JP2011052126A - Polyacetal resin composition, resin molded article, reforming method for polyacetal resin material composition, and reforming agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyacetal resin composition excellent in heat stability and weather resistance and suppressing the generation amount of formaldehyde and reduction of mechanical strength although it is colored by a pigment. <P>SOLUTION: In the polyacetal resin composition, 0.01-5 pts.wt. of a coloring agent selected from inorganic and organic pigments, 0.01-3 pts.wt. of a polyamide resin having at least either a physical property that the melting point or softening point is 180°C or less or a physical property that the amine value is 2 mgKOH/g or more, 0.01-1 pts.wt. of a dihydrazide compound, 0.01-5 pts.wt. of a hindered amine-based light stabilizer having a structure represented by formula (1) and 0.01-5 pts.wt. of a UV absorber are included in 100 pts.wt. of a polyacetal resin. In formula (1), X represents an organic group in which the bonding part with a nitrogen atom is a carbon atom, and Y represents an organic group bonded to a piperidyl group through an oxygen atom or a nitrogen atom, or a hydrogen atom. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyacetal resin composition and a resin molded article comprising the same. More specifically, the present invention relates to a colored polyacetal resin composition excellent in thermal stability and weather resistance, in which generation of formaldehyde and reduction in mechanical strength are suppressed, and a molded article comprising the same. The present invention also relates to a method for modifying a polyacetal resin raw material composition and a modifier.

  The polyacetal resin has an excellent balance of mechanical properties (friction resistance / abrasion resistance, creep resistance, dimensional stability, etc.) and has extremely excellent fatigue resistance. In addition, this resin is excellent in chemical resistance and has low water absorption. Therefore, polyacetal resin takes advantage of these characteristics, and as an engineering plastic, automotive interior parts, house interior parts (hot water mixer taps, etc.), clothing parts (fasteners, belt buckles, etc.), building materials applications (piping / pump parts) Etc.) and machine parts (gears, etc.), and demand is growing.

However, the polyacetal resin is thermally decomposed slightly due to the heat history during the production of the resin and during the processing and molding. As a result, formaldehyde is generated in a very small amount, and the mold is contaminated and the working (hygiene) environment during molding is deteriorated. Formaldehyde generated from resin products may cause sick house syndrome and the like.
In response to such a situation, the Ministry of Health, Labor and Welfare has issued a guideline value for formaldehyde concentration (upper limit 0.08 ppm) in the building room, and further reduction of the amount of formaldehyde generated from the polyacetal resin molded product is required.

  It is well known that by adding an additive to a polyacetal resin, the generation of formaldehyde from pellets and molded products can be suppressed, and various additives have been studied conventionally. For example, a melamine-formaldehyde polymer (Patent Document 1), a polyamine reaction product obtained by reacting a reaction product of polyamine and cyanuric chloride with ammonia or a derivative thereof (Patent Document 2), a dicyandiamide compound (Patent Document 3), a silane compound (Patent Document 4), nitrogen-containing compound-borate (Patent Document 5), glyoxydiureide compound (Patent Document 6), urea derivative and / or amidine derivative (Patent Document 7), phenols and basic nitrogen Condensates of compounds and aldehydes (Patent Document 8), triazine ring-containing spiro compounds (Patent Document 9) and the like have been proposed.

In addition, a method (Patent Document 10) for suppressing generation of formaldehyde by producing a polyacetal resin using a strong protonic acid such as trifluoromethanesulfonic acid as a catalyst has also been proposed. Furthermore, as an adsorbent for formaldehyde, aliphatic dihydrazide compounds such as adipic acid dihydrazide and 1,2,3,4-butanetetracarboxylic acid hydrazide compounds (Patent Document 11), combined use of these nitrogen-containing compounds and fatty acid metal salts (Patent Document 12) has also been proposed.
In general, inorganic pigments and organic pigments are used for coloring the polyacetal resin. However, when these pigments are blended, formaldehyde generation from the polyacetal resin pellets or molded articles thereof tends to increase. Therefore, in the case of a polyacetal resin colored with a pigment, it is a very important problem to suppress the generation of formaldehyde.

Japanese Patent Laid-Open No. 5-271516 JP-A-7-207118 JP-A-8-208946 Japanese Patent Laid-Open No. 9-235447 JP 10-36630 A Japanese Patent Laid-Open No. 10-182928 JP 2000-34417 A JP 2002-212384 A JP 2003-113289 A JP 2000-86738 A Japanese Patent Laid-Open No. 6-80619 JP-T-2004-522810

As described above, various methods for suppressing the generation of formaldehyde from the polyacetal resin have been studied, but no satisfactory method has yet been found.
In addition, the blending of the pigment not only lowers the thermal stability and weather resistance of the polyacetal resin, but also reduces the formaldehyde generation suppression effect by other additives. Therefore, in order to suppress the formaldehyde generation of the polyacetal resin colored with the pigment, it is necessary to add a large amount of additives in the conventional method. However, as a result of examination by the inventors of the present application, it was found that there is a problem that, when a large amount of the additive is blended, the mechanical properties of the resin are lowered and the moldability is deteriorated due to mold contamination during molding. . Accordingly, there is a need for a method that achieves both the coloring of the polyacetal resin with a pigment, the suppression of formaldehyde generation, the suppression of the deterioration of mechanical properties, the improvement of weather resistance and moldability.

  An object of the present invention is a polyacetal resin composition which is colored by blending of pigments, has excellent moldability, suppresses formaldehyde generation from pellets and molded products, and suppresses deterioration of mechanical properties of molded products, and has good weather resistance The object is to provide a product and a resin molded product comprising the same.

  The inventors of the present invention blended polyacetal resin colored with a conventional pigment with at least four kinds of specific additive components, which are excellent in moldability and weather resistance, and formaldehyde generation from pellets and resin molded products is remarkable. It was found that the reduction of the mechanical properties was also suppressed, and the present invention was completed. Specifically, the above object was achieved by the following means.

（式中、Ｘは窒素原子との結合部が炭素原子である有機基を示し、Ｙは、酸素原子または窒素原子を介してピペリジル基と結合する有機基または水素原子を示す。）
（２）（Ｃ）ポリアミド樹脂が、融点又は軟化点が１８０℃以下のポリアミド樹脂である、（１）に記載のポリアセタール樹脂組成物。
（３）（Ｃ）ポリアミド樹脂が、融点又は軟化点が１８０℃以下であり、かつ、アミン価２ｍｇＫＯＨ／ｇ以上である、（１）に記載のポリアセタール樹脂組成物。
（４）（Ｅ）ヒンダードアミン系光安定剤が、前記一般式（１）におけるＸが、炭素数１〜１０のアルキル基、下記式（２）または（３）で示される基から選ばれる基である、（１）〜（３）のいずれか１項に記載のポリアセタール樹脂組成物。

（５）（Ｅ）ヒンダードアミン系光安定剤が、下記式（４）〜（１２）で示される化合物から選ばれる少なくとも１種である、（１）〜（４）のいずれか１項に記載のポリアセタール樹脂組成物。

