WO2019187983A1 - Polyacetal resin composition - Google Patents
Polyacetal resin composition Download PDFInfo
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- WO2019187983A1 WO2019187983A1 PCT/JP2019/008116 JP2019008116W WO2019187983A1 WO 2019187983 A1 WO2019187983 A1 WO 2019187983A1 JP 2019008116 W JP2019008116 W JP 2019008116W WO 2019187983 A1 WO2019187983 A1 WO 2019187983A1
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
Definitions
- the present invention relates to a polyacetal resin composition in which the amount of formaldehyde generated is remarkably suppressed and the moldability is excellent.
- Polyacetal resin has excellent mechanical properties, fatigue resistance, friction and wear resistance, chemical resistance and moldability, so it can be used for automobile parts, electrical / electronic equipment parts, other precision machine parts, building materials / piping members, Widely used in fields such as daily life and cosmetic parts and medical parts.
- the demand for quality has been increasing.
- An object of the present invention is to provide a polyacetal resin composition that generates less formaldehyde even in a molded product molded under severe molding conditions such as high temperature and long-term residence.
- the present invention has been achieved by the following.
- R1, R2, and R3 represent a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms, or a hydrocarbon group having 1 to 9 carbon atoms, and at least one of R1, R2, and R3 has 1 to 4 carbon atoms.
- a hydroxyalkyl group 2. 2.
- the present invention also includes a polyacetal resin molded article composed of the polyacetal resin composition.
- the polyacetal resin composition of the present invention is (A) Polyacetal resin 100 parts by mass (B) Copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid (C) represented by the following formula (1) 0.01 to 10 parts by mass of an amine compound, It is characterized by containing.
- R1, R2, and R3 represent a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms, or a hydrocarbon group having 1 to 9 carbon atoms, and at least one of R1, R2, and R3 has 1 to 4 carbon atoms.
- the polyacetal resin of the present invention is a polymer compound having an oxymethylene group (—OCH 2 —) as a main structural unit, and is a polyacetal homopolymer (for example, trade name “Delrin” manufactured by DuPont, USA, Asahi Kasei Corporation) And a polyacetal copolymer containing other comonomer units in addition to the oxymethylene group (for example, trade name “Duracon”, etc., manufactured by Polyplastics Co., Ltd.).
- a polyacetal homopolymer for example, trade name “Delrin” manufactured by DuPont, USA, Asahi Kasei Corporation
- a polyacetal copolymer containing other comonomer units in addition to the oxymethylene group for example, trade name “Duracon”, etc., manufactured by Polyplastics Co., Ltd.
- the comonomer unit includes an oxyalkylene unit (for example, an oxyethylene group (—OCH 2 CH 2 —), an oxypropylene group, an oxytetramethylene group having about 2 to 6 carbon atoms (preferably about 2 to 4 carbon atoms). Group).
- the comonomer unit content is, for example, from 0.01 to 20 mol%, preferably from 0.03 to 10 mol% (eg, 0.05 to 5 mol%), more preferably from 0.1 to 20 mol%, based on the whole polyacetal resin. It can be selected from the range of about 1 to 5 mol%.
- the polyacetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like.
- the polyacetal copolymer may be a random copolymer, a block copolymer, a graft copolymer, or the like.
- the polyacetal resin may have a branched structure as well as a linear structure, and may have a crosslinked structure. Furthermore, the terminal of the polyacetal resin may be stabilized by esterification with a carboxylic acid such as acetic acid or propionic acid or an anhydride thereof.
- the polymerization degree, branching degree, and crosslinking degree of the polyacetal are not particularly limited as long as it can be melt-molded.
- the polyacetal resin is obtained by, for example, homopolymerizing formaldehyde, copolymerizing trioxane with cyclic ether or cyclic formal such as ethylene oxide, propylene oxide, 1,3-dioxolane, diethylene glycol formal, 1,4-butanediol formal. Can be manufactured.
- the copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid according to the present invention (hereinafter also referred to as ethylene copolymer) is composed of at least one selected from acrylic acid and methacrylic acid and ethylene. It is a copolymer, and acrylic acid or methacrylic acid is contained in an amount of 0.5 to 40% by mass, preferably 1 to 30% by mass.
- the ethylene copolymer of the present invention is commercially available, for example, as AC polyethylene (manufactured by Honeywell), Nucrel (manufactured by Mitsui / DuPont Polychemical).
- the ethylene copolymer of the present invention is, for example, 0.001 to 10 parts by mass, preferably 0.005 to 1 part by mass, particularly preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the polyacetal resin. .
- the amine compound of the present invention (hereinafter sometimes referred to as the amine compound (C) of the present invention) is a compound represented by the following formula (1).
- R1, R2, and R3 represent a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms, or a hydrocarbon group having 1 to 9 carbon atoms, and at least one of R1, R2, and R3 has 1 to 4 carbon atoms.
- the amine compound (C) of the present invention preferably has a basicity pKb in the range of 4-8.
- pKb is a logarithmic value of the reciprocal of the base dissociation constant in an aqueous solution at 25 ° C., and in the case of multi-stage dissociation, the first-stage dissociation constant (ie, pKb 1 ) is used.
- the amine compound (C) of the present invention is contained in an amount of 0.01 to 10 parts by mass, preferably 0.02 to 5 parts by mass, and most preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the polyacetal resin.
- the polyacetal resin composition of the present invention may further contain an antioxidant, an alkali or alkaline earth metal compound and a stabilizer.
- antioxidant a known antioxidant can be used, and examples thereof include phenolic (such as hindered phenols), amine, phosphorus, sulfur, hydroquinone, and quinoline antioxidants. It is done. These antioxidants can be used alone or in combination of two or more.
- antioxidants can be used alone or in combination of two or more.
- the content of the antioxidant is, for example, in the range of 0.01 to 5 parts by weight, preferably 0.05 to 2.5 parts by weight, particularly about 0.1 to 1 part by weight with respect to 100 parts by weight of the polyacetal resin. You can choose from.
- Alkali or alkaline earth metal compounds include aliphatic carboxylic acids (eg, acetic acid, propionic acid, succinic acid, adipic acid, etc.), aromatic carboxylic acids (eg, benzoic acid, phthalic acid, phenylacetic acid, etc.), single bases Sodium, calcium, magnesium metal salts of C 1-10 carboxylic acids such as dibasic or tribasic oxycarboxylic acids (eg, lactic acid, mandelic acid, malic acid, citric acid, etc.); metal oxides such as CaO, MgO; Examples thereof include metal hydroxides such as Ca (OH) 2 and Mg (OH) 2 ; metal carbonates such as CaCO 3 and MgCO 3 .
- aliphatic carboxylic acids eg, acetic acid, propionic acid, succinic acid, adipic acid, etc.
- aromatic carboxylic acids eg, benzoic acid, phthalic acid, phenylacetic acid, etc.
- the alkali or alkaline earth metal compounds can be used alone or in combination of two or more, and the proportion thereof is 0.001 to 10 parts by mass, preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the polyacetal resin. Part (especially 0.001 to 2 parts by mass).
- stabilizers include processing stabilizers and weathering (light) stabilizers.
- processing stabilizer at least one selected from known polyalkylene glycols, fatty acid esters, fatty acid amides, fatty acid metal salts and the like can be used.
- the processing stabilizers can be used alone or in combination.
- the proportion of the processing stabilizer is about 0.01 to 10 parts by weight, preferably about 0.03 to 5 parts by weight (eg 0.05 to 3 parts by weight), particularly 0.05 to 100 parts by weight of the polyacetal resin. About 2 parts by mass can be contained.
- (a) benzotriazole compound, (b) benzophenone compound, (c) aromatic benzoate compound, (d) cyanoacrylate compound, (e) oxalic acid anilide compound, (F) A hindered amine compound can be exemplified.
- the weathering (light) stabilizer may be used alone, but is preferably used alone or in combination of two or more, (a) benzotriazole compounds, (b) benzophenone compounds, (c) aromatic A combination of a weather resistant (light) stabilizer of a group benzoate compound, (d) a cyanoacrylate compound, and / or (e) an oxalic acid anilide compound, and (f) a hindered amine compound is preferred.
- the addition amount of the weathering (light) stabilizer is, for example, 0.01 to 5 parts by mass (for example, 0.01 to 3 parts by mass), preferably 0.01 to 2 parts by mass, relative to 100 parts by mass of the polyacetal resin More preferably, it is about 0.1 to 2 parts by mass (for example, 0.1 to 1.5 parts by mass).
- the antioxidant, alkali or alkaline earth metal compound and stabilizer may be used alone or in combination of two or more as required.
- a colorant with the polyacetal resin composition of the present invention.
- Various dyes or pigments can be used as the colorant.
