JP2015110714A - Polyacetal resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyacetal resin composition which has extremely high weather (light) resistance and suppresses the generation of a volatile organic compound (VOC) from a molded product, particularly the generation amount of formaldehyde, at a low level.SOLUTION: There is provided a polyacetal resin composition which comprises: (A) a polyacetal copolymer having 1.0 mmol/kg or less of a hemiformal terminal group, 2.0 mmol/kg or less of a formyl terminal group and 0.5 wt.% or less of an unstable terminal group; (B) a cyclohexylguanamine; (C) a piperidine derivative having a steric hindrance group in which nitrogen forming a cyclic amine is tertiary nitrogen; (D) a benzotriazole-based compound; and (E) a hindered phenol-based antioxidant. The resin composition further preferably comprises (F) a fatty acid ester and/or a polyalkylene glycol.

Description

  The present invention relates to a polyacetal resin composition.

  Polyacetal resin (also referred to as polyoxymethylene resin, abbreviated as POM resin) has excellent characteristics, and its molded products are used in a wide range of fields. With the recent progress, there is a tendency that a high degree of characteristics is required for the polyacetal resin material used. As such a demand, in the field of use as automobile interior parts, etc., there is a demand for a polyacetal resin material having excellent thermal stability, a small amount of volatile organic compounds generated from the resin, and excellent weather resistance (light). It has been.

  On the other hand, various improvement methods are known for individual and individual required characteristics.

  For example, in order to improve the thermal stability of a polyacetal resin, a hindered phenol compound as an antioxidant, a nitrogen-containing compound such as melamine or polyamide as a heat stabilizer, an oxide or hydroxide of an alkaline earth metal, In general, compounds such as inorganic acid salts and carboxylate salts are blended.

  Moreover, in order to reduce the generation amount of formaldehyde which is a volatile organic compound, the polyacetal resin composition which mix | blended various compounds is disclosed. For example, a polyacetal resin composition (Patent Document 1) containing a polyacetal resin and a glyoxydiureide compound, a polyacetal resin composition containing a polyacetal resin and a cyclic nitrogen-containing compound (glycocyanidin such as creatinine or a derivative thereof) ( Patent Document 2), polyacetal resin, at least one processing stabilizer selected from polyalkylene glycol, fatty acid ester, fatty acid amide and fatty acid metal salt, and at least one inhibition selected from urea or its derivatives and amidine derivatives A polyacetal resin composition containing an agent (Patent Document 3), a polyacetal resin composition containing a guanamine derivative such as benzoguanamine as a stabilizer in a polyacetal resin (Patent Document 4), and the like are disclosed. Patent Document 5 discloses a polyacetal resin composition composed of a polyacetal copolymer having a specific terminal group and a formaldehyde inhibitor. As the formaldehyde inhibitor, an aminotriazine compound, a guanamine compound, a urea compound, a carboxylic acid Hydrazide compounds and the like are disclosed.

  In addition, in order to improve the weather resistance (light) of the polyacetal resin, Patent Document 6 discloses a composition in which a benzotriazole-based material and a hindered amine-based material are added and coexisted with the polyacetal resin. Furthermore, in Patent Document 7, the antioxidant tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and the light stabilizer bis- [N-methyl-2] are disclosed. , 2,6,6-tetramethyl-4-piperidinyl] sebacate and UV absorber 2- [2′-hydroxy-3 ′, 5′-bis- (α, α-dimethylbenzyl) phenyl] benzotriazole A composition with improved weather resistance (light) and thermal stability is disclosed.

  Further, in order to improve the heat resistance and weather resistance (light) of the polyacetal resin, Patent Document 8 discloses at least one compound selected from the group consisting of a guanamine compound having a bicyclo ring in the polyacetal resin and a formaldehyde reaction product thereof. And a composition containing sterically hindered phenol. Furthermore, Patent Document 9 discloses a resin composition in which a polyacetal resin is blended with an amino resin obtained by reacting cyclohexanecarboguanamine and formaldehyde and a sterically hindered phenol.