（６）（Ｆ）紫外線吸収剤がベンゾトリアゾール系化合物である、（１）〜（５）のいずれか１項に記載のポリアセタール樹脂組成物。
（７）（Ｆ）紫外線吸収剤が、２０℃における蒸気圧が１×１０^-8Ｐａ以下のものである、（１）〜（６）のいずれか１項に記載のポリアセタール樹脂組成物。
（８）（Ｆ）紫外線吸収剤が、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４，６−ビス（１−メチル−１−フェニルエチル）フェノールまたは２,２'−メチレンビス[６−（２Ｈ−ベンゾトリアゾール−２−イル）−４−（１,１,３,３−テトラメチルブチル）フェノール]である、（１）〜（７）のいずれか１項に記載のポリアセタール樹脂組成物。
（９）（Ｂ）着色剤が、チタンイエロー、チタンホワイト、ペリノン系顔料、フタロシアニン系顔料及びカーボンブラックより成る群から選ばれたものである、（１）〜（８）のいずれか１項に記載のポリアセタール樹脂組成物。
（１０）（Ｃ）ポリアミド樹脂が、ポリアミド１２、ポリアミド６／６６共重合体、ポリアミド６／１２共重合体、ポリアミド６／６６／６１０三元共重合体、ポリアミド６／６６／６１０／１２四元共重合体及びダイマー酸ポリアミド樹脂より成る群から選ばれたものである、（１）〜（９）のいずれか１項に記載のポリアセタール樹脂組成物。
（１１）（Ｃ）ポリアミド樹脂が、ダイマー酸ポリアミド樹脂である、（１）〜（９）のいずれか１項に記載のポリアセタール樹脂組成物。
（１２）（Ｄ）ジヒドラジド化合物が、ナフタレンジカルボン酸ヒドラジド、テレフタル酸ジヒドラジド、イソフタル酸ジヒドラジド、セバシン酸ジヒドラジド及びドデカン二酸ジヒドラジドからなる群から選ばれたものである、（１）〜（１１）のいずれかに記載のポリアセタール樹脂組成物。
（１３）（Ａ）ポリアセタール樹脂１００重量部に対し、さらに（Ｇ）立体障害性フェノール化合物を０．０１〜１重量部含有することを特徴とする、（１）〜（１２）のいずれか１項に記載のポリアセタール樹脂組成物。
（１４）（Ａ）ポリアセタール樹脂１００重量部に対し、さらに（Ｈ）アミノ置換トリアジン化合物を０．０１〜１０重量部含有する、（１）〜（１３）のいずれか１項に記載のポリアセタール樹脂組成物。
（１５）引張強度が６０ＭＰａ以上である、（１）〜（１４）のいずれか１項に記載のポリアセタール樹脂組成物。本発明における引張強度の値は、後記の実施例に記載される手順にしたがって、ＩＳＯ５２７規格に準拠して測定した値である。
（１６）（１）〜（１５）のいずれか１項に記載のポリアセタール樹脂組成物を成形して成るポリアセタール樹脂成形品。
（１７）（Ａ）ポリアセタール樹脂１００重量部を含有するポリアセタール樹脂原料組成物に、
（Ｂ）無機及び有機顔料から選ばれた着色剤 ０．０１〜５重量部、
（Ｃ）融点又は軟化点が１８０℃以下であるという物性か、アミン価が２ｍｇＫＯＨ／ｇ以上であるという物性の少なくとも一方を備えるポリアミド樹脂 ０．０１〜３重量部、
（Ｄ）芳香族ジヒドラジド化合物及び２０℃における水１００ｇに対する溶解度が１ｇ未満の脂肪族ジヒドラジド化合物より成る群から選ばれたジヒドラジド化合物 ０．０１〜１重量部、
（Ｅ）上記一般式（１）で示される構造を有するヒンダードアミン系光安定剤 ０．０１〜５重量部、及び
（Ｆ）紫外線吸収剤 ０.０１〜５重量部
を混合することを特徴とするポリアセタール樹脂原料組成物の改質方法。この改質方法については、上記各（２）〜（１５）の限定を好ましく加えることができる。
（１８）成形品の耐候性を向上させ、引張強度低下とホルムアルデヒド発生を抑制する、（１７）に記載の改質方法。
（１９）（Ｂ）無機及び有機顔料から選ばれた着色剤 ０．０１〜５重量部、
（Ｃ）融点又は軟化点が１８０℃以下であるという物性か、アミン価が２ｍｇＫＯＨ／ｇ以上であるという物性の少なくとも一方を備えるポリアミド樹脂 ０．０１〜３重量部、
（Ｄ）芳香族ジヒドラジド化合物及び２０℃における水１００ｇに対する溶解度が１ｇ未満の脂肪族ジヒドラジド化合物より成る群から選ばれたジヒドラジド化合物 ０．０１〜１重量部、
（Ｅ）上記一般式（１）で示される構造を有するヒンダードアミン系光安定剤 ０．０１〜５重量部、及び
（Ｆ）紫外線吸収剤 ０.０１〜５重量部
を含有することを特徴とするポリアセタール樹脂原料組成物用改質剤。この改質剤については、上記各（２）〜（１５）の限定を好ましく加えることができる。
（２０）成形品の耐候性を向上させ、引張強度低下とホルムアルデヒド発生を抑制する、（１９）に記載のポリアセタール樹脂原料組成物用改質剤。 (1) (A) To 100 parts by weight of polyacetal resin,
(B) 0.01 to 5 parts by weight of a colorant selected from inorganic and organic pigments,
(C) 0.01-3 parts by weight of a polyamide resin having at least one of a physical property that a melting point or a softening point is 180 ° C. or less, or a physical property that an amine value is 2 mgKOH / g or more,
(D) 0.01 to 1 part by weight of a dihydrazide compound selected from the group consisting of an aromatic dihydrazide compound and an aliphatic dihydrazide compound having a solubility in 100 g of water at 20 ° C. of less than 1 g;
(E) 0.01 to 5 parts by weight of a hindered amine light stabilizer having a structure represented by the following general formula (1), and (F) 0.01 to 5 parts by weight of an ultraviolet absorber. Polyacetal resin composition.

(In the formula, X represents an organic group in which the bond to the nitrogen atom is a carbon atom, and Y represents an organic group or a hydrogen atom bonded to the piperidyl group via an oxygen atom or a nitrogen atom.)
(2) The polyacetal resin composition according to (1), wherein the (C) polyamide resin is a polyamide resin having a melting point or a softening point of 180 ° C. or lower.
(3) The polyacetal resin composition according to (1), wherein the polyamide resin (C) has a melting point or softening point of 180 ° C. or lower and an amine value of 2 mgKOH / g or higher.
(4) (E) The hindered amine light stabilizer is a group selected from X in the general formula (1) selected from a group having 1 to 10 carbon atoms and a group represented by the following formula (2) or (3). The polyacetal resin composition according to any one of (1) to (3).

(5) (E) The hindered amine light stabilizer is at least one selected from compounds represented by the following formulas (4) to (12), according to any one of (1) to (4). Polyacetal resin composition.