- the dye is preferably a solvent dye, and examples thereof include azo dyes, anthraquinone dyes, phthalocyanine dyes, and naphthoquinone dyes.
- As the pigment any of inorganic pigments and organic pigments can be used, and they may be used alone or in combination with a plurality of colorants.
- the content of the colorant is, for example, 0 to 5 parts by mass (for example, 0.01 to 5 parts by mass), preferably 0.1 to 4 parts by mass, and more preferably 0.1 parts by mass with respect to 100 parts by mass of the polyacetal resin. About 3 to 3 parts by mass.
- a mold release agent In addition to the polyacetal resin composition of the present invention, a mold release agent, a nucleating agent, an antistatic agent, a flame retardant, a surfactant, various polymers, a filler, and the like are added in combination of one or more as necessary. May be.
- the polyacetal resin composition of the present invention may be a powdery granular mixture or a molten mixture.
- the polyacetal resin, the ethylene copolymer of the present invention and the amine compound of the present invention, and other additives, if necessary, are conventionally used. It can be prepared by mixing by the method. For example, each component is mixed, kneaded by a single or twin screw extruder, extruded to prepare pellets, and then molded, and once a pellet (master batch) with a different composition is prepared, a predetermined amount of the pellets are prepared.
- a powder of a polyacetal resin as a substrate for example, a powder obtained by pulverizing part or all of a polyacetal resin
- other components amine compound, ethylene copolymer
- Molded articles obtained from the composition of the present invention are most suitable for use in the automotive field, but other mechanical / electrical parts such as mechanical parts (active parts and passive parts), building materials / piping, daily necessities (life). -It is suitably used as parts / members in the cosmetics field and medical field (medical / therapeutic field).
- the mechanical parts in the automotive field include inner handles, fael trunk openers, seat belt buckles, assist wraps, various interior parts such as switches, knobs, levers, clips, electrical system parts such as meters and connectors, Examples include in-vehicle electrical and electronic parts such as audio equipment and car navigation equipment, parts that come into contact with metal, such as window regulator carrier plates, door lock actuator parts, mirror parts, wiper motor system parts, fuel system parts, etc. it can.
- the amount of formaldehyde generated from the molded products was evaluated as follows.
- reaction product of DNPH and formaldehyde is extracted from the DNPH collection tube with acetonitrile, and the amount of generated formaldehyde is obtained by a calibration curve method using a standard substance of the reaction product of DNPH and formaldehyde by high performance liquid chromatography.
- the amount of formaldehyde generated per unit weight ( ⁇ g / g) was calculated.
- Molding machine FANUC ROBOSHOT ⁇ -S100ia * Molding conditions: Cylinder temperature (° C) nozzle -C1-C2-C3 220 220 220 220 Injection pressure 60 (MPa) Injection speed 1.0 (m / min) Residence time in molding machine 30 minutes Mold temperature 80 (°C)
- Polyacetal resin (A-1) a polyacetal copolymer obtained by copolymerizing 96.7% by mass of trioxane and 3.3% by mass of 1,3-dioxolane (measured at a melt index (190 ° C., load 2160 g) ): 9 g / 10 min)
- Ethylene copolymer (B-1): ethylene-acrylic acid copolymer, acrylic acid modification rate: 5% by mass, manufactured by Honeywell, “A-C540” (B-2): Ethylene-methacrylic acid copolymer, methacrylic acid modification rate: 4% by mass Mitsui DuPont Polychemical Co., Ltd. “Nucleel AN4214C” (B-3): Ethylene-methacrylic acid copolymer, methacrylic acid modification rate: 15% by mass, Mitsui-DuPont Polychemical Co., Ltd. “Nucleel N1525”
- C Amine compound (C-1): Tris (hydroxymethyl) aminomethane (THAM) pKb: 5.7 (C-2): 2-amino-2-methyl-propanol (AMP) pKb: 4.3 (C-3): Melamine pKb: 9 (C-4): Benzoguanamine pKb: 10.1 4).
- D Hindered phenol antioxidant (D-1): Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
- the resin compositions of the examples have a very small amount of formaldehyde generated from molded products molded under severe molding conditions of high temperature and long-time retention compared to the comparative examples. Therefore, the quality of the molded product can be improved.
Abstract
The purpose of the present invention is to provide a polyacetal resin composition which, even when used in a molding formed under rigorous conditions such as high temperature and prolonged residence time, generates less formaldehyde. This polyacetal resin composition at least comprises (A) 100 parts by mass of a polyacetal resin, (B) 0.001-10 parts by mass of a copolymer between ethylene and at least one selected from acrylic acid and methacrylic acid, and (C) 0.01-10 parts by mass of an amine compound represented by formula (1) (wherein R1, R2, and R3 each represent a hydrogen atom, a hydroxyalkyl group having 1-4 carbon atoms, or a hydrocarbon group having 1-9 carbon atoms, and at least one of R1, R2, and R3 is a hydroxyalkyl group having 1-4 carbon atoms).
Description
本発明は、ホルムアルデヒド発生量が著しく抑制され、成形加工性に優れたポリアセタール樹脂組成物に関する。
The present invention relates to a polyacetal resin composition in which the amount of formaldehyde generated is remarkably suppressed and the moldability is excellent.
ポリアセタール樹脂は、機械的性質、耐疲労性、耐摩擦・摩耗性、耐薬品性及び成形性に優れているため、自動車部品、電気・電子機器部品、その他の精密機械部品、建材・配管部材、生活・化粧用部品、医用部品などの分野において広く利用されている。
しかしながら、用途の拡大、多様化に伴い、その品質に対する要求はより高度化する傾向を示している。特に自動車部品としての、最終製品の使用周辺の環境をホルムアルデヒドの汚染から守るための要求は、極めて高いものがある。 Polyacetal resin has excellent mechanical properties, fatigue resistance, friction and wear resistance, chemical resistance and moldability, so it can be used for automobile parts, electrical / electronic equipment parts, other precision machine parts, building materials / piping members, Widely used in fields such as daily life and cosmetic parts and medical parts.
However, with the expansion and diversification of applications, the demand for quality has been increasing. In particular, there are extremely high demands for protecting the environment around the end product use as automobile parts from contamination of formaldehyde.
しかしながら、用途の拡大、多様化に伴い、その品質に対する要求はより高度化する傾向を示している。特に自動車部品としての、最終製品の使用周辺の環境をホルムアルデヒドの汚染から守るための要求は、極めて高いものがある。 Polyacetal resin has excellent mechanical properties, fatigue resistance, friction and wear resistance, chemical resistance and moldability, so it can be used for automobile parts, electrical / electronic equipment parts, other precision machine parts, building materials / piping members, Widely used in fields such as daily life and cosmetic parts and medical parts.
However, with the expansion and diversification of applications, the demand for quality has been increasing. In particular, there are extremely high demands for protecting the environment around the end product use as automobile parts from contamination of formaldehyde.
自動車業界では、ポリアセタール樹脂からホルムアルデヒドの発生を定める種々の規格を制定している。例えばＶＤＡ２７５（ドイツ自動車工業会規格）は、代表的な評価であり一般的によく使用されているが、ポリアセタール樹脂の汎用性が高まるにつれ、さらに厳しい種々の条件を満足することが必要となっている。
ホルムアルデヒドの発生を低減させるためにポリアセタールホモポリマー樹脂に、第１級アミンまたは第２級アミンを含有させる技術や、厳しい条件にも耐えられるポリアセタール樹脂組成物として、ヒドラジド化合物を含有させる技術が提案されている（特許文献１、２）。また、ポリアセタールコポリマー樹脂に、エチレン－メタクリル酸共重合体を含有させる技術が提案されている（特許文献３）。 In the automotive industry, various standards have been established that determine the generation of formaldehyde from polyacetal resins. For example, VDA275 (German Automobile Manufacturers Association Standard) is a typical evaluation and is commonly used. However, as the versatility of polyacetal resin increases, it is necessary to satisfy more stringent conditions. Yes.
In order to reduce the generation of formaldehyde, a technique for containing a primary amine or a secondary amine in a polyacetal homopolymer resin and a technique for containing a hydrazide compound as a polyacetal resin composition that can withstand severe conditions have been proposed. (Patent Documents 1 and 2). In addition, a technique for incorporating an ethylene-methacrylic acid copolymer into a polyacetal copolymer resin has been proposed (Patent Document 3).
ホルムアルデヒドの発生を低減させるためにポリアセタールホモポリマー樹脂に、第１級アミンまたは第２級アミンを含有させる技術や、厳しい条件にも耐えられるポリアセタール樹脂組成物として、ヒドラジド化合物を含有させる技術が提案されている（特許文献１、２）。また、ポリアセタールコポリマー樹脂に、エチレン－メタクリル酸共重合体を含有させる技術が提案されている（特許文献３）。 In the automotive industry, various standards have been established that determine the generation of formaldehyde from polyacetal resins. For example, VDA275 (German Automobile Manufacturers Association Standard) is a typical evaluation and is commonly used. However, as the versatility of polyacetal resin increases, it is necessary to satisfy more stringent conditions. Yes.