  According to the techniques disclosed in these documents, the generation of formaldehyde from the polyacetal resin can be remarkably reduced. In addition, it is also possible to impart excellent weather resistance (light) to the polyacetal resin.

Japanese Patent Laid-Open No. 10-182928 JP-A-11-335518 JP-A-12-26704 JP-A-62-190248 JP 2005-112995 A JP-A 61-36339 JP-A-6-256623 Japanese Patent Laid-Open No. Sho 63-314264 Japanese Unexamined Patent Publication No. 64-22954

  However, a simple combination of these technologies does not provide an additive effect. In particular, when hindered phenol and hindered amine are used in combination, thermal stability and weather resistance (light) resistance are reduced due to antagonism. It is extremely difficult to obtain a resin material that has excellent weather resistance (light), generation of formaldehyde is remarkably suppressed, and there are no problems such as poor appearance due to exudation of blended components.

  An object of the present invention is to provide a polyacetal resin composition having extremely high weather resistance (light) and suppressing generation of volatile organic compounds (VOC) from molded articles, particularly formaldehyde generation to a low level. It is to be.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by combining various materials contained in the polyacetal resin composition into a specific combination, thereby completing the present invention. It came to. Specifically, the present invention provides the following.

  (1) In the present invention, (A) hemi-formal terminal group amount is 1.0 mmol / kg or less, formyl terminal group amount is 2.0 mmol / kg or less, and unstable terminal group amount is 0.5% by weight or less. A polyacetal copolymer, (B) cyclohexylguanamine, (C) a piperidine derivative having a sterically hindering group, wherein the nitrogen forming the cyclic amine is tertiary nitrogen, and (D) a benzotriazole-based compound And (E) a hindered phenol antioxidant, a polyacetal resin composition.

  (2) Further, in the present invention, the component (C) is tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,3,4-butanetetracarboxylic acid and 1,2,2,6,6, -pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4, 8,10-tetraoxaspiro [5,5] undecane) -diethanol and / or a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol The polyacetal resin composition according to (1).

  (3) Further, in the present invention, the component (D) is 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol. Or a polyacetal resin composition according to (2).

  (4) Moreover, this invention is a polyacetal resin composition in any one of (1) to (3) which further contains (F) fatty acid ester and / or polyalkylene glycol.

  (5) Further, in the present invention, with respect to 100 parts by weight of the component (A), the component (B) is 0.01 part by weight or more and 1 part by weight or less, and the component (C) is 0.2 part by weight. 1 part by weight or less, the component (D) is 0.1 part by weight or more and 1 part by weight or less, and the component (E) is 0.03 part by weight or more and 0.3 part by weight or less, (1 The polyacetal resin composition according to any one of (4) to (4).

  (6) Moreover, this invention is comprised with the molded article of the polyacetal resin composition in any one of (1) to (5), and is a housing | casing for portable terminal devices or a car navigation, or an automotive interior part, or a building material It is a polyacetal resin molded product which is a constituent material of

  According to the present invention, it has high weather resistance (light), and the generation of volatile organic compounds (VOC) from molded articles, particularly the amount of formaldehyde generated, can be suppressed to an extremely low level.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

<Polyacetal resin composition>
The polyacetal resin composition of the present invention comprises (A) a specific polyacetal copolymer, (B) cyclohexylguanamine, (C) a sterically hindered group, and nitrogen forming a cyclic amine is tertiary nitrogen. A piperidine derivative, (D) 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, and (E) a hindered phenol antioxidant. , Containing. Hereinafter, each component will be described.