(6) The polyacetal resin composition according to any one of (1) to (5), wherein the ultraviolet absorber (F) is a benzotriazole-based compound.
(7) The polyacetal resin composition according to any one of (1) to (6), wherein the ultraviolet absorber (F) has a vapor pressure at 20 ° C. of 1 × 10 ⁻⁸ Pa or less.
(8) (F) The ultraviolet absorber is 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol or 2,2′-methylenebis [6- The polyacetal resin composition according to any one of (1) to (7), which is (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] .
(9) In any one of (1) to (8), (B) the colorant is selected from the group consisting of titanium yellow, titanium white, perinone pigment, phthalocyanine pigment, and carbon black. The polyacetal resin composition as described.
(10) (C) Polyamide resin is polyamide 12, polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 6/66/610 terpolymer, polyamide 6/66/610/12 The polyacetal resin composition according to any one of (1) to (9), which is selected from the group consisting of an original copolymer and a dimer acid polyamide resin.
(11) The polyacetal resin composition according to any one of (1) to (9), wherein the (C) polyamide resin is a dimer acid polyamide resin.
(12) (D) The dihydrazide compound is selected from the group consisting of naphthalenedicarboxylic acid hydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide and dodecanedioic acid dihydrazide. The polyacetal resin composition in any one.
(13) Any one of (1) to (12), further comprising (G) a sterically hindered phenol compound in an amount of 0.01 to 1 part by weight per 100 parts by weight of the (A) polyacetal resin. The polyacetal resin composition according to Item.
(14) The polyacetal resin according to any one of (1) to (13), further containing 0.01 to 10 parts by weight of (H) an amino-substituted triazine compound with respect to 100 parts by weight of the (A) polyacetal resin. Composition.
(15) The polyacetal resin composition according to any one of (1) to (14), wherein the tensile strength is 60 MPa or more. The value of the tensile strength in the present invention is a value measured according to the ISO 527 standard according to the procedure described in the examples described later.
(16) A polyacetal resin molded product obtained by molding the polyacetal resin composition according to any one of (1) to (15).
(17) In the polyacetal resin raw material composition containing 100 parts by weight of (A) polyacetal resin,
(B) 0.01 to 5 parts by weight of a colorant selected from inorganic and organic pigments,
(C) 0.01-3 parts by weight of a polyamide resin having at least one of a physical property that a melting point or a softening point is 180 ° C. or less or a physical property that an amine value is 2 mgKOH / g or more,
(D) 0.01 to 1 part by weight of a dihydrazide compound selected from the group consisting of an aromatic dihydrazide compound and an aliphatic dihydrazide compound having a solubility in 100 g of water at 20 ° C. of less than 1 g;
(E) 0.01 to 5 parts by weight of a hindered amine light stabilizer having the structure represented by the general formula (1), and (F) 0.01 to 5 parts by weight of an ultraviolet absorber are mixed. A method for modifying a polyacetal resin raw material composition. With respect to this modification method, the above limitations (2) to (15) can be preferably added.
(18) The modification method according to (17), wherein the weather resistance of the molded product is improved, and a decrease in tensile strength and formaldehyde generation are suppressed.
(19) (B) 0.01 to 5 parts by weight of a colorant selected from inorganic and organic pigments,
(C) 0.01-3 parts by weight of a polyamide resin having at least one of a physical property that a melting point or a softening point is 180 ° C. or less or a physical property that an amine value is 2 mgKOH / g or more,
(D) 0.01 to 1 part by weight of a dihydrazide compound selected from the group consisting of an aromatic dihydrazide compound and an aliphatic dihydrazide compound having a solubility in 100 g of water at 20 ° C. of less than 1 g;
(E) 0.01 to 5 parts by weight of a hindered amine light stabilizer having the structure represented by the general formula (1), and (F) 0.01 to 5 parts by weight of an ultraviolet absorber. A modifier for a raw material composition of polyacetal resin. About this modifier, the limitation of said each (2)-(15) can be added preferably.
(20) The modifier for a polyacetal resin raw material composition according to (19), which improves the weather resistance of a molded product and suppresses the decrease in tensile strength and the generation of formaldehyde.

  The polyacetal resin composition of the present invention is excellent in thermal stability and weather resistance, and since generation of formaldehyde and mold contamination during molding processing are suppressed, it not only improves the working environment but also occurs from molded products. There is little decrease in formaldehyde content and mechanical strength of molded products. Therefore, as a countermeasure against so-called sick house syndrome, automobile interior parts, interior parts such as houses (hot water mixing taps, etc.), clothing parts (fasteners, belt buckles, etc.) and building materials (piping, pump parts, etc.), machine parts (gears, etc.) ) Can be suitably used.

FIG. 1 is a schematic diagram of a drop mold used in the evaluation of mold contamination of the embodiment of the present application.

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

(A) Polyacetal resin The polyacetal resin used in the present invention is a polymer having a repeating acetal structure represented by-(-O-CRH-) _n- (wherein R represents a hydrogen atom or an organic group). In general, the main structural unit is an oxymethylene group (—CH ₂ O—) in which R is a hydrogen atom. The polyacetal resin used in the present invention may be a copolymer (block copolymer) or a terpolymer containing a structural unit other than the oxymethylene unit in addition to the homopolymer consisting of only the oxymethylene unit, and only a linear structure. Alternatively, it may have a branched or crosslinked structure.
As structural units other than the oxymethylene unit, an oxyethylene group (—CH ₂ CH ₂ O—), an oxypropylene group (—CH ₂ CH ₂ CH ₂ O—), an oxybutylene group (—CH ₂ CH ₂ CH ₂ CH) _An optionally branched oxyalkylene group such as ₂ O—) having 2 to 10 carbon atoms is exemplified. Among these, an oxyalkylene group having 2 to 4 carbon atoms which may be branched is preferable, and an oxyethylene group is particularly preferable. The content of oxyalkylene groups other than oxymethylene groups in the polyacetal resin is usually 0.1 to 20% by weight.

  A number of methods for producing a polyacetal resin are known. In the present invention, a polyacetal resin produced by any method can be used. For example, as a method for producing a polyacetal resin having an oxymethylene group and an oxyalkylene group having 2 to 4 carbon atoms as structural units, an oxymethylene group such as formaldehyde trimer (trioxane) or tetramer (tetraoxane) is used. Produced by copolymerizing a cyclic oligomer and a cyclic oligomer containing an oxyalkylene group having 2 to 4 carbon atoms such as ethylene oxide, 1,3-dioxolane, 1,3,6-trioxocan, 1,3-dioxepane. be able to. As the polyacetal resin, it is preferable to use a copolymer of a cyclic oligomer such as trioxane or tetraoxane and ethylene oxide or 1,3-dioxolane, and it is particularly preferable to use a copolymer of trioxane and 1,3-dioxolane. preferable. The melt index (ASTM-D1238 standard: 190 ° C., 2.16 Kg) of the polyacetal resin is usually 1 to 100 g / 10 minutes, but preferably 0.5 to 80 g / 10 minutes.

(B) Colorant As the inorganic and organic pigments constituting the colorant (B), general inorganic pigments and organic pigments described in “Pigment Handbook (edited by the Japan Pigment Technical Association)” can be used. Examples of the inorganic pigments include (complex) metal oxides containing titanium such as titanium oxide and titanium yellow, zinc oxide, iron oxide, carbon black, ultramarine blue, zinc sulfide, and antimony trioxide. Examples of the organic pigment include phthalocyanine, anthraquinone, quinacridone, azo, isoindolinone, quinophthalone, perinone, and perylene pigments.

Content of the inorganic and organic pigment in the polyacetal resin composition of the present invention is 0.01 to 5 parts by weight with respect to 100 parts by weight of the (A) polyacetal resin. If the content is less than 0.01 part by weight, it cannot be colored significantly. The pigment content is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more. The upper limit of the content is 5 parts by weight, preferably 3 parts by weight or less, and more preferably 2 parts by weight or less. Generation | occurrence | production of formaldehyde can be suppressed by making a pigment into 5 weight part or less.
In addition, when blending the pigment, a dispersion aid or a spreading agent may be blended. Examples of the dispersion aid include amide wax, ester wax, and olefin wax, and examples of the spreading agent include liquid paraffin. A pigment may be used in combination with a dye to achieve a desired color.

(C) Polyamide resin In the present invention, (C) a polyamide resin having at least one of the physical property that the melting point or the softening point is 180 ° C. or less or the physical property that the amine value is 2 mgKOH / g or more is blended. By blending such a polyamide resin, the generation of formaldehyde can be effectively suppressed.

(C) As the polyamide resin having a melting point or softening point of 180 ° C. or lower, any of an aliphatic polyamide resin, an alicyclic polyamide resin, and an aromatic polyamide resin can be used.
The polyamide resin may be composed of one type of structural unit or may be composed of a plurality of types of structural units. The raw material of the polyamide resin is an ω-amino acid, preferably a linear ω-amino acid having 6 to 12 carbon atoms and a lactam thereof; adipic acid, sebacic acid, dodecanedicarboxylic acid, heptadecanedicarboxylic acid, isophthalic acid, terephthalic acid and other dicarboxylic acids Examples include acids and dimethyl esters thereof; diamines such as hexamethylenediamine. In the case of a copolymerized polyamide comprising a plurality of types of structural units, the copolymerization ratio, copolymerization form (random copolymer, block copolymer, cross-linked polymer) and the like can be arbitrarily selected. In the present invention, as the polyamide resin (C), polyamide 12, polyamide 6/12 copolymer, polyamide 6/66/610 copolymer, polyamide 6/66/610/12 copolymer, or the like is used. preferable.
The melting point or softening point is preferably 175 ° C. or lower, more preferably 170 ° C. or lower. By using such a polyamide resin, the polyamide resin is in a molten state at the temperature at which it is kneaded with the polyacetal resin, so that there is an advantage that the dispersibility of the polyamide resin is further improved.