In order to reduce the generation of formaldehyde, a technique for containing a primary amine or a secondary amine in a polyacetal homopolymer resin and a technique for containing a hydrazide compound as a polyacetal resin composition that can withstand severe conditions have been proposed. (Patent Documents 1 and 2). In addition, a technique for incorporating an ethylene-methacrylic acid copolymer into a polyacetal copolymer resin has been proposed (Patent Document 3).
自動車業界において新たに設けられた規格も含め広範囲な目標を満足するポリアセタール樹脂が要求されているが、上記の技術では満足するものはいまだ存在していなかった。
本発明の目的は、高温、長時間滞留等の厳しい成形条件下で成形された成形品においてもホルムアルデヒドの発生の少ないポリアセタール樹脂組成物を提供することである。 There is a demand for a polyacetal resin that satisfies a wide range of targets, including newly established standards in the automotive industry, but none of the above technologies has yet been satisfactory.
An object of the present invention is to provide a polyacetal resin composition that generates less formaldehyde even in a molded product molded under severe molding conditions such as high temperature and long-term residence.
本発明の目的は、高温、長時間滞留等の厳しい成形条件下で成形された成形品においてもホルムアルデヒドの発生の少ないポリアセタール樹脂組成物を提供することである。 There is a demand for a polyacetal resin that satisfies a wide range of targets, including newly established standards in the automotive industry, but none of the above technologies has yet been satisfactory.
An object of the present invention is to provide a polyacetal resin composition that generates less formaldehyde even in a molded product molded under severe molding conditions such as high temperature and long-term residence.
本発明は、下記によって達成された。
１．少なくとも、
（Ａ）ポリアセタール樹脂１００質量部
（Ｂ）アクリル酸およびメタクリル酸から選択される少なくとも１種と、エチレンとの共重合体０．００１～１０質量部
（Ｃ）下記式（１）で表されるアミン化合物０．０１～１０質量部、
とを含有するポリアセタール樹脂組成物。
ここで、Ｒ１、Ｒ２、Ｒ３は、水素原子、炭素数１～４のヒドロキシアルキル基または炭素数１～９の炭化水素基を表し、Ｒ１、Ｒ２、Ｒ３の少なくとも１つが炭素数１～４のヒドロキシアルキル基である。
２．前記（Ｂ）共重合体が、アクリル酸およびメタクリル酸から選択される少なくとも１種が０．５～４０質量％である共重合体である前記１記載のポリアセタール樹脂組成物。
３．前記（Ｃ）が、トリス（ヒドロキシメチル）アミノメタン、２－アミノ－２－エチル－プロパンジオール、および、２－アミノ－２－メチル－プロパノールで表される請求項１または２記載のポリアセタール樹脂組成物。 The present invention has been achieved by the following.
1. at least,
(A) Polyacetal resin 100 parts by mass (B) Copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid (C) represented by the following formula (1) 0.01 to 10 parts by mass of an amine compound,
And a polyacetal resin composition.
Here, R1, R2, and R3 represent a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms, or a hydrocarbon group having 1 to 9 carbon atoms, and at least one of R1, R2, and R3 has 1 to 4 carbon atoms. A hydroxyalkyl group;
2. 2. The polyacetal resin composition according to 1, wherein the copolymer (B) is a copolymer in which at least one selected from acrylic acid and methacrylic acid is 0.5 to 40% by mass.
3. The polyacetal resin composition according to claim 1 or 2, wherein (C) is represented by tris (hydroxymethyl) aminomethane, 2-amino-2-ethyl-propanediol, and 2-amino-2-methyl-propanol. object.
１．少なくとも、
（Ａ）ポリアセタール樹脂１００質量部
（Ｂ）アクリル酸およびメタクリル酸から選択される少なくとも１種と、エチレンとの共重合体０．００１～１０質量部
（Ｃ）下記式（１）で表されるアミン化合物０．０１～１０質量部、
とを含有するポリアセタール樹脂組成物。
２．前記（Ｂ）共重合体が、アクリル酸およびメタクリル酸から選択される少なくとも１種が０．５～４０質量％である共重合体である前記１記載のポリアセタール樹脂組成物。
３．前記（Ｃ）が、トリス（ヒドロキシメチル）アミノメタン、２－アミノ－２－エチル－プロパンジオール、および、２－アミノ－２－メチル－プロパノールで表される請求項１または２記載のポリアセタール樹脂組成物。 The present invention has been achieved by the following.
1. at least,
(A) Polyacetal resin 100 parts by mass (B) Copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid (C) represented by the following formula (1) 0.01 to 10 parts by mass of an amine compound,
And a polyacetal resin composition.
2. 2. The polyacetal resin composition according to 1, wherein the copolymer (B) is a copolymer in which at least one selected from acrylic acid and methacrylic acid is 0.5 to 40% by mass.
3. The polyacetal resin composition according to claim 1 or 2, wherein (C) is represented by tris (hydroxymethyl) aminomethane, 2-amino-2-ethyl-propanediol, and 2-amino-2-methyl-propanol. object.
本発明によれば、高温、長時間滞留等の厳しい成形条件下で成形された成形品においてもホルムアルデヒドの発生の少ないポリアセタール樹脂組成物を提供することができる。
According to the present invention, it is possible to provide a polyacetal resin composition that generates less formaldehyde even in a molded product molded under severe molding conditions such as high temperature and long-term residence.
以下、本発明の実施形態について説明する。なお、本発明は以下の実施形態に限定されない。本発明には、前記ポリアセタール樹脂組成物で構成されたポリアセタール樹脂成形品も含まれる。
Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment. The present invention also includes a polyacetal resin molded article composed of the polyacetal resin composition.
＜ポリアセタール樹脂組成物＞
本発明のポリアセタール樹脂組成物は、
（Ａ）ポリアセタール樹脂１００質量部
（Ｂ）アクリル酸およびメタクリル酸から選択される少なくとも１種と、エチレンとの共重合体０．００１～１０質量部
（Ｃ）下記式（１）で表されるアミン化合物０．０１～１０質量部、
とを含有することを特徴とする。
ここで、Ｒ１、Ｒ２、Ｒ３は、水素原子、炭素数１～４のヒドロキシアルキル基または炭素数１～９の炭化水素基を表し、Ｒ１、Ｒ２、Ｒ３の少なくとも１つが炭素数１～４のヒドロキシアルキル基である。
<Polyacetal resin composition>
The polyacetal resin composition of the present invention is
(A) Polyacetal resin 100 parts by mass (B) Copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid (C) represented by the following formula (1) 0.01 to 10 parts by mass of an amine compound,
It is characterized by containing.
Here, R1, R2, and R3 represent a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms, or a hydrocarbon group having 1 to 9 carbon atoms, and at least one of R1, R2, and R3 has 1 to 4 carbon atoms. A hydroxyalkyl group;
本発明のポリアセタール樹脂組成物は、
（Ａ）ポリアセタール樹脂１００質量部
（Ｂ）アクリル酸およびメタクリル酸から選択される少なくとも１種と、エチレンとの共重合体０．００１～１０質量部
（Ｃ）下記式（１）で表されるアミン化合物０．０１～１０質量部、
とを含有することを特徴とする。
The polyacetal resin composition of the present invention is
(A) Polyacetal resin 100 parts by mass (B) Copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid (C) represented by the following formula (1) 0.01 to 10 parts by mass of an amine compound,
It is characterized by containing.
≪ポリアセタール樹脂≫
本発明のポリアセタール樹脂とは、オキシメチレン基（－ＯＣＨ2－）を主たる構成単位とする高分子化合物であり、ポリアセタールホモポリマー（例えば、米国デュポン社製、商品名「デルリン」、旭化成（株）製、商品名「テナック４０１０」など）、オキシメチレン基以外に他のコモノマー単位を含有するポリアセタールコポリマー（例えば、ポリプラスチックス（株）製、商品名「ジュラコン」など）が含まれる。 ≪Polyacetal resin≫
The polyacetal resin of the present invention is a polymer compound having an oxymethylene group (—OCH 2 —) as a main structural unit, and is a polyacetal homopolymer (for example, trade name “Delrin” manufactured by DuPont, USA, Asahi Kasei Corporation) And a polyacetal copolymer containing other comonomer units in addition to the oxymethylene group (for example, trade name “Duracon”, etc., manufactured by Polyplastics Co., Ltd.).