[(A) polyacetal copolymer]
In the present invention, (A) polyacetal copolymer having specific terminal properties is used as the base resin. (A) The polyacetal copolymer is a resin having an oxymethylene group (—OCH ₂ —) as a main constituent unit and other comonomer units in addition to the oxymethylene unit, and generally contains formaldehyde or a cyclic oligomer of formaldehyde. It is produced by copolymerizing a main monomer and a compound selected from cyclic ether and cyclic formal as a comonomer, and is usually stabilized against thermal decomposition by removing terminal unstable portions by hydrolysis. In particular, it is common to use trioxane, which is a cyclic trimer of formaldehyde, as the main monomer. Trioxane is generally obtained by reacting an aqueous formaldehyde solution in the presence of an acidic catalyst, and is used after being purified by a method such as distillation. As described below, trioxane used for polymerization is preferably one having as little content of impurities as water, methanol, formic acid and the like. Examples of the cyclic ether and cyclic formal which are comonomers include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, oxetane, tetrahydrofuran, trioxepane, 1,3-dioxane, 1,3-dioxolane, propylene glycol formal, diethylene glycol formal, trimethyl ether. Examples include ethylene glycol formal, 1,4-butanediol formal, 1,6-hexanediol formal, and the like. Further, a compound capable of forming a branched structure or a crosslinked structure can be used as a comonomer (or termonomer). Examples of such a compound include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, and 2-ethyl-hexyl. Alkyl or aryl glycidyl ethers such as glycidyl ether and phenyl glycidyl ether, alkylene glycols such as ethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, and butanediol diglycidyl ether, and diglycidyl ethers of polyalkylene glycols. These comonomers can be used alone or in combination of two or more.

  The polyacetal copolymer as described above can be generally obtained by cationic polymerization using a cationic polymerization catalyst by adding an appropriate amount of molecular weight regulator. The molecular weight regulator used, cationic polymerization catalyst, polymerization method, polymerization apparatus, deactivation treatment of the catalyst after polymerization, terminal stabilization treatment method of the crude polyacetal copolymer obtained by the polymerization, etc. are known from many literatures. Basically, any of them can be used.

  The molecular weight of the polyacetal copolymer used in the present invention is not particularly limited, but those having a weight average molecular weight of about 10,000 to 400,000 are preferred. In the present specification, the weight average molecular weight is a value in terms of polystyrene when measured by gel permeation chromatography (GPC).

  In addition, a melt index (measured at 190 ° C. under a load of 2.16 kg according to ASTM-D1238) of 0.1 to 100 g / 10 minutes, which is an index of resin fluidity, is preferable, and more preferably 0.5. ~ 80 g / 10 min.

  The (A) polyacetal copolymer used in the present invention has a specific terminal property as described above. Specifically, the hemi-formal terminal group amount is 1.0 mmol / kg or less, the formyl terminal group amount is 2 0.0 mmol / kg or less and the amount of unstable terminal groups is 0.5% by weight or less.

Here, the hemiformal terminal group is represented by —OCH ₂ OH, and is also referred to as a hydroxymethoxy group or a hemiacetal terminal group. The formyl end group is represented by -CHO. The amount of such hemi-formal end groups and formyl end groups can be determined by 1H-NMR measurement, and the specific measurement method can be referred to the method described in JP-A No. 2001-11143. The unstable terminal group amount is the amount of a portion which is present at the terminal portion of the polyacetal copolymer and is unstable and easily decomposed with respect to heat or a base. The amount of such unstable end groups is as follows: 1 g of polyacetal copolymer is placed in a pressure-resistant airtight container with 100 ml of 50% (volume%) aqueous methanol solution containing 0.5% (volume%) ammonium hydroxide, and at 180 ° C. for 45 minutes. The amount of formaldehyde decomposed and dissolved in the solution obtained by cooling and opening after heat treatment was quantified, and expressed in weight% with respect to the polyacetal copolymer.

  When the polyacetal copolymer used (A) does not have the above terminal properties and exceeds the upper limit value, it is not possible to obtain a polyacetal resin composition in which the amount of formaldehyde generated is sufficiently reduced. It is difficult to maintain the amount of formaldehyde generated by repeating the above at a low level. From such a point of view, the (A) polyacetal copolymer used in the present invention preferably has a hemi-formal terminal group content of 0.8 mmol / kg or less, more preferably 0.6 mmol / kg or less. Further, the formyl end group amount is preferably 1.5 mmol / kg or less, more preferably 1.0 mmol / kg or less. The amount of unstable terminal groups is preferably 0.4% by weight or less, more preferably 0.3% by weight or less. The lower limit of the amount of hemi-formal end groups, formyl end groups, and unstable end groups is not particularly limited.