  The melting point in the present invention is the temperature at the peak top of the endothermic peak observed by the differential scanning calorimetry (DSC) method. The endothermic peak is defined as an endothermic peak that is observed when the sample is heated and melted once to remove the influence of the thermal history on the crystallinity and then heated again. Specifically, in the case of polyamide 12, for example, it can be determined in the following manner. The temperature is raised from 30 to 210 ° C. at a rate of 10 ° C./min, held at 210 ° C. for 2 minutes, and then lowered to 50 ° C. at a rate of 20 ° C./min. Further, the temperature is raised to 210 ° C. at a rate of 10 ° C./min, and the melting point is obtained from the peak top of the endothermic peak observed at the time of temperature rise. The maximum temperature at the time of temperature increase may be appropriately adjusted according to the expected melting point of the polyamide resin, and is usually selected in the range of the melting point + 50 ° C. Further, the melting point of 180 ° C. or lower means that the melting point observed by DSC is always 180 ° C. or lower in the range of the weight average molecular weight of the polyamide resin from 500 to 100,000.

  The softening point in the present invention is a temperature measured in accordance with JIS K2207 standard.

  In the present invention, (C) a polyamide resin having an amine value of 2 mgKOH / g or more is also preferable. Such a polyamide resin having many amino groups at the terminal has an effect of neutralizing acidity caused by formic acid generated by oxidation of formaldehyde and suppressing decomposition of the polyacetal resin. The amine value is preferably 2.5 mgKOH / g or more, more preferably 3 mgKOH / g or more, still more preferably 5 mgKOH / g or more, and particularly preferably 8 mgKOH / g or more. By setting the amine value to 2 mgKOH / g or more, the decomposition of the polyacetal resin is more effectively suppressed. The upper limit of the amine value is not particularly defined, but is usually 100 mgKOH / g or less, preferably 80 mgKOH / g or less. The amine value is defined by the mass of calcium hydroxide (KOH) equivalent to perchloric acid necessary for neutralizing all basic components contained in the molecule per unit mass. . The amine value is obtained, for example, by dissolving 1 g of a sample in m-cresol, titrating with a perchloric acid methanol solution by potentiometric titration, and converting to mg of KOH.

  When a pigment is blended with the polyacetal resin, the polyacetal resin is easily decomposed and formaldehyde is easily generated. When this formaldehyde is oxidized, it becomes formic acid, and the acidity due to this formic acid further promotes the decomposition of the polyacetal resin. In the present invention, by blending a polyamide resin having many amino groups at the terminal, it is possible to neutralize the acidity caused by formic acid generated by oxidation of formaldehyde and to suppress the decomposition of the polyacetal resin, and it is surprising. In addition, there is an effect that the formaldehyde supplementation effect by the component (D) is not inhibited.

  Adjustment of the amine value of the polyamide resin is carried out by adjusting the charging ratio of dicarboxylic acid and diamine, or by heating and reacting the polyamide resin obtained by polymerization and a terminal adjusting agent such as amine. Can do. As the amine used as a terminal adjuster, those having 6 to 22 carbon atoms are preferable. For example, aliphatic amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine are used. Primary amines are mentioned.

  It is also preferable to use dimer acid. As is well known, dimer acid is a dimerization of unsaturated fatty acids such as oleic acid, linoleic acid, and erucic acid, one of which is a dibasic acid having 36 carbon atoms and / or a hydrogenated product. It is mainly composed of a small amount of a monobasic acid (monomer) having 18 carbon atoms and a tribasic acid (trimer) having 54 carbon atoms. The dimer acid polyamide resin obtained by reacting dimer acid and diamine has a softening point of 180 ° C. or less and can be suitably used.

  The weight average molecular weight of the polyamide resin is arbitrary, but is usually 500 to 100,000, preferably 1,000 to 50,000. In addition, a weight average molecular weight means the value of polystyrene conversion measured by the gel permeation chromatography (GPC) measurement.

  The (C) polyamide resin in the present invention is preferably a (C) polyamide resin having a melting point or softening point of 180 ° C. or less and an amine value of 2 mgKOH / g or more.

  (C) Content of a polyamide resin is 0.01-3 weight part with respect to 100 weight part of (A) polyacetal resin. When using 2 or more types, the total amount becomes the said range. If the content is less than 0.01 parts by weight, the effect of reducing the amount of formaldehyde generated from the molded product is too low. Conversely, if it exceeds 3 parts by weight, the mechanical strength of the molded article of the polyacetal resin composition will be reduced. The content of the polyamide resin is usually 0.05 parts by weight, particularly preferably 0.1 parts by weight or more with respect to 100 parts by weight of the polyacetal resin. Further, the upper limit is preferably 2 parts by weight or less, more preferably 1 part by weight or less.

(D) Dihydrazide Compound In the present invention, as the (D) dihydrazide compound, a dihydrazide compound selected from the group consisting of an aromatic dihydrazide compound and an aliphatic dihydrazide compound having a solubility in 100 g of water at 20 ° C. of less than 1 g is used.
(D) An aromatic dihydrazide compound is a compound in which hydrazine reacts with each acid group of an aromatic compound having two carboxylic acid groups or sulfonic acid groups. For example, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 1, 5-naphthalenedicarbohydrazide, 1,8-naphthalenedicarbohydrazide, 2,6-naphthalenedicarbohydrazide, 1,5-diphenylcarbonohydrazide, 2,4-toluenedisulfonyl hydrazide, 4,4′-oxybis Examples thereof include benzenesulfonyl hydrazide.

  Examples of the aliphatic dihydrazide compound having a solubility in 100 g of water at 20 ° C. (hereinafter sometimes referred to as water solubility) of less than 1 g include, for example, oxalic acid dihydrazide (water solubility of 0.2 g or less), sebacic acid dihydrazide (same as above). 0.01 g or less), 1,12-dodecanedicarbohydrazide (0.01 g or less), 1,18-octadecanedicarbohydrazide (0.1 g or less), and the like. An aliphatic dihydrazide compound having a water solubility of 1 g or more has an insufficient effect of suppressing the generation of formaldehyde from the polyacetal resin composition.

  (D) Preferred among the dihydrazide compounds include 2,6-naphthalenedicarbohydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, 1,12-dodecanedicarbohydrazide and the like. In particular, it is preferable to use sebacic acid dihydrazide, 1,12-dodecanedicarbohydrazide, terephthalic acid dihydrazide, or the like. The content of the dihydrazide compound is 0.01 to 1 part by weight with respect to 100 parts by weight of the polyacetal resin. If the content is less than 0.01 parts by weight, the effect of reducing the generation of formaldehyde from the molded product is insufficient. On the other hand, if the amount exceeds 1 part by weight, the deposit on the mold at the time of injection molding increases, and the molding cannot be performed efficiently. The preferred content of the dihydrazide compound is 0.03 to 0.3 parts by weight, and more preferably 0.05 to 0.15 parts by weight.

(E) A hindered amine light stabilizer (E) A hindered amine light stabilizer is an amine having a piperidine structure represented by the general formula (1). In the general formula (1), X is an organic group bonded to the nitrogen atom and carbon atom of the piperidyl group. Preferred examples of X include an alkyl group having 1 to 10 carbon atoms and a group represented by the formula (2) or (3). When X is an alkyl group, for example, a linear or branched alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a t-butyl group, a hexyl group, an octyl group, and a decyl group can be mentioned. A methyl group is particularly preferable. In addition, the (E) hindered amine light stabilizer used in the present invention can have a plurality of piperidine structures in the molecule, but all piperidine structures are N-carbon atoms-2,2,6,6. -A tetramethyl-4-piperidyl structure is preferred.

