volume average particle diameter (D) of the metal particles (B)50) Is 3-100 μm. The resin composition of the present embodiment may contain, as necessary, (D) a dispersing aid, (E) a formaldehyde inhibitor, and other additives.
((A) polyacetal resin)
The polyacetal resin (A) is not particularly limited, and conventionally known polyacetals can be used. (A) The polyacetal resins may be used singly or in combination of two or more.
Examples of the polyacetal resin (A) include: substantially consisting of oxymethylene units- (CH) obtained by homopolymerization of a cyclic oligomer such as formaldehyde, trioxymethylene or tetraformaldehyde2O) -a polyoxymethylene homopolymer; or a copolymer obtained by copolymerizing formaldehyde and/or trioxymethylene with a cyclic ether and/or a cyclic formal to which a hindered phenol antioxidant is added in an amount of 1 to 500 ppm by mass, and having an oxymethylene unit- (CH)2A polyoxymethylene copolymer having a structure in which oxyalkylene units represented by the following general formula (1) are randomly inserted into a chain of O) -.
(R in the formula1And R2Each is a hydrogen atom, an alkyl group or an aryl group, which may be the same or different, and n is an integer of 2 to 6)
The polyoxymethylene copolymer used in the present embodiment also includes a branched polyoxymethylene copolymer having a branched molecular chain and a polyoxymethylene block copolymer having a different-component block in which a repeating unit of an oxymethylene group is 50 mass% or more.
The insertion rate of the oxyalkylene unit in the polyoxymethylene copolymer is preferably 0.01 mol or more and 50 mol or less, and more preferably 0.03 mol or more and 20 mol or less, based on 100 mol of the oxymethylene unit. Examples of the oxyalkylene unit include: oxyethylene unit, oxypropylene unit, oxytetramethylene unit, oxygenButylene units, oxyphenylethylene units, and the like. Among these oxyalkylene units, oxypropylene units- [ (CH) are preferred from the viewpoint of improving the physical properties of the resin composition2)3O]And the oxytetramethylene unit- [ (CH)2)4O]-。
The polyacetal resin obtained by the above homopolymerization or copolymerization is desirably subjected to a terminal stabilization treatment. Examples of the method of stabilizing the terminal include a method of esterifying, etherifying, carbamating a hydroxyl group at the terminal, a method of stabilizing an unstable part at the terminal by hydrolysis, and the like.
The polyacetal resin having been subjected to the terminal stabilization treatment is obtained, for example, by: the polyoxymethylene copolymer obtained by copolymerization of formaldehyde and/or trioxymethylene and cyclic ether and/or cyclic formal is continuously fed to a counter-rotating non-intermeshing twin screw extruder capable of performing a step of stabilizing molecular terminals immediately after polymerization, a step of kneading by injecting water, alcohol or a mixture thereof in a molten state, and a devolatilization step of releasing steam of the hydroxyl group-containing compound such as water and free formaldehyde injected, and the like. When the above water, alcohol or mixture thereof is injected and kneaded, it is preferable to add a basic substance such as triethylamine as a pH adjuster.
The MFR (melt flow rate; temperature condition: 190 ℃ C. according to ASTM D57E) of the polyacetal resin is preferably 2.5g/10 min to 40g/10 min, more preferably 3g/10 min to 30g/10 min. By adjusting the MFR of the polyacetal resin within the above range, the balance between the mechanical physical properties of the resin composition, the thermal stability during residence molding, and the amount of formaldehyde generated becomes good.
((B) Metal particle)
The resin composition of the present embodiment contains (B) metal particles. In addition, the (B) metal particles can exhibit a more favorable metallic luster by having a flat shape such as a coin shape or a flake shape. The material of the metal particles (B) is not particularly limited, and examples thereof include aluminum, brass, stainless steel, copper, zinc, nickel, iron, and silver. (B) The metal particles may be used singly or in combination. Among the metal particles (B), aluminum, brass and copper are preferable from the viewpoint of easy availability and high degree of freedom in processing, and aluminum is more preferable from the viewpoint of high reflectance.
The content of the metal particles (B) in the resin composition of the present embodiment is 0.01 to 15 parts by mass with respect to 100 parts by mass of the polyacetal resin (a). The content of the metal particles (B) in the resin composition of the present embodiment is preferably 1 to 10 parts by mass, more preferably 1.5 to 7 parts by mass, and still more preferably 2 to 6 parts by mass, relative to 100 parts by mass of the polyacetal resin (a), from the viewpoint of suppressing the weight of the composition and the molded article obtained using the composition. By adjusting the content of the metal particles (B) within the above range, the molded article produced from the resin composition of the present embodiment can maintain the rigidity and impact resistance inherent in the polyacetal resin (a) more favorably, can effectively suppress the generation of formaldehyde, and can exhibit a better metallic luster.
From the viewpoint of further improving the metallic tone appearance, the content of the metal particles (B) in the resin composition of the present embodiment is preferably 4 to 10 parts by mass, more preferably 5 to 10 parts by mass, relative to 100 parts by mass of the polyacetal resin (a). In general, when the metal particles (B) are contained in such a large amount, mold fouling due to adhesion of the metal particles to a mold tends to occur frequently. However, in the present embodiment, the metal particles (B) are used in combination with the pearlescent pigment (C) described later, whereby mold deposit can be suppressed.
(B) Volume average particle diameter (D) of metal particles50) Is 3-100 μm. In addition, from the viewpoint of improving the reflectance, the volume average particle diameter (D) of the (B) metal particles50) Preferably 3 to 60 μm, more preferably 3 to 40 μm, and still more preferably 5 to 30 μm.
The volume average particle diameter (D)50) The measurement can be carried out by the method described in the examples described later.
From the viewpoint of brightness, the average particle thickness of the metal particles (B) is preferably 0.01 to 1.0. mu.m, more preferably 0.02 to 0.6. mu.m, and still more preferably 0.03 to 0.4. mu.m. The average particle thickness (t) of the metal particles (B) can be calculated by the following method.