  As described above, the polyacetal polymer (A) having specific terminal characteristics can be produced by reducing impurities contained in the monomer and comonomer, selecting a production process, optimizing production conditions, and the like.

  Although the specific example of the method of manufacturing the (A) polyacetal polymer which has the specific terminal characteristic which satisfy | fills the requirements of this invention for the following is given, it is not limited to this method at all.

First, it is important to reduce impurities such as water, alcohol (for example, methanol), and acid (for example, formic acid) contained in the monomer and comonomer, which are active impurities that form unstable terminals in the polymerization system. In addition, the total amount of these active impurities is preferably 1 × 10 ⁻² mol% or less, more preferably 5 × 10 ⁻³ mol% or less, based on all monomers in the reaction system. Naturally, if the content is excessive, it is not preferable for obtaining a polyacetal polymer having a small number of unstable terminal portions. It should be noted that chain transfer agents that do not form unstable ends, for example, low molecular weight linear acetals having both ends having an alkoxy group, such as methylal, are contained in an arbitrary amount to adjust the molecular weight of the polyacetal polymer. Can do.

Next, the amount of catalyst used during the polymerization reaction is also an important requirement. When a catalyst comprising boron trifluoride or a coordination compound thereof is used, it is preferably in the range of 5 × 10 ⁻³ to 1 × 10 ⁻² mol%, particularly 1 × 10 ^{−3 to} 7 based on the total monomers. × 10 ⁻³ mol% is preferable. Setting the amount of catalyst in such a limited range is effective in preventing the formation of unstable end portions. If the amount of the catalyst is too large, it is difficult to properly control the polymerization temperature, the decomposition reaction during the polymerization becomes dominant, and it becomes difficult to obtain a polyacetal polymer having a small number of unstable end portions that satisfies the requirements of the present invention. On the other hand, if the amount of the catalyst is too small, it is not preferable because the polymerization reaction rate is lowered and the polymerization yield is lowered.

  The amount and type of comonomer greatly affects the thermal stability of the polyacetal polymer. As the polyacetal polymer (A) of the present invention, a compound selected from trioxane (a-1), cyclic ether and cyclic formal ( One or more of a-2) are copolymerized at a ratio (weight ratio) of the former (a-1) / the latter (a-2) = 99.9 / 0.1 to 80.0 / 20.0. More preferably, the former / the latter are copolymerized at a ratio (weight ratio) of 99.5 / 0.5 to 90.0 / 10.0. Further, as the compound (a-2) selected from cyclic ether and cyclic formal, ethylene oxide, 1,3-dioxolane, 1,4-butanediol formal, and diethylene glycol formal are particularly preferable.

  As the polymerization method, any conventionally known method can be used, but a continuous bulk polymerization method for obtaining a solid powdery bulk polymer with the progress of polymerization using a liquid monomer is industrially preferable, and a polymerization temperature is 60 to It is desirable to maintain at 105 ° C, particularly 65 to 100 ° C.

  When a catalyst composed of boron trifluoride or a coordination compound thereof is used, a method of deactivating the catalyst after polymerization may be a method such as adding a polymer after polymerization into an aqueous solution containing a basic compound. In order to obtain a polyacetal polymer that satisfies the requirements of the present invention, it is preferable to pulverize and subdivide the polymer obtained by the polymerization reaction and bring it into contact with a deactivator to quickly deactivate the catalyst. For example, a polymer used for deactivation of the catalyst is pulverized, and 80% by weight or more, preferably 90% by weight thereof has a particle size of 1.5 mm or less, and 15% by weight or more, preferably 20% by weight or more is 0.00. It is desirable that the particle size is 3 mm or less. Basic compounds for neutralizing and deactivating the polymerization catalyst include ammonia, amines such as triethylamine, tributylamine, triethanolamine, and tributanolamine, or oxides of alkali metals and alkaline earth metals. , Hydroxides, salts, and other known catalyst deactivators can be used, and these basic compounds are added in an aqueous solution of 0.001 to 0.5% by weight, particularly 0.02 to 0.3% by weight. Is preferred. Moreover, the temperature of the preferable aqueous solution is 10-80 degreeC, Most preferably, it is 15-60 degreeC. Further, after the polymerization is completed, it is preferable that the catalyst is deactivated by promptly adding it to these aqueous solutions.