Specific examples of the preferred (E) hindered amine light stabilizer include the following compounds.
Formula (4): Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate Formula (5): 1- [2- [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine 6): Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate Formula (7): 1,2,2,6,6- Pentamethyl-4-piperidyl and tridecyl-1,2,3,4-butanetetracarboxylate (part of four Rs of butanetetracarboxylate are 1,2,2,6,6-pentamethyl-4-piperidyl groups A mixture of compounds in which is a tridecyl group)
Formula (8): 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β, β-tetramethyl-3,9 ( 2,4,8,10-tetraoxaspiro [5,5] udencan) -diethanol condensate (p is 1-3)
Formula (9): Condensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (n is 10 to 14)
1,2,2,6,6-Pentamethyl-4-piperidylmethacrylate represented by the above formula (10) Above formula (11): N, N ′, N ″, N ′ ″-tetrakis- (4,6 -Bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine (12): Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1 dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate

  In this invention, the said hindered amine compound may be used independently, or may use 2 or more types together. Particularly preferred among the hindered amines are hindered amines represented by formulas (5), (6), (7), (8), (9), (10) and (12).

  The content of the hindered amine light stabilizer is 0.01 to 5 parts by weight with respect to 100 parts by weight of the polyacetal resin. If the content is less than 0.01 parts by weight, sufficient weather resistance (cracking time delay effect) cannot be obtained. On the other hand, when the amount exceeds 5 parts by weight, the mechanical properties are remarkably deteriorated and the mold contamination increases. The preferable content of the hindered amine light stabilizer is 0.01 to 3 parts by weight, and more preferably 0.03 to 2 parts by weight.

(F) Ultraviolet absorber The (F) ultraviolet absorber used in the present invention is a compound having an action of absorbing ultraviolet rays. Preferably, it is selected from benzotriazole compounds, benzophenone compounds, aromatic benzoate compounds, cyanoacrylate compounds, and oxalic anilide ultraviolet absorbers.

  (F) Specific examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl)- 4- (1,1,3,3-tetramethylbutyl) phenol], 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2′-hydroxy-3 ′, 5′-di-isoamyl-phenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis- (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybe Zophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-oxybenzylbenzophenone, 2, -Hydroxy-4-methoxy-5-sulfobenzophenone, pt-butylphenyl salicylate, p-octylphenyl salicylate, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3, Examples thereof include 3′-diphenyl acrylate, N- (2-ethoxy-5-t-butylphenyl) oxalic acid diamide, N- (2-ethylphenyl) -N ′-(2-ethoxyphenyl) oxalic acid diamide, and the like.

These ultraviolet absorbers may be used alone or in combination of two or more. A preferable ultraviolet absorber is a benzotriazole-based compound, and a benzotriazole-based ultraviolet absorber having a vapor pressure of 1 × 10 ⁻⁸ Pa or less at 20 ° C. is particularly preferable. Specifically, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2,2′-methylenebis [6- (2H-benzotriazole- 2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol].

  Content of a ultraviolet absorber is 0.01-5 weight part with respect to 100 weight part of polyacetal resins. If the content is less than 0.01 parts by weight, sufficient weather resistance cannot be obtained. On the other hand, when the amount exceeds 5 parts by weight, the deterioration of mechanical properties becomes remarkable. The preferable content of the ultraviolet absorber is 0.01 to 3 parts by weight, and more preferably 0.03 to 2 parts by weight.

(G) Sterically hindered phenolic compound The polyacetal resin composition of the present invention comprises the above-mentioned components (B) to (F) as essential components in a polyacetal resin. It is preferable to add a functional phenol compound. (G) A sterically hindered phenol (hindered phenol) compound refers to a compound having in the molecule at least one structure having a substituent at the ortho position of the phenolic hydroxyl group represented by the following general formula (13).

In General Formula (13), R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group. Moreover, you may have arbitrary substituents R in a meta position and / or para position with respect to a phenolic hydroxyl group. n is an integer of 0 to 3, preferably 0 or 1.
Examples of the alkyl group represented by R ¹ and R ² include those having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, and amyl groups. Of these, a bulky branched alkyl group such as a t-butyl group is preferable, and at least one of R ¹ and R ² is preferably such a branched alkyl group. Examples of the substituent for the alkyl group include halogen atoms such as chlorine.
R preferably has 4 or more carbon atoms. Moreover, this substituent R may be couple | bonded with the carbon atom of the aromatic ring by the carbon-carbon bond, and may couple | bond together through atoms other than carbon.

  Examples of the (G) sterically hindered phenol compound used in the present invention include 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-methylene-bis (2,6-di). -T-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,5-di-t-butyl-4 -Hydroxybenzyldimethylamine, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2,6,7-trioxa -1-phospha-bicyclo [2,2,2] -oct-4-yl-methyl-3,5-di-t-butyl-4-hydroxyhydrocinnamate, 3,5-di-t-butyl- -Hydroxyphenyl-3,5-distearyl-thiotriazylamine, 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chlorobenzotriazole, 2,6-di-t-butyl -4-hydroxymethylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, N, N'- Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6- Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-t-butyl 4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3,5-dimethyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl- 4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2′-thiodiethyl-bis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] and the like.

  Among these, a compound having a structure represented by the following formula (14) such as N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) is preferable. It is.

In General formula (14), R < ¹ > and R < ² > are respectively synonymous with General formula (13), and its preferable range is also synonymous.

  Also, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3,5-dimethyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl- 4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2′-thiodiethyl-bis [3- (3,5 3,5-dialkyl-4-hydride in the 3-position, such as -di-t-butyl-4-hydroxyphenyl) propionate] Also preferred are esters of propionic acid and polyhydric alcohols having a roxyphenyl group.

  (G) Content of a sterically hindered phenol compound is 0.01-1 weight part with respect to 100 weight part of (A) polyacetal resin. When the content is less than 0.01 parts by weight, the effect of suppressing thermal decomposition is low, and as a result, the effect of suppressing the generation of formaldehyde from the molded product is small. On the other hand, if the amount exceeds 1 part by weight, bleeding from the surface of the molded product becomes prominent. The preferred content is 0.1 to 0.5 parts by weight.

(H) Amino-substituted triazine compound The polyacetal resin composition of the present invention comprises the above-mentioned components (B) to (F) as essential components in a polyacetal resin. It is preferable to add a compound. The amino-substituted triazine compound is an amino-substituted triazine having a structure represented by the following general formula (15), or an initial polycondensate of this with formaldehyde.

In the general formula (15), R ³ , R ⁴ and R ⁵ may each independently be substituted with a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group. A good aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an optionally substituted amino group is shown, but at least one of R ^{3 to} R ⁵ may be substituted. An amino group is shown.

  Specific examples of the amino-substituted triazine compound include, for example, guanamine, melamine, N-butylmelamine, N-butylmelamine, N-phenylmelamine, N, N-diphenylmelamine, N, N-diallylmelamine, N, N ′, N ″ -Triphenylmelamine, N, N ′, N ″ -trimethylolmelamine, benzoguanamine, 2,4-diamino-6-methyl-sym-triazine, 2,4-diamino-6-butyl-sym-triazine, 2,4-diamino-6-benzyloxy-sym-triazine, 2,4-diamino-6-butoxy-sym-triazine, 2,4-diamino-6-cyclohexyl-sym-triazine, 2,4-diamino-6 -Chloro-sym-triazine, 2,4-diamino-6-mercapto-sym-triazine, ameline (N, , N ', N'-tetramethyl-cyanoethyl benzoguanamine) and the like. These amino-substituted triazine compounds may be used as an initial polycondensate (prepolymer) with formaldehyde. For example, it is preferable to use an initial polycondensate of formaldehyde with melamine, methylolmelamine, benzoguanamine or the like, and it is particularly preferable to use a water-soluble melamine-formaldehyde resin.