1) Method for calculating average particle thickness from water surface diffusion area (WCA)
First, the constituent component (e.g., aluminum) of the metal particles (B) was pretreated with a mineral spirit solution of 5% stearic acid, and then the water surface diffusion area (WCA) of the constituent component of the metal particles was measured in accordance with JIS K5906-. Next, the water surface diffusion area (WCA) (m) per 1g of the constituent component of the (B) metal particles obtained by the measurement can be used2,/g) and is calculated by the following formula.
t is 0.4/WCA (in the case where the constituent of the (B) metal particles is aluminum)
The above-mentioned method for calculating the average particle thickness is described, for example, in aluminum Paint and Powder, j.d. edwards&The 16 th to 22 nd pages of R.I.Wray, 3 rd edition, Reinhold Publishing Corp.New York (1955). Further, "0.4" in the above formula means that the density of aluminum is 2.7g/cm3The reciprocal of (1/2.7 ═ about 0.4).
The method for measuring the water surface diffusion area described in JIS is a method for measuring the water surface diffusion area in a suspension type, whereas aluminum (aluminum pigment) is a non-suspension type. However, the method for measuring the water surface diffusion area (WCA) of aluminum can be performed in the same manner as the suspension type described in JIS K5906-. Pretreatment of the sample is described in "paint raw materials" , pages 2 to 16, 156 (1980.9.1, published by Kasei chemical Co., Ltd.).
2) Method of calculating the average particle thickness from the observation results of a Scanning Electron Microscope (SEM) in the case where the calculation cannot be performed by the method of 1) (for example, in the case where the WCA measurement cannot be performed), the average particle thickness can be obtained by a method of calculating an average value from a plurality of results obtained by observing (B) metal particles with a Scanning Electron Microscope (SEM), for example, the thicknesses of (B) metal particles observed at 100 positions.
By using (B) the metal particles having the volume average particle diameter and the average particle thickness in the above ranges, the metal particles can be suppressed from being broken at the time of extrusion processing or the like, and the appearance characteristics of the molded article produced from the resin composition of the present embodiment can be improved, and a more favorable metallic gloss can be exhibited.
(B) The metal particles can be produced by a known method. For example, the metal particles (B) are obtained by classifying atomized powder, cut powder, foil powder, vapor deposition powder, or metal powder obtained by another method in advance by primary classification or the like, wet-pulverizing the mixture by a ball mill, an attritor (アトライター), a planetary mill, a vibration mill, or the like in the presence of a pulverization medium containing a pulverization aid, a solvent, or the like, classifying the mixture by sieving in a wet state, and then performing solid-liquid separation by a filter press or the like. Thus, the metal particles (B) having less uneven fracture surfaces at the sheet ends can be produced.
As described above, the shape of the metal particles (B) is preferably a flat shape such as a coin shape or a sheet shape. The flat shape as used herein means an average shape ratio (average particle thickness (t)/volume average particle diameter (D)50) A value of 0.2 or less), preferably 0.1 or less, more preferably 0.05 or less. By adjusting the average shape ratio within this range, the surface area of the portion having high reflectance peculiar to the metal can be increased by the addition of a small amount of metal particles. Therefore, by adjusting the average shape ratio within this range, the brightness of the molded article can be effectively improved by the addition amount of a small amount of (B) metal particles.
((C) pearlescent pigment)
The resin composition of the present embodiment contains (C) a pearlescent pigment. Herein, the (C) pearl pigment means a pigment which contributes to the adjustment of color tone and has pearl luster. Examples of the pearlescent pigment (C) include particles having a surface portion containing a metal oxide. Examples of such a pearlescent pigment include pigments in which the surface of scaly particles such as mica is covered with a metal oxide. The metal oxide that may be contained in the pearlescent pigment (C) is not particularly limited as long as it does not affect the metallic color tone of the resin composition of the present embodiment, and examples thereof include oxides of metals such as titanium, iron, zirconium, silicon, aluminum, and cerium. The metal oxides may be used singly or in combination of two or more. Specific examples of the pearlescent pigment (C) include mica coated with titanium dioxide, mica coated with iron oxide, mica coated with titanium dioxide and iron oxide, glass flake coated with titanium oxide, talc coated with titanium oxide, and the like. Among them, the (C) pearl pigment is preferably mica coated with titanium dioxide or iron oxide.
The pearlescent pigment (C) is not included in the metal particles (B).
The content of the pearlescent pigment (C) in the resin composition of the present embodiment is not particularly limited, and is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyacetal resin from the viewpoint of effectively preventing contamination of the mold with the metal particles. From the same viewpoint, the content of the pearlescent pigment (C) in the resin composition of the present embodiment is preferably 0.05 to 7 parts by mass, more preferably 0.08 to 5 parts by mass, and still more preferably 0.1 to 6 parts by mass.
(C) Volume average particle diameter (D) of pearlescent pigment50) Preferably 1 to 300. mu.m. In addition, from the viewpoint of improving the reflectance and the FI value, (C) the volume average particle diameter (D) of the pearlescent pigment50) More preferably 2 to 200. mu.m, still more preferably 3 to 150. mu.m.
The Fe concentration in the pearlescent pigment (C) is preferably 10% by mass or less, more preferably 6% by mass or less, and further preferably 4% by mass or less, from the viewpoint of suppressing formaldehyde generation and enhancing the brightness. In order to adjust the Fe concentration to a desired concentration, a pigment synthesized by melt synthesis (melt synthesis) of raw materials is preferably used as the (C) pearlescent pigment.
(C) The shape of the pearlescent pigment is preferably flat or scaly, more preferably scaly. This can effectively suppress the volatilization of formaldehyde from the resin. The thickness of the pearlescent pigment (C) is preferably 0.01 to 10 μm, more preferably 0.02 to 8 μm, and still more preferably 0.05 to 5 μm.
(C) The pearlescent pigment is preferably a synthetic mineral, particularly a synthetic mineral obtained by melt-synthesizing a raw material mineral. Preferable examples of the raw material of the pearlescent pigment include mica, talc, and glass flake. In general, the melt synthesis is set to 1000 ℃ or higher, and the raw material mineral is melted and then cooled to be recrystallized, thereby obtaining a synthetic mineral. For example, in the case of mica, since it does not contain a transition metal unlike natural mica, colorless transparent pure crystals are obtained as a synthetic mineral.