  Prior to the polymerization, 0.01 to 0.1% by weight of a hindered phenolic antioxidant is added to the monomer in advance in the monomer, and the polymerization is performed in the presence of this to make the polymerization reaction system uniform. By making it exist, depolymerization during polymerization can be suppressed, and post-treatment such as drying after polymerization and oxidative degradation in a stabilization step can also be suppressed.

  Polyacetal polymers with a small amount of unstable terminals can be produced by reducing impurities contained in the monomers and comonomers as described above, selecting the production process and optimizing the production conditions. It is possible to further reduce the amount of unstable terminals by passing through the conversion step. As the stabilization step, the polyacetal polymer is heated to a temperature equal to or higher than its melting point and processed in a molten state to decompose and remove only unstable parts, or a non-uniform system is maintained in an insoluble liquid medium at 80 ° C. or higher. For example, the unstable end portion may be decomposed and removed by heat treatment at a temperature of 5 ° C.

[(B) Cyclohexylguanamine]
The polyacetal resin of the present invention contains (B) cyclohexylguanamine. (B) Cyclohexylguanamine functions as a scavenger for volatile organic compounds.

  As scavengers for volatile organic compounds, glyoxydiureide compounds, cyclic nitrogen-containing compounds (glycocyanidins such as creatinine or derivatives thereof), guanamine derivatives such as benzoguanamine, aminotriazine compounds, guanamine compounds, urea compounds, carboxylic acids Various compounds such as hydrazide compounds have been proposed. As a result of examining a large number of scavengers, the present invention shows that when cyclohexylguanamine is used as a scavenger, not only the amount of formaldehyde generated from the molded product can be suppressed to a very low level but also high weather resistance (light). This is the first time that I found out. As a result, the resin composition of the present invention is used in applications where both reduction of formaldehyde generation and high weather resistance (light) are strongly required, such as automobile parts, electrical / electronic parts, precision machine parts, building materials, piping parts. It can be suitably used for daily necessities, cosmetic parts, medical equipment parts and the like.

  In the present invention, the amount of (B) cyclohexylguanamine added is preferably 0.01 part by weight or more and 1 part by weight or less, and 0.03 part by weight or more and 0 part by weight or more with respect to 100 parts by weight of the (A) polyacetal copolymer. More preferably, it is 7 parts by weight or less. (B) If the amount of cyclohexylguanamine is too small, a polyacetal resin composition in which the amount of formaldehyde generated is sufficiently reduced cannot be obtained, and the amount of formaldehyde generated by repeated thermal history is maintained at a low level. On the contrary, when the amount of (B) cyclohexylguanamine is excessive, problems such as deterioration of mechanical properties and poor appearance due to bleeding occur.

[(C) Piperidine derivative]
The polyacetal resin of the present invention contains (C) a piperidine derivative having a sterically hindering group and the nitrogen forming the cyclic amine is tertiary nitrogen. This (C) piperidine derivative functions as a hindered amine stabilizer.

  Even if the hindered amine stabilizer is a piperidine derivative, if it does not have a steric hindrance group, the weather resistance (light) may be lowered, which is not preferable. Moreover, even if the hindered amine stabilizer is a piperidine derivative, if the nitrogen forming the cyclic amine is not tertiary nitrogen, the amount of formaldehyde generated from the molded piece may increase, which is not preferable.