  When (H) the amino-substituted triazine compound is contained, the content is preferably 0.01 to 10 parts by weight, more preferably 7 parts by weight or less, and particularly preferably 5 parts by weight or less with respect to 100 parts by weight of the polyacetal resin. If the content is too large, the resin composition may be poorly dispersed during the preparation of the resin composition, and may aggregate in the polyacetal resin composition, resulting in so-called foreign matter.

Other Components The polyacetal resin composition of the present invention may further contain an alkali metal or alkaline earth metal hydroxide, inorganic acid salt or alkoxide. For example, hydroxides such as sodium, potassium, calcium and magnesium, inorganic acid salts such as carbonate, phosphate, silicate and borate, and alkoxides such as methoxide and ethoxide are blended. In particular, an alkaline earth metal compound is preferably blended, and calcium hydroxide, magnesium hydroxide, calcium carbonate, or magnesium carbonate is particularly blended.

In addition to the above components, the polyacetal resin composition of the present invention may be blended with various known additives and fillers within a range that does not impair the object of the present invention. Examples of the additive include a lubricant, a release agent, an antistatic agent, a flame retardant, and the like. Examples of the filler include glass fiber, glass flake, glass bead, talc, mica, and potassium titanate whisker. .
Content of components other than said (A)-(F) in the polyacetal resin composition of this invention is 100 weight of polyacetal resin, when components other than said (A)-(F) are flame retardants and a filler. The amount is preferably 0 to 50 parts by weight, more preferably 5 to 40 parts by weight, and particularly preferably 10 to 30 parts by weight. When the components other than the above (A) to (F) are a lubricant and a release agent, 0 to 20 parts by weight is preferable, 0.05 to 10 parts by weight is more preferable, and 0 to 10 parts by weight with respect to 100 parts by weight of the polyacetal resin. .1 to 5 parts by weight is particularly preferable. When the component other than the above (A) to (F) is an antistatic agent, 0 to 10 parts by weight is preferable, 0.05 to 5 parts by weight is more preferable, and 0.1 to 100 parts by weight of the polyacetal resin. -3 parts by weight is particularly preferred.

Manufacturing method of polyacetal resin composition The manufacturing method of the polyacetal resin composition of this invention is not specifically limited, Said (A)-(F) component and the other component added as needed are included. It can be produced by mixing and kneading in any order. Conditions such as mixing and kneading temperature and pressure may be appropriately selected in view of a conventionally known method for producing a polyacetal resin composition. For example, the kneading may be performed at a temperature higher than the melting temperature of the polyacetal resin, but usually it is preferably performed at 180 ° C. or higher. As a manufacturing apparatus, a mixing and kneading apparatus conventionally used for manufacturing this type of resin composition may be used.

  Specifically, for example, for (A) polyacetal resin, (B) colorant, (C) polyamide, (D) dihydrazide compound, (E) hindered amine light stabilizer, and (F) ultraviolet absorber. Predetermined amounts are blended simultaneously or in any order, and if desired, (G) a sterically hindered phenol compound, (H) an amino-substituted triazine compound or other additives are blended, and then mixed by a tumbler blender or the like. . Next, the obtained mixture is melt-kneaded with a single-screw or twin-screw extruder, extruded into a strand, and pelletized to obtain a polyacetal resin composition having a desired composition.

As another method, for (A) polyacetal resin, (C) polyamide resin, (D) dihydrazide compound, (E) hindered amine light stabilizer, and (F) ultraviolet absorber, and optionally (G) After mixing the sterically hindered phenol compound and the (H) amino-substituted triazine compound, the mixture is melt-kneaded and pelletized. A polyacetal resin composition having a desired color tone can also be obtained by adding a colorant selected from (B) inorganic and organic pigments to this, and then mixing, melting and kneading again to form pellets.
The polyacetal resin composition of the present invention thus obtained has high weather resistance, and has a mechanical strength, for example, a tensile strength measured according to the ISO 527 standard of 60 MPa or more, preferably 62 MPa or more can be achieved, the amount of formaldehyde generated and mold contamination is small, and the balance of these performances is excellent compared to conventional polyacetal resin compositions.

Method for modifying polyacetal resin material composition The method for modifying a polyacetal resin material composition of the present invention is a method for modifying a polyacetal resin material composition containing a polyacetal resin. In particular, it is a method of modifying the polyacetal resin raw material composition so as to color the polyacetal resin raw material composition, improve the weather resistance of the molded article, and suppress the decrease in tensile strength and the generation of formaldehyde. In the present invention, a composition containing a polyacetal resin to be modified is particularly referred to as a polyacetal resin raw material composition.

  In the modifying method of the present invention, 0.01 to 5 parts by weight of a colorant selected from (B) inorganic and organic pigments with respect to 100 parts by weight of (A) polyacetal resin contained in the polyacetal resin raw material composition, C) 0.01-3 parts by weight of a polyamide resin having at least one of a physical property that a melting point or a softening point is 180 ° C. or less, or a physical property that an amine value is 2 mgKOH / g or more, (D) an aromatic dihydrazide compound, and 0.01-1 part by weight of a dihydrazide compound selected from the group consisting of aliphatic dihydrazide compounds having a solubility in 100 g of water at 20 ° C. of less than 1 g, (E) a hindered amine light having a structure represented by the above general formula (1) It is characterized by mixing 0.01 to 5 parts by weight of stabilizer and 0.01 to 5 parts by weight of (F) ultraviolet absorber. The polyacetal resin raw material composition may contain components other than the components (A) to (F) within a range not impairing the object of the present invention. Moreover, you may add components other than the component of (A)-(F) to the polyacetal resin raw material composition in the range which does not impair the objective of this invention. For details of each component, reference can be made to the above description of each component.

The modifier of the polyacetal resin raw material composition The modifier of the present invention is (B) 0.01 to 5 parts by weight of a colorant selected from inorganic and organic pigments, and (C) the melting point or softening point is 180 ° C. or less. 0.01-3 parts by weight of a polyamide resin having at least one of the physical property of having an amine value of 2 mgKOH / g or more, (D) solubility in 100 g of aromatic dihydrazide compound and water at 20 ° C. is less than 1 g 0.01 to 1 part by weight of a dihydrazide compound selected from the group consisting of aliphatic dihydrazide compounds, (E) 0.01 to 5 parts by weight of a hindered amine light stabilizer having a structure represented by the above general formula (1), and (F) 0.01 to 5 parts by weight of an ultraviolet absorber is contained. The modifier of this invention is added with respect to the polyacetal resin raw material composition containing polyacetal resin. By adding the modifier of the present invention, the polyacetal resin raw material composition is colored, and at the same time, in particular, the polyacetal resin raw material composition is improved so as to improve the weather resistance of the molded article and suppress the decrease in tensile strength and formaldehyde generation. It can be modified. The modifier of the present invention may contain components other than the components (A) to (F) as long as the object of the present invention is not impaired. The details of each component of the modifier of the present invention can also be referred to the above description of each component.

  The addition amount of the modifier of the present invention is such that the amount of (B) colorant contained in the modifier is 0.01 to 5 with respect to 100 parts by weight of (A) polyacetal resin contained in the polyacetal resin raw material composition. The amount to be parts by weight is preferred. (B) The lower limit of the amount of the colorant is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and the upper limit is preferably 3 parts by weight or less. It is more preferable that the amount is not more than parts by weight.

Molding Method The resin composition of the present invention can be molded according to a known polyacetal resin molding method. From the viewpoint of fluidity and workability, injection molding is preferred. As a molded article made of the resin composition of the present invention, materials such as pellets, round bars, thick plates, sheets, tubes, various containers, machines, electricity, automobiles, building materials, and other various parts have been conventionally used. There are various products known as applications.

Hereinafter, the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
The raw materials and measurement methods used in Examples and Comparative Examples are shown below.