It should be noted that the particle size of the synthetic mineral obtained by melt synthesis can be freely adjusted. Specifically, for example, the particle size may be controlled by controlling the cooling rate after melting, or by synthesizing a large synthetic mineral and then pulverizing the synthetic mineral. Further, for example, in the case of synthetic mica, the amount of heavy metal mixed may be adjusted to 1ppm or less, and the Fe concentration as a coloring source may be adjusted to 100ppm or less, and even in the case where various metals are added for producing a colored (C) pearl pigment, color development can be stably performed with respect to the amount of addition.
The proportion of the synthetic mineral in the pearlescent pigment (C) is preferably 40% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, from the viewpoints of free adjustment of particle size and reduction in the amount of heavy metal mixed.
Although not intending to be bound by theory, by adding an appropriate amount of (C) pearl pigment, heat transfer in the mold in molding is good, or warpage does not occur when the composition in which (C) pearl pigment and (B) metal particles are mixed is cooled in the mold, and minute gaps invisible to the naked eye are not generated between the mold and the composition. Therefore, the falling off of the metal particles in the resin composition that has not been sufficiently cooled is reduced, and therefore the adhesion of the metal particles on the mold surface is reduced.
(D) dispersing aid
The resin composition of the present embodiment preferably further contains (D) a dispersing aid. The dispersion aid includes an aid for dispersing (B) the metal particles and (C) the pearl pigment in (a) the polyacetal resin, and a dispersion aid for processing for improving the thermal stability of (a) the polyacetal resin. When the resin composition contains (D) a dispersing aid, higher gloss and FI value described later can be obtained. (D) The dispersion aid may be used singly or in combination of two or more.
Examples of the dispersing aid (D) include: hydrocarbons, higher fatty acids, higher alcohols, fatty amides, metal soaps, alkylene glycols (e.g. C)3-6Alkylene glycol), esterified derivatives of polyalkylene glycols, other modified polyalkylene glycols, and the like.
Examples of the homopolymer include polypropylene glycol, polytetramethylene ether glycol, polypentamethylene ether glycol, and polyneopentylene ether glycol.
Examples of the hydrocarbons include liquid paraffin and mineral spirits.
Examples of the copolymer include a polyethylene glycol-polytetramethylene ether glycol copolymer, a polypropylene glycol-polytetramethylene ether glycol copolymer, a polyethylene glycol-polypentamethylene ether glycol copolymer, a polypropylene glycol-polypentamethylene ether glycol copolymer, a polyethylene glycol-polypivalenemethylene ether glycol copolymer, a polypropylene glycol-polypivalenemethylene ether glycol copolymer, and a Tetrahydrofuran (THF) -neopentyl glycol copolymer.
Examples of the esterified derivative of the polyalkylene glycol include polytetramethylene glycol monostearate, polytetramethylene glycol distearate, polypentamethylene glycol monostearate, polypentamethylene glycol distearate, polyneopentylene ether glycol monostearate, and polyneopentylene ether glycol distearate.
Among them, from the viewpoint of easy availability, as the (D) dispersing aid, hydrocarbons, polypropylene glycol, polytetramethylene ether glycol, and THF-neopentyl glycol copolymer are preferable.
The content of the dispersion aid (D) in the resin composition of the present embodiment is not particularly limited as long as it does not interfere with extrusion and injection molding, and is preferably 0.01 to 2.0 parts by mass, more preferably 0.01 to 1.5 parts by mass, further preferably 0.02 to 1.0 part by mass, and further preferably 0.05 to 0.8 part by mass, relative to 100 parts by mass of the polyacetal resin (a). When the content of the (D) dispersing aid is within the above range, a molded article having higher gloss can be obtained, and the running state of the extruder and the resin metering and the like at the time of injection molding become stable (for example, occurrence of bending at the time of extrusion processing is suppressed), so that it is preferable.
((E) Formaldehyde inhibitor)
The resin composition of the present embodiment preferably contains (E) a formaldehyde inhibitor as necessary within a range not to impair the object of the present invention. Examples of (E) the formaldehyde inhibitor include: aminotriazine compounds, guanamine compounds, urea compounds, carboxylic acid hydrazide compounds, and the like. The formaldehyde inhibitor may be used singly or in combination of two or more.
Examples of the aminotriazine compound include: melamine condensates such as melamine, melam, melem, and tricyano melamine (メロン); melamine resins such as melamine-formaldehyde resins; n-hydroxyarylalkyl melamine compounds such as N, N' -mono-, di-, tri-, tetra-, penta-, or hexa- (o-, m-, or p-hydroxyphenylmethyl) melamine; and the like.
Examples of the guanamine compound include: aliphatic guanamine compounds such as pentylguanamine, hexylguanamine, heptylguanamine, octylguanamine and stearylguanamine; alkylene biguanides such as ethylene biguanide, propylene biguanide, butylene biguanide, pentylene biguanide, hexylene biguanide, heptylene biguanide, and octylene biguanide; alicyclic guanamine compounds such as cyclohexyl guanamine, norbornenyl guanamine, cyclohexenyl guanamine, norbornanyl guanamine, and functional group-substituted derivatives thereof; aromatic guanamine compounds such as phenylguanamine, α -or β -naphthylguanamine, and functional group-substituted derivatives thereof; polyguanamines such as o-phenylendiguanamine, m-phenylendiguanamine, p-phenylendiguanamine, naphthalenediguanamine, and biphenylbiguanideamine; aralkyl or aralkylene guanamines such as phenethylguanamine, β -phenylpropylguanamine, and o-, m-or p-xylylene biguanideamine; heteroatom-containing guanamine compounds such as acetal group-containing guanamines, dioxane ring-containing guanamines, tetraoxaspiro ring-containing guanamines, isocyanurate ring-containing guanamines, and the like; and the like.