本発明のポリアセタール樹脂とは、オキシメチレン基（－ＯＣＨ2－）を主たる構成単位とする高分子化合物であり、ポリアセタールホモポリマー（例えば、米国デュポン社製、商品名「デルリン」、旭化成（株）製、商品名「テナック４０１０」など）、オキシメチレン基以外に他のコモノマー単位を含有するポリアセタールコポリマー（例えば、ポリプラスチックス（株）製、商品名「ジュラコン」など）が含まれる。 ≪Polyacetal resin≫
The polyacetal resin of the present invention is a polymer compound having an oxymethylene group (—OCH 2 —) as a main structural unit, and is a polyacetal homopolymer (for example, trade name “Delrin” manufactured by DuPont, USA, Asahi Kasei Corporation) And a polyacetal copolymer containing other comonomer units in addition to the oxymethylene group (for example, trade name “Duracon”, etc., manufactured by Polyplastics Co., Ltd.).
コポリマーにおいて、コモノマー単位には、炭素数２～６程度（好ましくは炭素数２～４程度）のオキシアルキレン単位（例えば、オキシエチレン基（－ＯＣＨ2ＣＨ2－）、オキシプロピレン基、オキシテトラメチレン基など）が含まれる。
コモノマー単位の含有量は、例えば、ポリアセタール樹脂全体に対して、０．０１～２０モル％、好ましくは０．０３～１０モル％（例えば、０．０５～５モル％）、さらに好ましくは０．１～５モル％程度の範囲から選択できる。 In the copolymer, the comonomer unit includes an oxyalkylene unit (for example, an oxyethylene group (—OCH 2 CH 2 —), an oxypropylene group, an oxytetramethylene group having about 2 to 6 carbon atoms (preferably about 2 to 4 carbon atoms). Group).
The comonomer unit content is, for example, from 0.01 to 20 mol%, preferably from 0.03 to 10 mol% (eg, 0.05 to 5 mol%), more preferably from 0.1 to 20 mol%, based on the whole polyacetal resin. It can be selected from the range of about 1 to 5 mol%.
コモノマー単位の含有量は、例えば、ポリアセタール樹脂全体に対して、０．０１～２０モル％、好ましくは０．０３～１０モル％（例えば、０．０５～５モル％）、さらに好ましくは０．１～５モル％程度の範囲から選択できる。 In the copolymer, the comonomer unit includes an oxyalkylene unit (for example, an oxyethylene group (—OCH 2 CH 2 —), an oxypropylene group, an oxytetramethylene group having about 2 to 6 carbon atoms (preferably about 2 to 4 carbon atoms). Group).
The comonomer unit content is, for example, from 0.01 to 20 mol%, preferably from 0.03 to 10 mol% (eg, 0.05 to 5 mol%), more preferably from 0.1 to 20 mol%, based on the whole polyacetal resin. It can be selected from the range of about 1 to 5 mol%.
ポリアセタールコポリマーは、二成分で構成されたコポリマー、三成分で構成されたターポリマーなどであってもよい。ポリアセタールコポリマーは、ランダムコポリマーの他、ブロックコポリマー、グラフトコポリマーなどであってもよい。
The polyacetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like. The polyacetal copolymer may be a random copolymer, a block copolymer, a graft copolymer, or the like.
また、ポリアセタール樹脂は、線状のみならず分岐構造であってもよく、架橋構造を有していてもよい。さらに、ポリアセタール樹脂の末端は、例えば、酢酸、プロピオン酸などのカルボン酸又はそれらの無水物とのエステル化などにより安定化してもよい。ポリアセタールの重合度、分岐度や架橋度も特に制限はなく、溶融成形可能であればよい。
Moreover, the polyacetal resin may have a branched structure as well as a linear structure, and may have a crosslinked structure. Furthermore, the terminal of the polyacetal resin may be stabilized by esterification with a carboxylic acid such as acetic acid or propionic acid or an anhydride thereof. The polymerization degree, branching degree, and crosslinking degree of the polyacetal are not particularly limited as long as it can be melt-molded.
前記ポリアセタール樹脂は、例えば、ホルムアルデヒドの単独重合、トリオキサンと、エチレンオキサイド、プロピレンオキサイド、１、３－ジオキソラン、ジエチレングリコールホルマール、１、４－ブタンジオールホルマールなどの環状エーテルや環状ホルマールを共重合することにより製造できる。
The polyacetal resin is obtained by, for example, homopolymerizing formaldehyde, copolymerizing trioxane with cyclic ether or cyclic formal such as ethylene oxide, propylene oxide, 1,3-dioxolane, diethylene glycol formal, 1,4-butanediol formal. Can be manufactured.
≪アクリル酸およびメタクリル酸から選択される少なくとも１種、とエチレンとの共重合体≫
本発明のアクリル酸およびメタクリル酸から選択される少なくとも１種とエチレンとの共重合体（以下、エチレン共重合体ともいう）は、アクリル酸およびメタクリル酸から選択される少なくとも１種とエチレンとの共重合体であり、アクリル酸またはメタクリル酸は、共重合体中０．５～４０質量％含まれるものであり、好ましくは、１～３０質量％含まれるものである。
本発明のエチレン共重合体は、例えば、Ａ－Ｃポリエチレン（ハネウェル社製）、ニュクレル（三井・デュポンポリケミカル社製）などとして市販されている。 << Copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid >>
The copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid according to the present invention (hereinafter also referred to as ethylene copolymer) is composed of at least one selected from acrylic acid and methacrylic acid and ethylene. It is a copolymer, and acrylic acid or methacrylic acid is contained in an amount of 0.5 to 40% by mass, preferably 1 to 30% by mass.
The ethylene copolymer of the present invention is commercially available, for example, as AC polyethylene (manufactured by Honeywell), Nucrel (manufactured by Mitsui / DuPont Polychemical).
本発明のアクリル酸およびメタクリル酸から選択される少なくとも１種とエチレンとの共重合体（以下、エチレン共重合体ともいう）は、アクリル酸およびメタクリル酸から選択される少なくとも１種とエチレンとの共重合体であり、アクリル酸またはメタクリル酸は、共重合体中０．５～４０質量％含まれるものであり、好ましくは、１～３０質量％含まれるものである。
本発明のエチレン共重合体は、例えば、Ａ－Ｃポリエチレン（ハネウェル社製）、ニュクレル（三井・デュポンポリケミカル社製）などとして市販されている。 << Copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid >>
The copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid according to the present invention (hereinafter also referred to as ethylene copolymer) is composed of at least one selected from acrylic acid and methacrylic acid and ethylene. It is a copolymer, and acrylic acid or methacrylic acid is contained in an amount of 0.5 to 40% by mass, preferably 1 to 30% by mass.
The ethylene copolymer of the present invention is commercially available, for example, as AC polyethylene (manufactured by Honeywell), Nucrel (manufactured by Mitsui / DuPont Polychemical).
本発明のエチレン共重合体は、ポリアセタール樹脂１００質量部に対して、例えば、０．００１～１０質量部、好ましくは０．００５～１質量部、特に０．０１～０．５質量部が好ましい。
The ethylene copolymer of the present invention is, for example, 0.001 to 10 parts by mass, preferably 0.005 to 1 part by mass, particularly preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the polyacetal resin. .
≪下記式（１）で表されるアミン化合物≫
本発明のアミン化合物（以下、本発明のアミン化合物（Ｃ）ということもある）は、下記式（１）で表される化合物である。
ここで、Ｒ１、Ｒ２、Ｒ３は、水素原子、炭素数１～４のヒドロキシアルキル基または炭素数１～９の炭化水素基を表し、Ｒ１、Ｒ２、Ｒ３の少なくとも１つが炭素数１～４のヒドロキシアルキル基である。
本発明のアミン化合物（Ｃ）は、好ましくは、４～８の範囲の塩基性度ｐＫｂを有する。本明細書において、ｐＫｂとは、２５℃の水溶液中における塩基解離定数の逆数の対数値であり、多段解離の場合、第１段の解離定数（すなわちｐＫｂ1）を使用する。 << Amine compound represented by the following formula (1) >>
The amine compound of the present invention (hereinafter sometimes referred to as the amine compound (C) of the present invention) is a compound represented by the following formula (1).
Here, R1, R2, and R3 represent a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms, or a hydrocarbon group having 1 to 9 carbon atoms, and at least one of R1, R2, and R3 has 1 to 4 carbon atoms. A hydroxyalkyl group;
The amine compound (C) of the present invention preferably has a basicity pKb in the range of 4-8. In this specification, pKb is a logarithmic value of the reciprocal of the base dissociation constant in an aqueous solution at 25 ° C., and in the case of multi-stage dissociation, the first-stage dissociation constant (ie, pKb 1 ) is used.