<Raw material>
(1) Acetal copolymer produced by using 1,3-dioxolane as a polyacetal resin comonomer so as to be 4.2% by weight based on the resin, melt index (ASTM-D1238 standard: 190 ° C., 2.16 Kg) 5g / 10min

(2) Inorganic pigment Inorganic pigment-1: Titanium white; Pigment White 6 (Ishihara Sangyo Co., Ltd., trade name: Taipei CR-63)
Inorganic pigment-2: Carbon black; Pigment Black 7 (product name: Printex, manufactured by Evonik Degussa Japan)

(3) Organic Pigment Organic Pigment-1: Perinone Orange; Pigment Orange 43 (manufactured by Clariant Japan, trade name: PV Fast Orange GRL)
Organic pigment-2: phthalocyanine blue; Pigment Blue 15: 3 (manufactured by Sumika Color Co., Ltd., trade name: Sumitocyanin Blue GH)

(4) Polyamide resin Polyamide resin-1: Polyamide 6/66/610 ternary copolymer (trade name: Amilan CM4000, melting point 140 ° C., amine value 3.0 mgKOH / g, manufactured by Toray Industries, Inc.)
Polyamide resin-2: Dimer acid polyamide (manufactured by Kao Corporation, trade name: Rheamide FT-409, melting point 115 ° C., amine value 10.4 mg KOH / g)
Polyamide resin-3: Polyamide 6 (Mitsubishi Engineering Plastics Co., Ltd., trade name: Novamid (registered trademark) 1010C2, melting point 220 ° C., amine value 1.5 mgKOH / g). This is not a polyamide resin as defined in the present invention.

(5) Dihydrazide compound Dihydrazide compound-1: terephthalic acid dihydrazide; solubility in water of 100 g (20 ° C.) is 0.01 g or less (manufactured by Nippon Finechem, product number: TDH)
Dihydrazide compound-2: 1,10-dodecanedioic acid dihydrazide; solubility in water of 100 g (20 ° C.) is 0.01 g or less (manufactured by Nippon Finechem Co., Ltd., product number: N-12)
Dihydrazide compound-3: adipic acid dihydrazide; solubility in 9.1 g of water (100 ° C.) (Nippon Finechem, product number: ADH), which is not a dihydrazide compound defined in the present invention.

(6) Hindered amine light stabilizer Hindered amine light stabilizer-1: 1,2,3,4-butanetetracarboxylate mixed with 1,2,2,6,6-pentamethyl-4-piperidyl- and tridecyl- ADEKA, product name: ADK STAB LA-62)
Hindered amine light stabilizer-2: condensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, (Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 622)
Hindered amine light stabilizer-3: bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (manufactured by Sankyo Lifetech Co., Ltd., trade name: SANOL LS-765)
Hindered amine light stabilizer-4: bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, manufactured by Sankyo Lifetech Co., Ltd., trade name: Sanol LS-770), which is the present invention It is not a hindered amine light stabilizer.

(7) Ultraviolet absorber 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 234, vapor pressure at 20 ° C. 2.0 × 10 ⁻¹⁰ Pa)

(8) Steric hindrance phenol compound N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) (manufactured by Ciba Specialty Chemicals, trade name: Iruga) Knox 1098)

(9) Amino-substituted triazine compound melamine (Mitsui Chemicals, product number: melamine)

<Measurement and evaluation>
Measurement and evaluation were performed by the following methods.
(A) Amine value 3 g of polyamide resin-1 to polyamide resin-3 were weighed and dissolved in 80 ml of m-cresol. For potential difference determination, AT-500N manufactured by Kyoto Electronics Industry Co., Ltd. is used, and titration is performed by a potentiometric method using a 0.05 mol / l perchloric acid methanol solution as a titrant. The amine value is converted to mg of KOH. Asked.

(B) Formaldehyde generation amount A flat plate of 100 mm × 40 mm × 2 mm was molded as a test piece at a cylinder temperature of 215 ° C. using a PS-40E5ASE molding machine manufactured by Nissei Plastic Industries. On the day after molding, the amount of formaldehyde was measured by the following method for this test piece in accordance with the method described in German Automobile Manufacturers Association Standard VDA275 (automobile interior parts-quantitative determination of formaldehyde emission by revised flask method).
(I) 50 ml of distilled water was put in a polyethylene container, the lid was closed with the test piece suspended in the air, and heated in a sealed state at 60 ° C. for 3 hours.
(Ii) After leaving at room temperature for 60 minutes, the test piece was taken out.
(Iii) The amount of formaldehyde absorbed in distilled water in a polyethylene container was measured by an acetylacetone colorimetric method using a UV spectrometer.

(C) Crack generation time (weather resistance)
A flat plate of 100 mm × 40 mm × 2 mm was molded as a test piece at a cylinder temperature of 215 ° C. using a PS-40E5ASE molding machine manufactured by Nissei Plastic Industry. The resulting molded product was exposed to 83 ° C with a sunshine weatherometer “WEL-SUN-DCH-B” manufactured by Suga Test Instruments Co., Ltd., and observed for deterioration phenomena such as whitening and cracks on the surface of the molded product with an optical microscope. The time until the start of cracking was defined as the crack occurrence time. The longer the crack occurrence time, the better the weather resistance.

(D) Mold Contamination 3000 shots at a molding temperature of 230 ° C. and a mold temperature of 35 ° C. using a drop mold as shown in FIG. 1 using a mini mat M8 / 7A molding machine manufactured by Sumitomo Heavy Industries, Ltd. Continuous molding was carried out, and after completion, the state of the mold deposit was observed with the naked eye and evaluated according to the following two standards. The drop mold shown in FIG. 1 is a mold designed so that the generated gas is easily collected at the tip P portion by introducing the resin composition from the gate G. The width of the gate G is 1 mm, the thickness is 1 mm, h1 in FIG. 1 is 14.5 mm, h2 is 7 mm, h3 is 27 mm, and the thickness of the molded part is 3 mm.
○: Mold adhesion is small and mold contamination is good.
X: There are many mold deposits and the mold contamination is poor.

(E) Tensile strength Using an SG-75 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., an ISO tensile test specimen was prepared in accordance with the ISO9988-2 standard. Using the obtained test piece, the tensile strength was measured according to the ISO 527 standard.

[Examples 1 to 10, Comparative Examples 1 to 14]
Each component is blended according to the weight blending formulation shown in Tables 1 and 2 below with respect to 100 parts by weight of the polyacetal resin, 0.1 parts by weight of ethylenebisstearylamide as a dispersion aid, and 0 liquid paraffin as a spreading agent. .1 part by weight was mixed and mixed with a tumbler type blender. The obtained mixture was melt-kneaded and pelletized with a 40 mmφ single screw extruder (manufactured by Tanabe Plastics, model: VS-40) at a cylinder temperature of 200 ° C. and a discharge rate of 13 kg / hr to obtain a polyacetal resin composition. It was. The resin composition was dried at 80 ° C. for 4 hours and then injection molded, and the amount of formaldehyde generated, crack generation time, mold contamination, and tensile strength were measured.
The results are shown in Tables 1 and 2. The formaldehyde generation amount was displayed as a relative value when the value of Comparative Example 1 was used as a reference (1.00).

  As is clear from Tables 1 and 2, the polyacetal resin composition of the present invention is not colored with a pigment, but suppresses formaldehyde generation, improves weather resistance, suppresses mold contamination, and reduces mechanical strength. It turns out that it is an excellent one that plays an effect at the same time. In particular, when a polyamide resin having a high amine value of the polyamide resin is contained, the effect of suppressing the generation of formaldehyde is high. On the other hand, in Comparative Examples 1 to 4, 7, 10, 11, 13, and 14 that do not contain the polyamide resin of the present invention, a large amount of formaldehyde was generated, and a comparison was made in which the content of the dihydrazide compound was increased without containing the polyamide resin. In Example 8, the amount of formaldehyde generated is reduced, but the mold contamination is significant and the tensile strength is also reduced. Comparative Example 9 containing no dihydrazide compound of the present invention and Comparative Example 12 containing aliphatic dihydrazide (dihydrazide compound-3) having high water solubility have a large amount of formaldehyde generated. In Comparative Examples 1, 3, and 5 containing no ultraviolet absorber, the crack generation time is short and the weather resistance is poor.