Examples of the functional group-substituted derivative in the alicyclic guanamine compound include: and derivatives of cycloalkane residue substituted with 1 to 3 functional groups such as alkyl, hydroxyl, amino, acetylamino, nitrile, carboxyl, alkoxycarbonyl, carbamoyl, alkoxy, phenyl, cumyl, hydroxyphenyl, and the like.
Examples of the functional group-substituted derivative in the aromatic guanamine compound include derivatives in which a phenyl residue of phenyl guanamine or a naphthyl residue of naphthyl guanamine is substituted with 1 to 5 functional groups such as an alkyl group, a hydroxyl group, an amino group, an acetamido group, a nitrile group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkoxy group, a phenyl group, a cumyl group, and a hydroxyphenyl group, and examples of such aromatic guanamine compounds include: o-, m-or p-tolylguanamine, o-, m-or p-xylylguanamine, o-, m-or p-phenylphenylguanamine, o-, m-or p-hydroxyphenylguanamine, 4- (4' -hydroxyphenyl) phenylguanamine, o-, m-or p-cyanophenylguanamine, 3, 5-dimethyl-4-hydroxyphenylguanamine, 3, 5-di-t-butyl-4-hydroxyphenylguanamine, etc.
Examples of the guanamines containing an acetal group include 2, 4-diamino-6- (3, 3-dimethoxypropyl) s-triazine.
Examples of the guanidine amines containing a dioxane ring include: [2- (4',6' -diamino-s-triazin-2 '-yl) ethyl ] -1, 3-dioxane, [2- (4',6 '-diamino-s-triazin-2' -yl) ethyl ] -4-ethyl-4-hydroxymethyl-1, 3-dioxane, and the like.
Examples of the guanamines containing a tetraoxaspiro ring include: CTU-guanamine, CMTU-guanamine, and the like.
Examples of the guanamines having an isocyanurate ring include: 1,3, 5-tris [2- (4',6' -diamino-s-triazin-2 '-yl) ethyl ] isocyanurate, 1,3, 5-tris [3- (4',6 '-diamino-s-triazin-2' -yl) propyl ] isocyanurate, and the like.
Examples of the urea compound include a chain urea compound and a cyclic urea compound.
Examples of the chain urea compound include: condensates of urea such as biurea, biuret, urea formaldehyde (ホルム asphyxian) and formaldehyde, and polyalkylene or arylene ureas such as polyneurylene urea.
Examples of the cyclic urea compound include: hydantoin compounds, 2-butenylidene diurea (クロチリデンジウレア), acetylene urea, mono-, di-, tri-or tetraalkoxymethyl glycoluril such as mono-, di-, tri-or tetramethoxymethyl glycoluril, cyanuric acid, isocyanuric acid, uric acid and urazole. Examples of the hydantoin include: and metal salts such as aluminum salts of allantoin, for example, hydantoin salts of 5-methylhydantoin, 5-ethylhydantoin, 5-isopropylhydantoin, 5-phenylhydantoin, 5-benzylhydantoin, 5-dimethylhydantoin, 5-pentamethylenehydantoin, 5-methyl-5-phenylhydantoin, 5-diphenylhydantoin, 5- (o-, m-or p-hydroxyphenyl) hydantoin, 5- (o-, m-or p-aminophenyl) hydantoin, allantoin, 5-methyliallantoin, and allantoin dihydroxyaluminum salts.
Examples of the carboxylic acid hydrazide compound include: aliphatic carboxylic acid hydrazide compounds, alicyclic carboxylic acid hydrazide compounds, and aromatic carboxylic acid hydrazide compounds.
Examples of the aliphatic carboxylic acid hydrazide compound include: monocarboxylic acid hydrazides such as lauric acid hydrazide, stearic acid hydrazide, 12-hydroxystearic acid hydrazide and 1,2,3, 4-butanetetracarboxylic acid hydrazide; polycarboxylic acid hydrazides such as succinic acid mono-or dihydrazide, glutaric acid mono-or dihydrazide, adipic acid mono-or dihydrazide, pimelic acid mono-or dihydrazide, suberic acid mono-or dihydrazide, azelaic acid mono-or dihydrazide, sebacic acid mono-or dihydrazide, dodecanedioic acid mono-or dihydrazide, hexadecanedioic acid mono-or dihydrazide, eicosanedioic acid mono-or dihydrazide, and 7, 11-octadecadien-1, 18-dicarboxylic acid hydrazide.
Examples of the alicyclic carboxylic acid hydrazide compound include: monocarboxylic acid hydrazides such as cyclohexanecarboxylic acid hydrazide; and polycarboxylic acid hydrazides such as dimer acid mono-or dihydrazide, trimer acid mono-, di-or trihydrazide, 1,2-, 1, 3-or 1, 4-cyclohexanedicarboxylic acid mono-or dihydrazide, and cyclohexanetricarboxylic acid mono-, di-or trihydrazide.