本発明のアミン化合物（以下、本発明のアミン化合物（Ｃ）ということもある）は、下記式（１）で表される化合物である。
本発明のアミン化合物（Ｃ）は、好ましくは、４～８の範囲の塩基性度ｐＫｂを有する。本明細書において、ｐＫｂとは、２５℃の水溶液中における塩基解離定数の逆数の対数値であり、多段解離の場合、第１段の解離定数（すなわちｐＫｂ1）を使用する。 << Amine compound represented by the following formula (1) >>
The amine compound of the present invention (hereinafter sometimes referred to as the amine compound (C) of the present invention) is a compound represented by the following formula (1).
The amine compound (C) of the present invention preferably has a basicity pKb in the range of 4-8. In this specification, pKb is a logarithmic value of the reciprocal of the base dissociation constant in an aqueous solution at 25 ° C., and in the case of multi-stage dissociation, the first-stage dissociation constant (ie, pKb 1 ) is used.
具体例には、これらに限定はされないが、例えば、トリス（ヒドロキシメチル）アミノメタン、２－アミノ－２－エチル－プロパンジオール、および２－アミノ－２－メチル－プロパノールが挙げられ、特にトリス（ヒドロキシメチル）アミノメタンが好ましい。
本発明のアミン化合物（Ｃ）は、ポリアセタール樹脂１００質量部に対し０．０１～１０質量部、好ましくは０．０２～５質量部、そして最も好ましくは０．０５～２質量部含有させる。
＜その他の添加剤＞
本発明のポリアセタール樹脂組成物は、さらに、酸化防止剤、アルカリ又はアルカリ土類金属化合物及び安定剤などを含んでもよい。 Specific examples include, but are not limited to, for example, tris (hydroxymethyl) aminomethane, 2-amino-2-ethyl-propanediol, and 2-amino-2-methyl-propanol, particularly tris ( Hydroxymethyl) aminomethane is preferred.
The amine compound (C) of the present invention is contained in an amount of 0.01 to 10 parts by mass, preferably 0.02 to 5 parts by mass, and most preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the polyacetal resin.
<Other additives>
The polyacetal resin composition of the present invention may further contain an antioxidant, an alkali or alkaline earth metal compound and a stabilizer.
本発明のアミン化合物（Ｃ）は、ポリアセタール樹脂１００質量部に対し０．０１～１０質量部、好ましくは０．０２～５質量部、そして最も好ましくは０．０５～２質量部含有させる。
＜その他の添加剤＞
本発明のポリアセタール樹脂組成物は、さらに、酸化防止剤、アルカリ又はアルカリ土類金属化合物及び安定剤などを含んでもよい。 Specific examples include, but are not limited to, for example, tris (hydroxymethyl) aminomethane, 2-amino-2-ethyl-propanediol, and 2-amino-2-methyl-propanol, particularly tris ( Hydroxymethyl) aminomethane is preferred.
The amine compound (C) of the present invention is contained in an amount of 0.01 to 10 parts by mass, preferably 0.02 to 5 parts by mass, and most preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the polyacetal resin.
<Other additives>
The polyacetal resin composition of the present invention may further contain an antioxidant, an alkali or alkaline earth metal compound and a stabilizer.
酸化防止剤には、公知の酸化防止剤を使用することができ、例えば、フェノール系（ヒンダードフェノール類など）、アミン系、リン系、イオウ系、ヒドロキノン系、キノリン系酸化防止剤などが挙げられる。これらの酸化防止剤は一種又は二種以上併用することができる。
As the antioxidant, a known antioxidant can be used, and examples thereof include phenolic (such as hindered phenols), amine, phosphorus, sulfur, hydroquinone, and quinoline antioxidants. It is done. These antioxidants can be used alone or in combination of two or more.
これらの酸化防止剤は単独で又は二種以上使用できる。酸化防止剤の含有量は、例えば、ポリアセタール樹脂１００質量部に対して、０．０１～５質量部、好ましくは０．０５～２．５質量部、特に０．１～１質量部程度の範囲から選択できる。
These antioxidants can be used alone or in combination of two or more. The content of the antioxidant is, for example, in the range of 0.01 to 5 parts by weight, preferably 0.05 to 2.5 parts by weight, particularly about 0.1 to 1 part by weight with respect to 100 parts by weight of the polyacetal resin. You can choose from.
アルカリ又はアルカリ土類金属化合物としては、脂肪族カルボン酸（例えば、酢酸、プロピオン酸、コハク酸、アジピン酸など）、芳香族カルボン酸（例えば、安息香酸、フタル酸、フェニル酢酸など）、一塩基、二塩基又は三塩基オキシカルボン酸（例えば、乳酸、マンデル酸、リンゴ酸、クエン酸など）などのＣ1-10カルボン酸のナトリウム、カルシウム、マグネシウム金属塩；ＣａＯ、ＭｇＯなどの金属酸化物；Ｃａ（ＯＨ）2、Ｍｇ（ＯＨ）2などの金属水酸化物；ＣａＣＯ3、ＭｇＣＯ3などの金属炭酸塩などが例示できる。
Alkali or alkaline earth metal compounds include aliphatic carboxylic acids (eg, acetic acid, propionic acid, succinic acid, adipic acid, etc.), aromatic carboxylic acids (eg, benzoic acid, phthalic acid, phenylacetic acid, etc.), single bases Sodium, calcium, magnesium metal salts of C 1-10 carboxylic acids such as dibasic or tribasic oxycarboxylic acids (eg, lactic acid, mandelic acid, malic acid, citric acid, etc.); metal oxides such as CaO, MgO; Examples thereof include metal hydroxides such as Ca (OH) 2 and Mg (OH) 2 ; metal carbonates such as CaCO 3 and MgCO 3 .
前記アルカリ又はアルカリ土類金属化合物は、単独又は二種以上を組合せて使用でき、その割合は、ポリアセタール樹脂１００質量部に対して、０．００１～１０質量部、好ましくは０．００１～５質量部（特に０．００１～２質量部）程度の範囲から選択できる。
The alkali or alkaline earth metal compounds can be used alone or in combination of two or more, and the proportion thereof is 0.001 to 10 parts by mass, preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the polyacetal resin. Part (especially 0.001 to 2 parts by mass).
安定剤としては、特に加工安定剤や耐候（光）安定剤などが挙げられる。加工安定剤としては、公知のポリアルキレングリコール、脂肪酸エステル、脂肪酸アミド及び脂肪酸金属塩などから選択された少なくとも一種が使用できる。前記加工安定剤は、一種又は二種以上組合せて使用できる。
Examples of stabilizers include processing stabilizers and weathering (light) stabilizers. As the processing stabilizer, at least one selected from known polyalkylene glycols, fatty acid esters, fatty acid amides, fatty acid metal salts and the like can be used. The processing stabilizers can be used alone or in combination.
加工安定剤の割合は、ポリアセタール樹脂１００質量部に対して、０．０１～１０質量部、好ましくは０．０３～５質量部（例えば、０．０５～３質量部）程度、特に０．０５～２質量部程度含有させることができる。
The proportion of the processing stabilizer is about 0.01 to 10 parts by weight, preferably about 0.03 to 5 parts by weight (eg 0.05 to 3 parts by weight), particularly 0.05 to 100 parts by weight of the polyacetal resin. About 2 parts by mass can be contained.
耐候（光）安定剤としては、（ａ）ベンゾトリアゾール系化合物、（ｂ）ベンゾフェノン系化合物、（ｃ）芳香族ベンゾエート系化合物、（ｄ）シアノアクリレート系化合物、（ｅ）シュウ酸アニリド系化合物、（ｆ）ヒンダードアミン系化合物などが例示できる。
As the weather resistance (light) stabilizer, (a) benzotriazole compound, (b) benzophenone compound, (c) aromatic benzoate compound, (d) cyanoacrylate compound, (e) oxalic acid anilide compound, (F) A hindered amine compound can be exemplified.
耐候（光）安定剤は、単独で用いてもよいが、１種又は２種以上を組み合わせて使用するのが好ましく、（ａ）ベンゾトリアゾール系化合物、（ｂ）ベンゾフェノン系化合物、（ｃ）芳香族ベンゾエート系化合物、（ｄ）シアノアクリレート系化合物、及び／又は（ｅ）シュウ酸アニリド系化合物の耐候（光）安定剤と、（ｆ）ヒンダードアミン系化合物との併用が好ましい。
耐候（光）安定剤の添加量は、例えば、ポリアセタール樹脂１００質量部に対して０．０１～５質量部（例えば、０．０１～３質量部）、好ましくは０．０１～２質量部、さらに好ましくは０．１～２質量部（例えば、０．１～１．５質量部）程度である。 The weathering (light) stabilizer may be used alone, but is preferably used alone or in combination of two or more, (a) benzotriazole compounds, (b) benzophenone compounds, (c) aromatic A combination of a weather resistant (light) stabilizer of a group benzoate compound, (d) a cyanoacrylate compound, and / or (e) an oxalic acid anilide compound, and (f) a hindered amine compound is preferred.