  In Examples 1 to 10, with respect to 100 parts by weight of the polyacetal resin, if the amount of the colorant added is less than 0.01 parts by weight, the coloring effect is greatly reduced, and if it exceeds 5 parts by weight, the formaldehyde generation suppressing effect is greatly reduced. To do. Moreover, in Examples 1-10, when the addition amount of the polyamide resin satisfying the conditions of the present invention is less than 0.01 parts by weight with respect to 100 parts by weight of the polyacetal resin, the effect of suppressing formaldehyde generation is greatly reduced, and 3 parts by weight. If it is too high, the mechanical strength of the molded product is greatly reduced. Furthermore, in Examples 1-10, when the addition amount of the dihydrazide compound satisfying the conditions of the present invention is less than 0.01 parts by weight with respect to 100 parts by weight of the polyacetal resin, the formaldehyde generation inhibitory effect is greatly reduced, and 1 part by weight. If it is too high, the effect of suppressing mold contamination is greatly reduced. In Examples 1 to 10, the weather resistance is greatly reduced when the amount of the hindered amine light stabilizer is less than 0.01 parts by weight with respect to 100 parts by weight of the polyacetal resin, and the mechanical properties are more than 5 parts by weight. Greatly reduces mold contamination. Further, in Examples 1 to 10, with respect to 100 parts by weight of the polyacetal resin, the weather resistance is greatly lowered when the addition amount of the ultraviolet absorber is less than 0.01 parts by weight, and when the amount exceeds 5 parts by weight, the mechanical properties are large. descend. The polyacetal resin composition of the present invention has a coloring effect, formaldehyde generation suppression effect, weather resistance improvement effect, mold contamination suppression effect, and mechanical strength by controlling the amount of each component added to the polyacetal resin within a specific range. All of the reduction suppressing effects can be satisfied.

G Gate P Tip

Claims (20)

(A) To 100 parts by weight of polyacetal resin,
(B) 0.01 to 5 parts by weight of a colorant selected from inorganic and organic pigments,
(C) 0.01-3 parts by weight of a polyamide resin having at least one of a physical property that a melting point or a softening point is 180 ° C. or less, or a physical property that an amine value is 2 mgKOH / g or more,
(D) 0.01 to 1 part by weight of a dihydrazide compound selected from the group consisting of an aromatic dihydrazide compound and an aliphatic dihydrazide compound having a solubility in 100 g of water at 20 ° C. of less than 1 g;
(E) 0.01 to 5 parts by weight of a hindered amine light stabilizer having a structure represented by the following general formula (1), and (F) 0.01 to 5 parts by weight of an ultraviolet absorber. Polyacetal resin composition.

(In the formula, X represents an organic group in which the bond to the nitrogen atom is a carbon atom, and Y represents an organic group or a hydrogen atom bonded to the piperidyl group via an oxygen atom or a nitrogen atom.) (C) Polyacetal resin composition of Claim 1 whose polyamide resin is a polyamide resin whose melting | fusing point or softening point is 180 degrees C or less. The polyacetal resin composition according to claim 1, wherein (C) the polyamide resin has a melting point or softening point of 180 ° C or lower and an amine value of 2 mgKOH / g or higher. (E) The hindered amine light stabilizer, wherein X in the general formula (1) is a group selected from an alkyl group having 1 to 10 carbon atoms and a group represented by the following formula (2) or (3) Item 4. The polyacetal resin composition according to any one of Items 1 to 3.

(E) The polyacetal resin composition of any one of Claims 1-4 whose hindered amine light stabilizer is at least 1 sort (s) chosen from the compound shown by following formula (4)-(12).

(F) The polyacetal resin composition of any one of Claims 1-5 whose ultraviolet absorber is a benzotriazole type compound. The polyacetal resin composition according to any one of claims 1 to 6, wherein the ultraviolet absorber (F) has a vapor pressure at 20 ° C of 1 × 10 ^-8 Pa or less. (F) The ultraviolet absorber is 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol or 2,2′-methylenebis [6- (2H— The polyacetal resin composition according to claim 1, which is benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol]. The polyacetal resin composition according to any one of claims 1 to 8, wherein (B) the colorant is selected from the group consisting of titanium yellow, titanium white, perinone pigment, phthalocyanine pigment, and carbon black. object. (C) Polyamide resin is polyamide 12, polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 6/66/610 ternary copolymer, polyamide 6/66/610/12 quaternary copolymer The polyacetal resin composition according to any one of claims 1 to 9, which is selected from the group consisting of a coalescence and a dimer acid polyamide resin. (C) Polyacetal resin composition of any one of Claims 1-9 whose polyamide resin is a dimer acid polyamide resin. (D) The dihydrazide compound is selected from the group consisting of naphthalenedicarboxylic acid hydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide and dodecanedioic acid dihydrazide. Polyacetal resin composition. The polyacetal according to any one of claims 1 to 12, further comprising 0.01 to 1 part by weight of (G) a sterically hindered phenol compound with respect to 100 parts by weight of the (A) polyacetal resin. Resin composition. The polyacetal resin composition according to any one of claims 1 to 13, further comprising 0.01 to 10 parts by weight of (H) an amino-substituted triazine compound with respect to 100 parts by weight of the (A) polyacetal resin. The polyacetal resin composition of any one of Claims 1-14 whose tensile strength is 60 Mpa or more. The polyacetal resin molded product formed by shape | molding the polyacetal resin composition of any one of Claims 1-15. (A) To a polyacetal resin raw material composition containing 100 parts by weight of a polyacetal resin,
(B) 0.01 to 5 parts by weight of a colorant selected from inorganic and organic pigments,
(C) 0.01-3 parts by weight of a polyamide resin having at least one of a physical property that a melting point or a softening point is 180 ° C. or less, or a physical property that an amine value is 2 mgKOH / g or more,
(D) 0.01 to 1 part by weight of a dihydrazide compound selected from the group consisting of an aromatic dihydrazide compound and an aliphatic dihydrazide compound having a solubility in 100 g of water at 20 ° C. of less than 1 g;
(E) 0.01 to 5 parts by weight of a hindered amine light stabilizer having a structure represented by the following general formula (1), and (F) 0.01 to 5 parts by weight of an ultraviolet absorber are mixed. A method for modifying a polyacetal resin raw material composition.

(In the formula, X represents an organic group in which the bond to the nitrogen atom is a carbon atom, and Y represents an organic group or a hydrogen atom bonded to the piperidyl group via an oxygen atom or a nitrogen atom.) The reforming method according to claim 17, wherein the weather resistance of the molded article is improved, and a decrease in tensile strength and generation of formaldehyde are suppressed. (B) 0.01 to 5 parts by weight of a colorant selected from inorganic and organic pigments,
(C) 0.01-3 parts by weight of a polyamide resin having at least one of a physical property that a melting point or a softening point is 180 ° C. or less, or a physical property that an amine value is 2 mgKOH / g or more,
(D) 0.01 to 1 part by weight of a dihydrazide compound selected from the group consisting of an aromatic dihydrazide compound and an aliphatic dihydrazide compound having a solubility in 100 g of water at 20 ° C. of less than 1 g;
(E) 0.01 to 5 parts by weight of a hindered amine light stabilizer having a structure represented by the following general formula (1), and (F) 0.01 to 5 parts by weight of an ultraviolet absorber. A modifier for a raw material composition of polyacetal resin.

(In the formula, X represents an organic group in which the bond to the nitrogen atom is a carbon atom, and Y represents an organic group or a hydrogen atom bonded to the piperidyl group via an oxygen atom or a nitrogen atom.) The modifier for a polyacetal resin raw material composition according to claim 19, which improves the weather resistance of the molded product and suppresses the decrease in tensile strength and the generation of formaldehyde.

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