Examples of the aromatic carboxylic acid hydrazide compound include: monocarboxylic acid hydrazides such as benzoic acid hydrazide and a functional group-substituted derivative thereof, α -or β -naphthoic acid hydrazide and a functional group-substituted derivative thereof; isophthalic acid mono or dihydrazide, terephthalic acid mono or dihydrazide, 1, 4-or 2, 6-naphthalenedicarboxylic acid mono or dihydrazide, 3' -, 3,4' -or 4,4' -biphenyldicarboxylic acid mono or dihydrazide, diphenylether dicarboxylic acid mono or dihydrazide, diphenylmethane dicarboxylic acid mono or dihydrazide, diphenylethane dicarboxylic acid mono or dihydrazide, diphenyloxyethane dicarboxylic acid mono or dihydrazide, diphenylsulfone dicarboxylic acid mono or dihydrazide, diphenylketone dicarboxylic acid mono or dihydrazide, and polycarboxylic acid hydrazides such as 4,4 '-terphthalic acid mono-or dihydrazide, 4' -tetrabenzodicarboxylic acid mono-or dihydrazide, 1,2, 4-benzenetricarboxylic acid mono-, di-or trihydrazide, pyromellitic acid mono-, di-, tri-or tetrahydrazide, and 1,4,5, 8-naphthalenetetracarboxylic acid mono-, di-, tri-or tetrahydrazide. Examples of the benzoic acid hydrazide and a functional group-substituted derivative thereof include: o-, m-or p-methylbenzoic acid hydrazide, 2,4-, 3, 5-or 2, 5-dimethylbenzoic acid hydrazide, o-, m-or p-hydroxybenzoic acid hydrazide, o-, m-or p-acetoxybenzoic acid hydrazide, 4-hydroxy-3-phenylbenzoic acid hydrazide, 4-acetoxy-3-phenylbenzoic acid hydrazide, 4- (4' -phenyl) benzoic acid hydrazide, 4-hydroxy-3, 5-dimethylbenzoic acid hydrazide, 4-hydroxy-3, 5-di-tert-butylbenzoic acid hydrazide and the like, wherein 1 to 5 alkyl groups, hydroxy groups, acetoxy groups, amino groups, hydroxyl groups, amino groups, and the like are substituted on the phenyl residue of the benzoic acid hydrazide, And derivatives of functional groups such as acetylamino, nitrile, carboxyl, alkoxycarbonyl, carbamoyl, alkoxy, phenyl, benzyl, cumyl, hydroxyphenyl, and the like. Examples of the α -or β -naphthoic acid hydrazide and a functional group-substituted derivative thereof include 3-hydroxy-2-naphthoic acid hydrazide and 6-hydroxy-2-naphthoic acid hydrazide.
The formaldehyde inhibitor may be used in the form of a layered product or a porous product (hydrotalcite, montmorillonite, silica gel, alumina, titanium dioxide, zirconium dioxide, sepiolite, smectite, palygorskite, imogolite, zeolite, activated carbon, etc.).
Among the above formaldehyde inhibitors (E), aliphatic carboxylic acid hydrazide compounds and aromatic carboxylic acid hydrazide compounds are preferable, and aliphatic carboxylic acid hydrazide compounds are more preferable.
The content of the formaldehyde inhibitor (E) in the resin composition of the present embodiment is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 2 parts by mass, and still more preferably 0.02 to 1 part by mass, relative to 100 parts by mass of the polyacetal resin (a). (E) When the content of the formaldehyde inhibitor is within the above range, a sufficient formaldehyde-inhibiting effect can be obtained and mold deposit can be inhibited.
(other additives)
The resin composition of the present embodiment may contain other conventional additives. The additive is not particularly limited, and a stabilizer or the like used in the conventional polyacetal resin (a) is preferably used.
The stabilizer may include an antioxidant, a weather-resistant stabilizer, and the like, and may further include a scavenger for formic acid or formaldehyde. In addition, the resin composition of the present embodiment may contain various colorants as additives as necessary in order to improve the design properties.
The above additives may be used singly or in combination of two or more.
Antioxidant agent
The antioxidant is preferably a hindered phenol-based antioxidant, and examples thereof include: octadecyl 3- (3', 5' -di-tert-butyl-4 ' -hydroxyphenyl) -propionate, n-octadecyl 3- (3' -methyl-5 ' -tert-butyl-4 ' -hydroxyphenyl) -propionate, n-tetradecyl 3- (3', 5' -di-tert-butyl-4 ' -hydroxyphenyl) -propionate, 1, 6-hexanediol bis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), 1, 4-butanediol bis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), triethylene glycol bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate), and the like.
The content of the antioxidant in the resin composition of the present embodiment is preferably 0.01 to 2 parts by mass, and more preferably 0.02 to 1 part by mass, relative to 100 parts by mass of the polyacetal resin (a). When the content of the antioxidant is 0.01 to 2 parts by mass, the resin composition of the present embodiment can be improved in thermal stability during molding and processing, and thus can be a good resin composition.
Weather-resistant stabilizer
Examples of the weather-resistant stabilizer include hindered amine stabilizers. Further, as the hindered amine-based stabilizer, a piperidine derivative having a sterically hindered group may be mentioned, and examples thereof include: and ester group-containing piperidine derivatives, ether group-containing piperidine derivatives, amide group-containing piperidine derivatives, high molecular weight piperidine derivative polycondensates, and the like.
The content of the hindered amine-based stabilizer in the resin composition of the present embodiment is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, and still more preferably 0.1 to 1.5 parts by mass, relative to 100 parts by mass of the polyacetal resin (a).
The resin composition of the present embodiment preferably further contains an ultraviolet absorber as the weather resistant stabilizer. As a result, the molded article obtained from the resin composition of the present embodiment has an effect of improving weather resistance (light stability). Examples of the ultraviolet absorber include: benzotriazole compounds, benzophenone compounds, oxalic anilide compounds and hydroxyphenyl-1, 3, 5-triazine compounds.
When the resin composition of the present embodiment contains an ultraviolet absorber and a hindered amine stabilizer, the mass ratio of the hindered amine stabilizer to the ultraviolet absorber is preferably 10/90 to 80/20, more preferably 10/90 to 70/30, and even more preferably 20/80 to 60/40 in terms of ultraviolet absorber/hindered amine stabilizer (mass ratio).
Capture agent for formic acid or formaldehyde
The resin composition of the present embodiment preferably further contains the above-mentioned trapping agent for formic acid or formaldehyde. Examples of the capturing agent for formic acid or formaldehyde include: formaldehyde-reactive nitrogen-containing compounds and polymers, fatty acid calcium salts, alkali metal or alkaline earth metal hydroxides, inorganic acid salts, carboxylates, alkoxides, and the like.
Examples of the formaldehyde-reactive nitrogen-containing compound include: dicyandiamide, amino-substituted triazines, cocondensates of amino-substituted triazines with formaldehyde, and the like.
The content of each of the formaldehyde-reactive nitrogen-containing compound and the polymer, the fatty acid calcium salt, the alkali metal or alkaline earth metal hydroxide, the inorganic acid salt, the carboxylate, or the alkoxide is preferably in the range of 0.01 to 1 part by mass, more preferably 0.02 to 0.5 part by mass, based on 100 parts by mass of the polyacetal resin. When the content is 0.01 to 1 part by mass, the resin composition of the present embodiment can improve the thermal stability during molding, reduce the amount of formaldehyde generated from the molded article, and improve the heat aging resistance.