  Examples of (C) piperidine derivatives suitable for the present invention include bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1-octyloxy-2,2,6,6-tetra Aliphatic di- or tricarboxylic acid-bis or tripiperidyl ester (such as C2-20 aliphatic dicarboxylic acid-bispiperidyl ester) such as methyl-4-piperidyl sepacate, 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, dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer, bis (2,2,6,6, -tetramethyl decanedioate) Ru-1 (octyloxy) -4-piperidinyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4- Hydroxyphenyl] methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, tetrakis ( 1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6 Condensate of 6, -pentamethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidino And β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) -diethanol, 4 peroxidized -Butylamino-2,2,6,6, -tetramethylpiperidine and 2,4,6-trichloro-1,3,5-triazine, and cyclohexane, N, N'-ethane-1,2-diylbis (1 , 3-propanediamine), 1- [2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine and the like.

  Among these, (C) piperidine derivatives are (i) tetrakis (1,2,2,6,6-pentamethyl-) in that there is little seepage from the molded piece and there is little deterioration in weather resistance (light) during use. 4-piperidyl) 1,2,3,4-butanetetracarboxylate, (ii) 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6, -pentamethyl-4-piperidinol β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) -condensate with diethanol and / or (iii) succinate A polymer of dimethyl acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol is preferred.

  The amount of the (C) hindered amine stabilizer added is not particularly limited, but is preferably 0.2 parts by weight or more and 1 part by weight or less with respect to 100 parts by weight of the (A) polyacetal copolymer. 4 parts by weight or more and 0.8 parts by weight or less.

  (C) When the blending amount of the hindered amine stabilizer is too small, a polyacetal resin composition having excellent weather resistance (light) properties cannot be obtained. Conversely, when the blending amount is excessive, the mechanical properties are reduced. Problems such as poor appearance due to seepage occur.

[(D) Benzotriazole compound]
The polyacetal resin of the present invention contains (D) a benzotriazole-based compound. The component (D) functions as an ultraviolet absorber.

  In addition to benzotriazole compounds, oxalic anilide compounds, triazine compounds, benzophenone compounds, benzoate compounds and the like are known as ultraviolet absorbers. However, even if the polyacetal resin contains an ultraviolet absorber, it is not preferable that the ultraviolet absorber is different from the benzotriazole-based compound because weather resistance (light) may be lowered.

  Examples of the benzotriazole compounds include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenyl) Ethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2,4-di-tert-butyl-6- (5- Chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- ( 1,1,3,3-tetramethylbutyl) phenol, 2- (2′-hydroxy-3 ′, 5′-di-isoamylphenyl) benzotriazole and the like And benzotriazoles having an aryl group and an alkyl (C1-6 alkyl) group-substituted aryl group, hydroxyl such as 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] benzotriazole And aralkyl (or aryl) group-substituted benzotriazoles, hydroxyl groups such as 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole and alkoxy (C1-12 alkoxy) group-substituted aryl groups Benzotriazoles having

  These benzotriazole compounds can be used alone or in combination of two or more.

  Among these benzotriazole compounds, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) is a point that the weather resistance (light) improvement is remarkable. Phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3- Tetramethylbutyl) phenol and the like are preferable.

  In the present invention, the amount of the (D) ultraviolet absorber as described above is preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the (A) polyacetal copolymer. More preferably, it is 2 parts by weight or more and 0.8 parts by weight or less. (D) When the blending amount of the ultraviolet absorber is too small, it is not possible to obtain a polyacetal resin composition excellent in weather resistance (light) properties. Conversely, when the blending amount is excessive, the mechanical properties are reduced. Problems such as poor appearance due to seepage occur.

[(E) hindered phenolic antioxidant]
Examples of the (E) hindered phenol antioxidant used in the present invention include a monocyclic hindered phenol compound, a polycyclic hindered phenol compound linked with a hydrocarbon group or a group containing a sulfur atom, an ester group, or Examples thereof include hindered phenol compounds having an amide group. Specific examples of these compounds include 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-methylenebis (2,6 -Di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 4,4′-thiobis (3-methyl-6-tert-butylphenol) ), N-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, n-octadecyl-2- (4′- Loxy-3 ′, 5′-di-tert-butylphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis ( Oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] Undecane, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxyben ) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-dihydrocinnamamide), N, N ′ -Ethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], N, N'-tetramethylenebis [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionamide], N, N′-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propio Amido], N, N′-ethylenebis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionamide], N, N′-hexamethylenebis [3- (3-tert-butyl) -5-methyl-4-hydroxyphenyl) propionamide], N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N'-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionyl] hydrazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1, Examples thereof include 3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate.