The addition amount of the weathering (light) stabilizer is, for example, 0.01 to 5 parts by mass (for example, 0.01 to 3 parts by mass), preferably 0.01 to 2 parts by mass, relative to 100 parts by mass of the polyacetal resin More preferably, it is about 0.1 to 2 parts by mass (for example, 0.1 to 1.5 parts by mass).
耐候（光）安定剤の添加量は、例えば、ポリアセタール樹脂１００質量部に対して０．０１～５質量部（例えば、０．０１～３質量部）、好ましくは０．０１～２質量部、さらに好ましくは０．１～２質量部（例えば、０．１～１．５質量部）程度である。 The weathering (light) stabilizer may be used alone, but is preferably used alone or in combination of two or more, (a) benzotriazole compounds, (b) benzophenone compounds, (c) aromatic A combination of a weather resistant (light) stabilizer of a group benzoate compound, (d) a cyanoacrylate compound, and / or (e) an oxalic acid anilide compound, and (f) a hindered amine compound is preferred.
The addition amount of the weathering (light) stabilizer is, for example, 0.01 to 5 parts by mass (for example, 0.01 to 3 parts by mass), preferably 0.01 to 2 parts by mass, relative to 100 parts by mass of the polyacetal resin More preferably, it is about 0.1 to 2 parts by mass (for example, 0.1 to 1.5 parts by mass).
前記酸化防止剤、アルカリ又はアルカリ土類金属化合物及び安定剤は、それぞれ単独で用いてもよく、必要に応じて二種以上を組み合わせて使用してもよい。
The antioxidant, alkali or alkaline earth metal compound and stabilizer may be used alone or in combination of two or more as required.
本発明のポリアセタール樹脂組成物に、さらに着色剤を混合することも可能である。着色剤としては、各種染料または顔料が使用できる。染料はソルベント染料が好ましく、アゾ系染料、アントラキノン系染料、フタロシアニン系染料、又はナフトキノン系染料などが挙げられる。顔料については、無機顔料及び有機顔料のいずれも使用でき、単独で用いてもよく、また複数の着色剤を組み合わせて用いてもよい。
It is possible to further mix a colorant with the polyacetal resin composition of the present invention. Various dyes or pigments can be used as the colorant. The dye is preferably a solvent dye, and examples thereof include azo dyes, anthraquinone dyes, phthalocyanine dyes, and naphthoquinone dyes. As the pigment, any of inorganic pigments and organic pigments can be used, and they may be used alone or in combination with a plurality of colorants.
着色剤の含有量は、例えば、ポリアセタール樹脂１００質量部に対して、０～５質量部（例えば、０．０１～５質量部）、好ましくは０．１～４質量部、さらに好ましくは０．３～３質量部程度である。
The content of the colorant is, for example, 0 to 5 parts by mass (for example, 0.01 to 5 parts by mass), preferably 0.1 to 4 parts by mass, and more preferably 0.1 parts by mass with respect to 100 parts by mass of the polyacetal resin. About 3 to 3 parts by mass.
本発明のポリアセタール樹脂組成物には、必要に応じてその他、離型剤、核剤、帯電防止剤、難燃剤、界面活性剤、各種ポリマー、充填剤などを１種又は２種以上組み合わせて添加してもよい。
In addition to the polyacetal resin composition of the present invention, a mold release agent, a nucleating agent, an antistatic agent, a flame retardant, a surfactant, various polymers, a filler, and the like are added in combination of one or more as necessary. May be.
＜ポリアセタール樹脂組成物の製造方法＞
本発明のポリアセタール樹脂組成物は、粉粒状混合物や溶融混合物であってもよく、ポリアセタール樹脂と、本発明のエチレン共重合体および本発明のアミン化合物と、必要により他の添加剤とを慣用の方法で混合することにより調製できる。例えば、各成分を混合して、一軸又は二軸の押出機により混練して押出してペレットを調製した後、成形する方法、一旦組成の異なるペレット（マスターバッチ）を調製し、そのペレットを所定量混合（希釈）して成形に供し、所定の組成の成形品を得る方法、ポリアセタール樹脂のペレットに抑制剤を散布などにより付着させた後、成形し、所定の組成の成形品を得る方法などが採用できる。 <Method for producing polyacetal resin composition>
The polyacetal resin composition of the present invention may be a powdery granular mixture or a molten mixture. The polyacetal resin, the ethylene copolymer of the present invention and the amine compound of the present invention, and other additives, if necessary, are conventionally used. It can be prepared by mixing by the method. For example, each component is mixed, kneaded by a single or twin screw extruder, extruded to prepare pellets, and then molded, and once a pellet (master batch) with a different composition is prepared, a predetermined amount of the pellets are prepared. A method of obtaining a molded product having a predetermined composition by mixing (diluting), a method of obtaining a molded product having a predetermined composition, etc. after applying an inhibitor to the polyacetal resin pellets by spraying or the like. Can be adopted.
本発明のポリアセタール樹脂組成物は、粉粒状混合物や溶融混合物であってもよく、ポリアセタール樹脂と、本発明のエチレン共重合体および本発明のアミン化合物と、必要により他の添加剤とを慣用の方法で混合することにより調製できる。例えば、各成分を混合して、一軸又は二軸の押出機により混練して押出してペレットを調製した後、成形する方法、一旦組成の異なるペレット（マスターバッチ）を調製し、そのペレットを所定量混合（希釈）して成形に供し、所定の組成の成形品を得る方法、ポリアセタール樹脂のペレットに抑制剤を散布などにより付着させた後、成形し、所定の組成の成形品を得る方法などが採用できる。 <Method for producing polyacetal resin composition>
The polyacetal resin composition of the present invention may be a powdery granular mixture or a molten mixture. The polyacetal resin, the ethylene copolymer of the present invention and the amine compound of the present invention, and other additives, if necessary, are conventionally used. It can be prepared by mixing by the method. For example, each component is mixed, kneaded by a single or twin screw extruder, extruded to prepare pellets, and then molded, and once a pellet (master batch) with a different composition is prepared, a predetermined amount of the pellets are prepared. A method of obtaining a molded product having a predetermined composition by mixing (diluting), a method of obtaining a molded product having a predetermined composition, etc. after applying an inhibitor to the polyacetal resin pellets by spraying or the like. Can be adopted.
また、成形品に用いられる組成物の調製において、基体であるポリアセタール樹脂の粉粒体（例えば、ポリアセタール樹脂の一部又は全部を粉砕した粉粒体）と他の成分（アミン化合物、エチレン共重合体、アミン化合物とエチレン共重合体とのマスターバッチなど）を混合して溶融混練すると、添加物の分散を向上させるのに有利である。
Further, in the preparation of a composition used for a molded article, a powder of a polyacetal resin as a substrate (for example, a powder obtained by pulverizing part or all of a polyacetal resin) and other components (amine compound, ethylene copolymer) Mixing and melting and kneading a polymer, a master batch of an amine compound and an ethylene copolymer, etc. is advantageous in improving dispersion of the additive.
本発明の組成物から得られる成形品は、自動車分野での使用に最も適しているが、その他電気・電子分野の機構部品（能動部品や受動部品など）、建材・配管分野、日用品（生活）・化粧品分野、及び医用分野（医療・治療分野）の部品・部材として好適に使用される。
Molded articles obtained from the composition of the present invention are most suitable for use in the automotive field, but other mechanical / electrical parts such as mechanical parts (active parts and passive parts), building materials / piping, daily necessities (life). -It is suitably used as parts / members in the cosmetics field and medical field (medical / therapeutic field).
より具体的には、自動車分野の機構部品としては、インナーハンドル、フェーエルトランクオープナー、シートベルトバックル、アシストラップ、各種スイッチ、ノブ、レバー、クリップなどの内装部品、メーターやコネクターなどの電気系統部品、オーディオ機器やカーナビゲーション機器などの車載電気・電子部品、ウインドウレギュレーターのキャリアープレートに代表される金属と接触する部品、ドアロックアクチェーター部品、ミラー部品、ワイパーモーターシステム部品、燃料系統の部品などが例示できる。
More specifically, the mechanical parts in the automotive field include inner handles, fael trunk openers, seat belt buckles, assist wraps, various interior parts such as switches, knobs, levers, clips, electrical system parts such as meters and connectors, Examples include in-vehicle electrical and electronic parts such as audio equipment and car navigation equipment, parts that come into contact with metal, such as window regulator carrier plates, door lock actuator parts, mirror parts, wiper motor system parts, fuel system parts, etc. it can.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
なお、実施例及び比較例において、成形品からのホルムアルデヒドの発生量について、以下のようにして評価した。
In the examples and comparative examples, the amount of formaldehyde generated from the molded products was evaluated as follows.