Coloring agent
The colorant includes, but is not limited to, an organic pigment and an inorganic pigment, and may be a single colorant or a combination of two or more colorants.
Examples of the organic pigment include: phthalocyanine pigment, condensed azo pigment, azo lake pigment, quinacridone pigment, and perylene
Oxazine pigments, isoindolinone pigments, fused polycyclic pigments, and the like.
Examples of the inorganic pigment include: zinc white, titanium dioxide, red iron oxide, chromium oxide, iron black and other simple oxides, cadmium yellow, cadmium orange, cadmium red and other sulfides, chromium yellow, zinc yellow, molybdenum-chromium red and other chromates, iron blue and other ferrocyanides, ultramarine blue and other silicates, carbon black and the like.
The content of the colorant in the resin composition of the present embodiment is preferably 0.0001 to 2 parts by mass, and more preferably 0.0005 to 1 part by mass, based on 100 parts by mass of the polyacetal resin (a). By setting the content of the colorant within the above range, the effect of improving the design can be obtained without promoting the reduction of the mechanical strength of the molded article, particularly the generation of formaldehyde from the polyacetal resin (a).
The resin composition of the present embodiment may further contain various inorganic fillers, other thermoplastic resins, softeners, crystal nucleating agents, mold release agents, and the like, which have been conventionally used, as necessary, within a range not to impair the object of the present invention.
(method for producing resin composition)
The resin composition of the present embodiment can be obtained by, for example, melting and mixing a part of the above-described raw materials using a commonly used melt kneader. Examples of the melt-kneading machine include a kneader, a roll mill, a single-screw extruder, a twin-screw extruder, and a multi-screw extruder.
The temperature for melt kneading may be appropriately selected depending on the melting point or softening point of the polyacetal resin (A) to be used, and is preferably a temperature higher by 1 to 100 ℃ than the melting point or softening point of the polyacetal resin (A), more preferably a temperature higher by 10 to 60 ℃ than the melting point or softening point of the polyacetal resin (A), and still more preferably a temperature higher by 20 to 50 ℃ than the melting point or softening point of the polyacetal resin (A). The melting point or softening point of the polyacetal resin (a) can be determined by Differential Scanning Calorimetry (DSC) according to JIS K7121. In order to maintain quality and working environment, it is preferable to replace the inside of the system with an inert gas or to degas the inside with one-stage or multi-stage exhaust ports.
(Properties of resin composition)
The resin composition of the present embodiment has good retention stability during molding and extrusion, is less in appearance defects, is less in volatilization of an organic solvent from the resin composition, and can give a molded article having an excellent metallic tone appearance, high glossiness and FI value, and an aesthetically excellent metallic tone appearance.
The formaldehyde emission amount of the resin composition of the present embodiment is preferably 5mg/kg or less, and more preferably 3mg/kg or less.
The formaldehyde emission can be measured by the method described in examples described later.
The FI value of the resin composition of the present embodiment is preferably 9 or more, more preferably 13 or more, and further preferably 14 or more. The FI value is one of the indicators of the metallic appearance, and can be measured by the method described in the examples described later.
Here, a phenomenon in which lightness varies with a change in observation angle is referred to as a flop (F/F) phenomenon, and a quantitative value representing the phenomenon is referred to as an FI (dynamic index) value. The FI value may be calculated from the lightness (L) at 15 degrees, 45 degrees and 110 degrees using the formula first proposed by DuPont (DuPont)15°、L*45°And L110°) Values were determined (A.B.J.Rodriguez, JOCCA, (1992(4)), p.150 to 153). Specifically, the FI value is obtained by the following equation, and the higher the FI value, that is, the larger the difference between the lightness (L ×) in the highlight direction (the regular reflection direction with respect to the incident angle of light) and the shadow direction (the non-regular reflection direction), the higher the metallic feeling is generally perceived.
The gloss of the resin composition of the present embodiment immediately after injection molding is preferably 45 or more, more preferably 60 or more, and still more preferably 70 or more. The gloss can be measured by the method described in the examples described later.
Here, the glossiness is one of the indicators of the metallic tone appearance. The glossiness depends on the smoothness of the surface of the molded article, and a metallic material molded by kneading a bright material such as a metallic pigment generally tends to have a reduced glossiness. When the glossiness is lowered, the lightness, FI value, and the like are lowered due to the influence of scattering of reflected light on the surface of the molded article, and the quality of the metallic tone appearance tends to be lowered.
(use of molded article obtained from resin composition)
The molded article obtained from the resin composition of the present embodiment can be used for, in particular, internal and external parts having a mechanism part or a sliding part. For example, the resin composition is used as any one member selected from the group consisting of members provided in office automation equipment, music, video, information equipment, and communication equipment, industrial members provided in office furniture and home equipment, and members for use in and out of automobiles. In particular, it is suitable for use as any one member selected from the group consisting of a handle, a switch and a button, which requires excellent appearance. In addition, in order to use the molded article obtained from the resin composition of the present embodiment as an appearance member, an effect of improving the appearance is preferably exhibited when an embossing die (シボ gold type) is used at the time of molding or when an appearance design surface is imparted by embossing (シボ processing) the molded article.
Further, according to the resin composition of the present embodiment, a molded article having metallic luster without plating, coating, or other processing on the surface, excellent thermal stability and weather resistance, good mechanical properties (e.g., tensile properties and impact strength), high glossiness and FI value, and good appearance properties can be obtained. Further, since the molded article obtained from the resin composition of the present embodiment has good appearance characteristics as described above, a molded article having good practical use and excellent appearance can be obtained without coating. Therefore, an appearance excellent in design can be effectively obtained without using a solvent. The resin composition of the present embodiment is excellent in production stability, can be produced in a good working environment, and is also excellent in cost and environment.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples described below.
(1) Preparation of the main raw materials
The polyacetal resin (A) used is as follows.