  These (E) hindered phenolic antioxidants can be used alone or in combination of two or more. (E) It is preferable that the addition amount of hindered phenolic antioxidant is 0.03 weight part or more and 0.30 weight part or less with respect to 100 weight part of (A) polyacetal copolymer. When the amount is less than this amount, the effect is insufficient. When the amount is more than this amount, the weather resistance (light) is inferior due to the antagonistic action with the hindered amine stabilizer.

[(F) Compound selected from fatty acid ester and polyalkylene glycol]
Moreover, although it is not an essential component, it is preferable that the polyacetal resin composition of this invention contains the compound chosen from (F) fatty acid ester and polyalkylene glycol.

The fatty acid that is a constituent of the fatty acid ester is one or more saturated or unsaturated fatty acids. Examples of such fatty acids include acetic acid, propionic acid, butyric acid, caproic acid, capric acid, undecylic acid, Hivalic acid, caprylic acid, lauric acid, tridecyl acid, isotridecyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, 12 hydroxystearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, Examples include heptacosanoic acid, montanic acid, mellic acid, laceric acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, cetreic acid, erucic acid, and the like, and preferably fatty acids having 12 or more carbon atoms. On the other hand, as an alcohol which is a constituent component of a fatty acid ester, a homopolymer of alkylene glycol (for example, C2-6 alkylene glycol (preferably C2-4 alkylene glycol) such as ethylene glycol, propylene glycol, tetramethylene glycol, etc.), Copolymers and derivatives thereof are included. Specific examples include poly C2-6 oxyalkylene glycols (preferably poly C2-4 oxyalkylene glycols) such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyoxyethylene-polyoxypropylene copolymers (random or block). Copolymers), polyoxyethylene polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene monobutyl ether, and the like. Preferred polyoxyalkylene glycols are polymers having oxyethylene units, such as polyethylene glycol, polyoxyethylene polyoxypropylene copolymers and derivatives thereof. The number average molecular weight of the polyoxyalkylene glycol is 1 × 10 ³ to 1 × 10 ⁶ (for example, 1 × 10 ^{3 to} 5 × 10 ⁵ ), preferably 2 × 10 ³ to 1 × 10 ⁵ (for example, 2 × 10 ^{3 to} 5 × 10 ⁴ ).

  Preferred fatty acid esters include esters of fatty acids having 12 or more carbon atoms and polyalkylene glycols having an average degree of polymerization of about 20 to 300.

  As the polyalkylene glycol, at least one selected from homopolymers and copolymers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and polyglycerin can be used, and a polyalkylene having an average degree of polymerization of about 20 to 300 Glycol is preferred.

  In the present invention, blending of the compound selected from (F) fatty acid ester and polyalkylene glycol as described above is not essential, but when these compounds are blended, an effect of improving weather resistance (light) is produced.

  A preferable blending amount when the component (F) is added is preferably 0.01 parts by weight or more and 5.0 parts by weight or less, and 0.05 parts by weight or more with respect to 100 parts by weight of the (A) polyacetal copolymer. 2.0 parts by weight or less.

[Other additives]
In addition, an organic carboxylic acid metal salt, metal oxide, or metal hydroxide can be added to the polyacetal resin composition of the present invention to improve thermal stability, long-term thermal stability, and the like.