［成形品からのホルムアルデヒド発生量］
実施例及び比較例で調製したポリアセタール樹脂組成物を用い、下記条件で平板状試験片（１００ｍｍ×４０ｍｍ×２ｍｍ）を成形した。この平板状試験片を２３℃、５０％ＲＨの雰囲気下で放置した後、平板状試験片２枚を１０Ｌのフッ化ビニル製サンプリングバッグに封入し脱気して、４Ｌの窒素を入れ、６５℃で２時間加熱した後、サンプリングバッグ内の窒素を０．５ｍｌ／ｍｉｎで３Ｌ抜き取り、発生したホルムアルデヒドをＤＮＰＨ（２、４－ジニトロフェニルヒドラジン）捕集管（Ｗａｔｅｒｓ社製 Ｓｅｐ－Ｐａｋ ＤＮＰＨ－Ｓｉｌｉｃａ）に吸着させた。その後、ＤＮＰＨ捕集管からＤＮＰＨとホルムアルデヒドとの反応物をアセトニトリルで溶媒抽出し、高速液体クロマトグラフでＤＮＰＨとホルムアルデヒドとの反応物の標準物質を用いた検量線法により、発生したホルムアルデヒド量を求め、試験片単位重量あたりのホルムアルデヒド発生量（μｇ／ｇ）を算出した。
[Formaldehyde generation from molded products]
Using the polyacetal resin compositions prepared in Examples and Comparative Examples, flat plate test pieces (100 mm × 40 mm × 2 mm) were molded under the following conditions. After leaving this flat test piece in an atmosphere of 23 ° C. and 50% RH, two flat test pieces were sealed in a 10 L vinyl fluoride sampling bag, deaerated, and 4 L of nitrogen was added. After heating at 0 ° C. for 2 hours, 3 L of nitrogen in the sampling bag was extracted at 0.5 ml / min, and the generated formaldehyde was collected from a DNPH (2,4-dinitrophenylhydrazine) collection tube (Water-Sep-Pak DNPH-Silica). ). Thereafter, the reaction product of DNPH and formaldehyde is extracted from the DNPH collection tube with acetonitrile, and the amount of generated formaldehyde is obtained by a calibration curve method using a standard substance of the reaction product of DNPH and formaldehyde by high performance liquid chromatography. The amount of formaldehyde generated per unit weight (μg / g) was calculated.
実施例及び比較例で調製したポリアセタール樹脂組成物を用い、下記条件で平板状試験片（１００ｍｍ×４０ｍｍ×２ｍｍ）を成形した。この平板状試験片を２３℃、５０％ＲＨの雰囲気下で放置した後、平板状試験片２枚を１０Ｌのフッ化ビニル製サンプリングバッグに封入し脱気して、４Ｌの窒素を入れ、６５℃で２時間加熱した後、サンプリングバッグ内の窒素を０．５ｍｌ／ｍｉｎで３Ｌ抜き取り、発生したホルムアルデヒドをＤＮＰＨ（２、４－ジニトロフェニルヒドラジン）捕集管（Ｗａｔｅｒｓ社製 Ｓｅｐ－Ｐａｋ ＤＮＰＨ－Ｓｉｌｉｃａ）に吸着させた。その後、ＤＮＰＨ捕集管からＤＮＰＨとホルムアルデヒドとの反応物をアセトニトリルで溶媒抽出し、高速液体クロマトグラフでＤＮＰＨとホルムアルデヒドとの反応物の標準物質を用いた検量線法により、発生したホルムアルデヒド量を求め、試験片単位重量あたりのホルムアルデヒド発生量（μｇ／ｇ）を算出した。
[Formaldehyde generation from molded products]
Using the polyacetal resin compositions prepared in Examples and Comparative Examples, flat plate test pieces (100 mm × 40 mm × 2 mm) were molded under the following conditions. After leaving this flat test piece in an atmosphere of 23 ° C. and 50% RH, two flat test pieces were sealed in a 10 L vinyl fluoride sampling bag, deaerated, and 4 L of nitrogen was added. After heating at 0 ° C. for 2 hours, 3 L of nitrogen in the sampling bag was extracted at 0.5 ml / min, and the generated formaldehyde was collected from a DNPH (2,4-dinitrophenylhydrazine) collection tube (Water-Sep-Pak DNPH-Silica). ). Thereafter, the reaction product of DNPH and formaldehyde is extracted from the DNPH collection tube with acetonitrile, and the amount of generated formaldehyde is obtained by a calibration curve method using a standard substance of the reaction product of DNPH and formaldehyde by high performance liquid chromatography. The amount of formaldehyde generated per unit weight (μg / g) was calculated.
* 成形機 ：ＦＡＮＵＣ ＲＯＢＯＳＨＯＴ α―Ｓ１００ｉａ
* 成形条件：シリンダー温度（℃）ノズル －Ｃ１－Ｃ２－Ｃ３
２２０ ２２０ ２２０ ２２０
射出圧力 ６０（ＭＰａ）
射出速度 １．０（ｍ／ｍｉｎ）
成形機内滞留時間 ３０分
金型温度 ８０（℃） * Molding machine: FANUC ROBOSHOT α-S100ia
* Molding conditions: Cylinder temperature (° C) nozzle -C1-C2-C3
220 220 220 220
Injection pressure 60 (MPa)
Injection speed 1.0 (m / min)
Residence time in molding machine 30 minutes Mold temperature 80 (℃)
* 成形条件：シリンダー温度（℃）ノズル －Ｃ１－Ｃ２－Ｃ３
２２０ ２２０ ２２０ ２２０
射出圧力 ６０（ＭＰａ）
射出速度 １．０（ｍ／ｍｉｎ）
成形機内滞留時間 ３０分
金型温度 ８０（℃） * Molding machine: FANUC ROBOSHOT α-S100ia
* Molding conditions: Cylinder temperature (° C) nozzle -C1-C2-C3
220 220 220 220
Injection pressure 60 (MPa)
Injection speed 1.0 (m / min)
Residence time in molding machine 30 minutes Mold temperature 80 (℃)
実施例及び比較例としてポリアセタール樹脂１００質量部に、表１、表２に示す材料、割合で混合した後、二軸押出機により溶融混合し、ペレット状の組成物を調製した。さらに、射出成形機により、試験片を成形し、この試験片からのホルムアルデヒド発生量を測定した。評価を表３に示す。なお、表１、表２における数値の単位は、質量部である。
As examples and comparative examples, 100 parts by mass of polyacetal resin were mixed in the materials and proportions shown in Tables 1 and 2, and then melt mixed by a twin screw extruder to prepare a pellet-shaped composition. Furthermore, the test piece was shape | molded with the injection molding machine, and the amount of formaldehyde generated from this test piece was measured. The evaluation is shown in Table 3. In addition, the unit of the numerical value in Table 1 and Table 2 is a mass part.
実施例および比較例で使用したポリアセタール樹脂等の材料は、以下の通りである。
１．（Ａ）ポリアセタール樹脂
（Ａ－１）：トリオキサン９６．７質量％と１、３－ジオキソラン３．３質量％とを共重合させてなるポリアセタール共重合体（メルトインデックス（１９０℃、荷重２１６０ｇで測定）：９ｇ／１０ｍｉｎ） Materials such as polyacetal resin used in Examples and Comparative Examples are as follows.
1. (A) Polyacetal resin (A-1): a polyacetal copolymer obtained by copolymerizing 96.7% by mass of trioxane and 3.3% by mass of 1,3-dioxolane (measured at a melt index (190 ° C., load 2160 g) ): 9 g / 10 min)
１．（Ａ）ポリアセタール樹脂
（Ａ－１）：トリオキサン９６．７質量％と１、３－ジオキソラン３．３質量％とを共重合させてなるポリアセタール共重合体（メルトインデックス（１９０℃、荷重２１６０ｇで測定）：９ｇ／１０ｍｉｎ） Materials such as polyacetal resin used in Examples and Comparative Examples are as follows.