(a-1) Asahi Kasei-Co Ltd, "Tenac C4513"
(a-2) Asahi Kabushiki Kaisha "Tenac C4520"
(a-3) Asahi Kasei-Co Ltd, "Tenac C7520"
((B) Metal particle)
A ball mill having an inner diameter of 30cm and a length of 35cm was filled with a mixture containing 250g of atomized aluminum powder (volume average particle diameter: 2.5 μm), 1.2kg of mineral spirit and 250g of stearic acid, and ground using 15kg of glass beads having a diameter of 3mm (specific gravity: 2.6) at 60rpm for 10 hours.
After completion of the milling, the slurry in the mill was washed with mineral oil and flowed out, and the slurry was applied to a 400-mesh vibrating screen, and the passed slurry was filtered by a filter, concentrated and decompressed to obtain 95% of aluminum particles (b-1) as metal particles as a heated residue.
The same operations as described above were carried out except that the particle diameter and grinding time of the atomized powdery aluminum were changed to obtain aluminum particles (b-2) to (b-5) having different volume average particle diameters and average particle thicknesses, respectively.
The particle size distribution of the obtained aluminum particles was measured by a laser diffraction particle size distribution measuring apparatus (manufactured by Shimadzu corporation, trade name "SALD-2300"), and the volume average particle diameter (D) of the aluminum particles was determined from the 50% value of the measured particle size distribution50). The results are shown in table 1. The aluminum particles as the sample were subjected to ultrasonic dispersion for 3 minutes as a pretreatment using mineral spirit as a measurement solvent.
Further, 1 to 2ml of a mineral spirit solution of 5% stearic acid was added to 1g of the obtained aluminum particles to perform preliminary dispersion (pretreatment), 50ml of petroleum ether was added thereto and mixed, and the mixture was heated at 40 to 45 ℃ for 2 hours, followed by suction filtration with a filter, and the water surface diffusion area (WCA) of the powder obtained by pulverization was measured. The average particle thickness (t) was calculated from the measurement value of WCA according to the following equation. The results are shown in table 1.
t(μm)＝0.4/WCA(m2/g)
TABLE 1
((C) pearlescent pigment)
The pearlescent pigment (C) used is as follows.
(c-1) manufactured by Nippon Guangyi industries Ltd., "TWINCLEPEARL SXB", (D)5015 μm) mica covered with titanium dioxide, scaly, content of synthetic minerals: about 67% by mass
(c-2) manufactured by Nippon Guangyi industries Ltd., "TWINCLEPEARL RYXD", (D)5030 μm) mica coated with titanium dioxide, scaly, content of synthetic minerals: about 58 percent
(c-3) PEARL-GLAZE MXL-100R manufactured by NIPPON PHOTOKINESS INDUSTRIAL CO., LTD50230 μm), scaly, natural mica (content of synthetic minerals: 0% by mass
(c-4) manufactured by Nippon Guangyi Kogyo, Inc. 'TWINCLEPEARL SX', (D)5090 μm), mica coated with titanium dioxide, scaly, content of synthetic minerals: about 87%
(c-5) manufactured by Nippon Guangyi industries Ltd., "TWINCLEPEARL VXE", (D)5040 μm), mica coated with titanium dioxide, scaly, content of synthetic minerals: about 63 percent
In addition, the following pigments were used as other pigments in the comparative examples.
(c-6) a "Tioxide RTC-30" manufactured by Huntsman, titanium oxide, crystal size: 0.21 μm, particle shape.
(D) dispersing aid
The dispersing aid (D) used is as follows.
(d-1) Polytetrahydrofuran (ポリテトラメチレンオキシド) (number average molecular weight: 2000)
(d-2) production of Wako pure chemical industries, Polypropylene glycol (diol type, number average molecular weight: 2000)
(d-3) production of Wako pure chemical industries, polyethylene glycol (number average molecular weight: 2000)
(d-4) production of Wako pure chemical industries, polyethylene glycol (number average molecular weight: 1000)
(d-5) production of Wako pure chemical industries, polyethylene glycol (number average molecular weight: 400)
(d-6) Sonmuran Petroleum research, Inc.' スモイル PS-260 "
((E) Formaldehyde inhibitor)
The formaldehyde inhibitor (E) used is as follows.
(e-1) Dihalohidydrazide sebacate, manufactured by Nippon Kogyo Seiki Kogyo Co., Ltd
(e-2) adipic acid dihydrazide, manufactured by Nippon Fine chemical Co., Ltd
(e-3) Dodecanedioic dihydrazide, manufactured by Nippon Fine chemical Co., Ltd
(2) Evaluation method
(evaluation of mold Scale)
Pellets of the resin composition produced as described below were injection-molded into an embossed flat test piece having a thickness of 2mm, a width of 80mm and a length of 80mm by using an injection molding machine (product name "IS-100 GN" manufactured by Toshiba mechanical Co., Ltd.) with a cylinder temperature of 180 ℃ and a mold temperature of 30 ℃ under injection conditions of an injection time of 60 seconds and a cooling time of 15 seconds, that IS, under conditions in which the inside of the mold IS not completely filled with the resin composition. The mass of the test piece was adjusted so as to be 95% by mass of the test piece obtained by completely filling the mold with the resin composition.
Mold fouling in the mold after 100 injection-molding test pieces under the present conditions was observed visually with a wiper (wiper き and pot ウェス) and evaluated according to the following criteria. In the case where the evaluation of mold deposit is x, the subsequent evaluation is not performed.
Very good: no mold fouling was observed visually and little adhesion on the wipe was observed.
O: a small amount of mold fouling was observed visually and little adhesion on the wipe was observed.
And (delta): no mold deposit was visually observed and a small amount of adhesion to the wipe was observed.
X: mold fouling was clearly observed, or adhesion on the wipe was clearly observed.
(FI value)
Pellets of the resin composition produced as described below were molded by an injection molding machine (product name "IS-100 GN" manufactured by toshiba corporation) under injection conditions of a cylinder temperature of 220 ℃, a mold temperature of 77 ℃, an injection time of 15 seconds, and a cooling time of 20 seconds to produce test pieces. The test piece was produced using a mold having a length of 90mm, a width of 50mm and a thickness of 2.5 mm.
For the above test piece, the appearance was confirmed by using BYK-mac manufactured by BYK-Gardner.
A method of measuring the FI value will be described with reference to fig. 1. Fig. 1 is a diagram illustrating an FI value evaluation method. As for the FI value, first, as shown in fig. 1, the surface of the molded article was irradiated with light from a certain direction, and L values (L ×) when the light receiving angle was shifted by 15 °, 45 °, and 110 ° from the regular reflection light were measured15°、L*45°And L110°) (lightness). Next, the FI value is obtained by substituting each measured value of L into the above-described equation. Generally, a higher FI value indicates a higher metallic texture.
(gloss degree)
The gloss was measured at an angle of 60 ° on the surface of the molded article according to JIS Z8741 using the above test piece used for FI value measurement and using a gloss meter ("IG-320" manufactured by horiba ltd.). In general, the higher the gloss, the smoother the surface of the molded article is, and the higher the degree of following the surface of the mold is.
(amount of Formaldehyde produced)
Pellets of the resin composition produced as described below were molded by an injection molding machine (product name "IS-100 GN" from toshiba corporation) under injection conditions of a cylinder temperature of 180 ℃, a mold temperature of 90 ℃, an injection time of 15 seconds, and a cooling time of 10 seconds to produce test pieces. Subsequently, the test piece was placed in a thermostatic bath at room temperature of 23 ℃ and a humidity of 50% for 48 hours.
Next, the amount of formaldehyde released from the test piece was determined by the following method (VDA275 method). First, 50mL of distilled water and a test piece (length 100 mm. times. width 40 mm. times. thickness 3mm) were placed in a 500mL polyethylene container and sealed, and heated at 60 ℃ for 2 hours. Then, formaldehyde in distilled water is reacted with acetylacetone in the presence of ammonium ions. The reaction product was measured for its absorption peak at a wavelength of 412nm by a UV spectrometer to determine the amount of formaldehyde generated (mg/kg).
(3) Production of pellets of resin composition
In the formulation shown in table 2, the raw materials selected from (a) to (E) were put into a polyethylene bag, and the operation was repeated three times with vigorous mixing manually for about 10 minutes continuously to obtain a mixture. The resulting mixture was melt-kneaded (melt-mixed) while degassing from the vent using a twin-screw extruder with a vent of 30mm at a set temperature of 200 ℃, a rotation speed of 80rpm, and a discharge amount of 12 kg/hour, and then dried at 80 ℃ for 3 hours, thereby producing pellets of the resin composition.
The pellets of the resin composition were used to conduct the above-mentioned various evaluations. The results are shown in table 2.
According to table 2, in examples 1 to 15 according to the present invention, no clear mold deposit was observed, and the results of a small formaldehyde generation amount and excellent glossiness and FI value were obtained. In addition, it is clear from these examples that the volume average particle diameter (D) is used50) The FI value can be further improved by a smaller (e.g., 200 μm or less) (C) pearl pigment. Further, it can be seen from these examples that the volume average particle diameter (D) is used50) The FI value can be further improved by the metal particles (B) having a small size (for example, 40 μm or less).
In example 12, although there was no problem in terms of characteristics, slight bending was observed during extrusion processing.
In contrast, in comparative example 1, significant mold fouling was observed. This is considered to be caused by not using (C) a pearl pigment or the like.
In addition, in comparative example 2, a clear mold deposit was observed, and aluminum particles were transferred to hands when the pellets of the resin composition were handled. This is considered to be caused by an excessive content of (B) metal particles, etc.
In comparative example 3, formaldehyde generation was not suppressed, and the FI value was low. This is considered to be caused by the use of a pigment other than the (C) pearl pigment, or the like.
From the evaluation results in table 2, it is understood that the addition of the metal particles having a specific shape and the pearlescent pigment according to examples 1 to 15 produces a resin composition which can produce a molded article having excellent metallic appearance with less formaldehyde generation and can suppress mold deposit at the time of molding.
Industrial applicability
The resin composition of the present invention has industrial applicability as a material for a member for a design part, for example.
Claims (6)
1. A resin composition comprising:
(A) 100 parts by mass of a polyacetal resin,
(B) 0.01 to 15 parts by mass of metal particles, and
(C) a pearlescent pigment, a pigment-based pigment,
the volume average particle diameter D of the metal particles (B)50Is 3 μm to 100 μm, and
the resin composition contains 0.01 to 10 parts by mass of the pearlescent pigment (C) per 100 parts by mass of the polyacetal resin (A).
2. The resin composition according to claim 1, wherein the resin composition comprises more than 1 part by mass and 15 parts by mass or less of the metal particles (B) per 100 parts by mass of the polyacetal resin (A).
3. The resin composition according to claim 1 or 2, wherein (C)Volume average particle diameter D of pearl pigment50Is 1-300 μm.
4. The resin composition according to claim 1 or 2, wherein the (C) pearlescent pigment contains 40% by mass or more of a synthetic mineral.
5. The resin composition according to claim 1 or 2, wherein the (C) pearl pigment is mica coated with titanium dioxide or iron oxide.
6. The resin composition according to claim 1 or 2, wherein the resin composition further comprises (D) a dispersing aid.
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| JP2012092185A (en) | 2010-10-26 | 2012-05-17 | Mitsubishi Engineering Plastics Corp | Polyacetal resin composition and molding composed of the same |
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| JP2004237551A (en) * | 2003-02-05 | 2004-08-26 | Pilot Ink Co Ltd | Resin composition for metallic luster-toned writing utensil member and writing utensil member using the same |
| CN102844374A (en) * | 2010-04-16 | 2012-12-26 | 旭化成化学株式会社 | Polyacetal resin composition, process for production of the composition, and molded article |
| CN102627827A (en) * | 2012-03-19 | 2012-08-08 | 上海锦湖日丽塑料有限公司 | Aesthetic resin composition having metal appearance and preparation method thereof |
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| JP7048311B2 (en) | 2022-04-05 |
| JP2019119773A (en) | 2019-07-22 |
| CN110003609A (en) | 2019-07-12 |
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