1. (A) Polyacetal resin (A-1): a polyacetal copolymer obtained by copolymerizing 96.7% by mass of trioxane and 3.3% by mass of 1,3-dioxolane (measured at a melt index (190 ° C., load 2160 g) ): 9 g / 10 min)
２．（Ｂ）エチレン共重合体
（Ｂ－１）：エチレン－アクリル酸共重合体、アクリル酸変性率：５質量％ハネウェル社製、「Ａ－Ｃ５４０」
（Ｂ－２）：エチレン－メタクリル酸共重合体、メタクリル酸変性率：４質量％三井・デュポンポリケミカル（株）製、「ニュクレルＡＮ４２１４Ｃ」
（Ｂ－３）：エチレン－メタクリル酸共重合体、メタクリル酸変性率：１５質量％三井・デュポンポリケミカル（株）製、「ニュクレルＮ１５２５」 2. (B) Ethylene copolymer (B-1): ethylene-acrylic acid copolymer, acrylic acid modification rate: 5% by mass, manufactured by Honeywell, “A-C540”
(B-2): Ethylene-methacrylic acid copolymer, methacrylic acid modification rate: 4% by mass Mitsui DuPont Polychemical Co., Ltd. “Nucleel AN4214C”
(B-3): Ethylene-methacrylic acid copolymer, methacrylic acid modification rate: 15% by mass, Mitsui-DuPont Polychemical Co., Ltd. “Nucleel N1525”
（Ｂ－１）：エチレン－アクリル酸共重合体、アクリル酸変性率：５質量％ハネウェル社製、「Ａ－Ｃ５４０」
（Ｂ－２）：エチレン－メタクリル酸共重合体、メタクリル酸変性率：４質量％三井・デュポンポリケミカル（株）製、「ニュクレルＡＮ４２１４Ｃ」
（Ｂ－３）：エチレン－メタクリル酸共重合体、メタクリル酸変性率：１５質量％三井・デュポンポリケミカル（株）製、「ニュクレルＮ１５２５」 2. (B) Ethylene copolymer (B-1): ethylene-acrylic acid copolymer, acrylic acid modification rate: 5% by mass, manufactured by Honeywell, “A-C540”
(B-2): Ethylene-methacrylic acid copolymer, methacrylic acid modification rate: 4% by mass Mitsui DuPont Polychemical Co., Ltd. “Nucleel AN4214C”
(B-3): Ethylene-methacrylic acid copolymer, methacrylic acid modification rate: 15% by mass, Mitsui-DuPont Polychemical Co., Ltd. “Nucleel N1525”
３．（Ｃ）アミン化合物
（Ｃ－１）：トリス（ヒドロキシメチル）アミノメタン（ＴＨＡＭ）ｐＫｂ：５．７
（Ｃ－２）：２－アミノ－２－メチル－プロパノール（ＡＭＰ）ｐＫｂ：４．３
（Ｃ－３）：メラミン ｐＫｂ：９
（Ｃ－４）：ベンゾグアナミン ｐＫｂ：１０．１
４．（Ｄ）ヒンダートフェノール系酸化防止剤
（Ｄ－１）：ペンタエリスリトールテトラキス［３－（３、５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］ 3. (C) Amine compound (C-1): Tris (hydroxymethyl) aminomethane (THAM) pKb: 5.7
(C-2): 2-amino-2-methyl-propanol (AMP) pKb: 4.3
(C-3): Melamine pKb: 9
(C-4): Benzoguanamine pKb: 10.1
4). (D) Hindered phenol antioxidant (D-1): Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
（Ｃ－１）：トリス（ヒドロキシメチル）アミノメタン（ＴＨＡＭ）ｐＫｂ：５．７
（Ｃ－２）：２－アミノ－２－メチル－プロパノール（ＡＭＰ）ｐＫｂ：４．３
（Ｃ－３）：メラミン ｐＫｂ：９
（Ｃ－４）：ベンゾグアナミン ｐＫｂ：１０．１
４．（Ｄ）ヒンダートフェノール系酸化防止剤
（Ｄ－１）：ペンタエリスリトールテトラキス［３－（３、５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］ 3. (C) Amine compound (C-1): Tris (hydroxymethyl) aminomethane (THAM) pKb: 5.7
(C-2): 2-amino-2-methyl-propanol (AMP) pKb: 4.3
(C-3): Melamine pKb: 9
(C-4): Benzoguanamine pKb: 10.1
4). (D) Hindered phenol antioxidant (D-1): Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
表１～表３より明らかなように、比較例に比べて、実施例の樹脂組成物は、高温、長時間滞留という厳しい成形条件下で成形された成形品からのホルムアルデヒドの発生量が極めて小さいため、成形品の品質を向上できる。
As is apparent from Tables 1 to 3, the resin compositions of the examples have a very small amount of formaldehyde generated from molded products molded under severe molding conditions of high temperature and long-time retention compared to the comparative examples. Therefore, the quality of the molded product can be improved.
Claims (3)
- 少なくとも、
（Ａ）ポリアセタール樹脂１００質量部
（Ｂ）アクリル酸およびメタクリル酸から選択される少なくとも１種と、エチレンとの共重合体０．００１～１０質量部
（Ｃ）下記式（１）で表されるアミン化合物０．０１～１０質量部、
とを含有するポリアセタール樹脂組成物。
(A) Polyacetal resin 100 parts by mass (B) Copolymer of ethylene and at least one selected from acrylic acid and methacrylic acid (C) represented by the following formula (1) 0.01 to 10 parts by mass of an amine compound,
And a polyacetal resin composition.
- 前記（Ｂ）共重合体が、アクリル酸およびメタクリル酸から選択される少なくとも１種が０．５～４０質量％である共重合体である請求項１記載のポリアセタール樹脂組成物。 The polyacetal resin composition according to claim 1, wherein the copolymer (B) is a copolymer in which at least one selected from acrylic acid and methacrylic acid is 0.5 to 40% by mass.
- 前記（Ｃ）が、トリス（ヒドロキシメチル）アミノメタン、２－アミノ－２－エチル－プロパンジオール、および、２－アミノ－２－メチル－プロパノールから選択される少なくとの１種である請求項１または２記載のポリアセタール樹脂組成物。 2. (C) is at least one selected from tris (hydroxymethyl) aminomethane, 2-amino-2-ethyl-propanediol, and 2-amino-2-methyl-propanol. Or the polyacetal resin composition of 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2018066451A JP7109962B2 (en) | 2018-03-30 | 2018-03-30 | Polyacetal resin composition |
| JP2018-066451 | 2018-03-30 |
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| PCT/JP2019/008116 WO2019187983A1 (en) | 2018-03-30 | 2019-03-01 | Polyacetal resin composition |
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| WO2019204863A1 (en) | 2018-04-23 | 2019-10-31 | Netcomm Wireless Limited | Lightweight radome for housing an antenna |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09286899A (en) * | 1996-04-24 | 1997-11-04 | Polyplastics Co | Polyacetal resin composition |
| JP2000239484A (en) * | 1998-12-22 | 2000-09-05 | Polyplastics Co | Polyacetal resin composition and molded article |
| WO2000078898A1 (en) * | 1999-06-22 | 2000-12-28 | The Lubrizol Corporation | Aromatic mannich compound-containing composition and process for making same |
| JP2001192530A (en) * | 2000-01-07 | 2001-07-17 | Du Pont Kk | Polyacetal resin material for molding, molded article such as slide fastener emitting aroma, and method for producing molded article emitting aroma |
| JP2002020580A (en) * | 2000-07-11 | 2002-01-23 | Mitsubishi Engineering Plastics Corp | Polyacetal resin composition |
| JP2002020579A (en) * | 2000-07-11 | 2002-01-23 | Mitsubishi Engineering Plastics Corp | Polyacetal resin composition |
| JP2002541288A (en) * | 1999-04-07 | 2002-12-03 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Polyacetal resin with reduced formaldehyde odor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001142176A (en) | 1999-11-12 | 2001-05-25 | Fuji Photo Film Co Ltd | Molded article for photographic sensitive material |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09286899A (en) * | 1996-04-24 | 1997-11-04 | Polyplastics Co | Polyacetal resin composition |
| JP2000239484A (en) * | 1998-12-22 | 2000-09-05 | Polyplastics Co | Polyacetal resin composition and molded article |
| JP2002541288A (en) * | 1999-04-07 | 2002-12-03 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Polyacetal resin with reduced formaldehyde odor |
| WO2000078898A1 (en) * | 1999-06-22 | 2000-12-28 | The Lubrizol Corporation | Aromatic mannich compound-containing composition and process for making same |
| JP2001192530A (en) * | 2000-01-07 | 2001-07-17 | Du Pont Kk | Polyacetal resin material for molding, molded article such as slide fastener emitting aroma, and method for producing molded article emitting aroma |
| JP2002020580A (en) * | 2000-07-11 | 2002-01-23 | Mitsubishi Engineering Plastics Corp | Polyacetal resin composition |
| JP2002020579A (en) * | 2000-07-11 | 2002-01-23 | Mitsubishi Engineering Plastics Corp | Polyacetal resin composition |
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| JP2019178186A (en) | 2019-10-17 |
| JP7109962B2 (en) | 2022-08-01 |
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