As the organic carboxylic acid forming the organic carboxylic acid metal salt, various aliphatic carboxylic acids having about 1 to 34 carbon atoms can be used, saturated aliphatic monocarboxylic acid, saturated aliphatic dicarboxylic acid, unsaturated fat. Group monocarboxylic acid, unsaturated aliphatic dicarboxylic acid, and oxyacids thereof. These aliphatic carboxylic acids may have a hydroxyl group. Further, it may be a copolymer of a polymerizable unsaturated carboxylic acid ((meth) acrylic acid, maleic acid, fumaric acid, maleic anhydride, monoethyl maleate, etc.) and an olefin. Specific examples of organic carboxylic acid metal salts include alkali metal organic carboxylates such as lithium citrate, potassium citrate, sodium citrate, lithium stearate, lithium 12-hydroxystearate, magnesium acetate, calcium acetate, Examples thereof include alkaline earth metal organic carboxylates such as magnesium oxide, calcium citrate, calcium stearate, magnesium stearate, magnesium 12-hydroxystearate, and calcium 12-hydroxystearate, ionomer resins, and the like. Of these organic carboxylic acid metal salts, alkaline earth metal salts such as calcium citrate, magnesium stearate, calcium stearate, magnesium 12-hydroxystearate, and calcium 12-hydroxystearate and ionomer resins are preferred.
As the metal oxide and metal hydroxide, calcium oxide, magnesium oxide, zinc oxide, calcium hydroxide, magnesium hydroxide and the like are preferable.

  The polyacetal resin composition of the present invention further includes an impact resistance improver, a gloss control agent, a slidability improver, a filler, a colorant, a nucleating agent, a release agent, an antistatic agent, a surfactant, Antibacterial agents, antifungal agents, fragrances, foaming agents, compatibilizers, physical property improvers (boric acid or derivatives thereof), fragrances, and the like can be blended without impairing the purpose of the present invention, Various characteristics according to each additive can be improved. In addition, antioxidants, heat stabilizers, processability improvers and the like other than those described above can be used in combination.

  Examples of the impact resistance improver include thermoplastic polyurethane resins, acrylic core-shell polymers, thermoplastic polyester elastomers, styrene elastomers, olefin elastomers, polyamide elastomers, rubber components (natural rubber, etc.), and the like.

  Gloss control agents include acrylic core-shell polymers, thermoplastic polyurethanes, thermoplastic polyester elastomers, polyamide elastomers, alkyl (meth) acrylate homo- or copolymers (polymethyl methacrylate, etc.), polycarbonate resins, styrene resins ( Polystyrene, AS resin, AES resin, etc.), olefinic resins (polypropylene, cyclic polyolefin, etc.) and the like.

  Examples of the slidability improver include olefin polymers (polyethylene, polypropylene, copolymers of ethylene and α-olefin, modified products thereof such as acid anhydrides), waxes (polyethylene wax, etc.), silicone oils and silicones. Resin, fluorine resin (polytetrafluoroethylene, etc.), fatty acid ester and the like are included.

  As fillers, inorganic or organic fibrous fillers such as glass fiber, carbon fiber, boron fiber, potassium titanate fiber, metal fiber, aramid fiber, plate-like filler such as glass flake, mica, graphite, milled fiber, Examples thereof include powdery fillers such as glass beads, glass balloons, talc, kaolin, silica, diatomaceous earth, clay, wollastonite, alumina, graphite fluoride, silicon carbide, boron nitride, and metal powder.

  Examples of the release agent include long chain fatty acid amides, and acid amides (monoamides, bisamides, etc.) of long chain fatty acids (monovalent or divalent long chain fatty acids) and amines (monoamines, diamines, polyamines, etc.). ) Can be used. Examples of the monoamide include capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, montanic acid amide, etc. Examples include primary acid amides of unsaturated fatty acids such as amides, secondary acid amides of saturated and / or unsaturated fatty acids and monoamines such as stearyl stearic acid amide and stearyl oleic acid amide. The bisamide includes bisamides of C1-6 alkylene diamine (especially C1-2 alkylene diamine) and the fatty acid, and specific examples thereof include ethylenediamine-dipalmitic acid amide, ethylenediamine-distearic acid amide ( Ethylene bisstearylamide), hexamethylenediamine-distearic acid amide, ethylenediamine-dibehenic acid amide, ethylenediamine-dimantanoic acid amide, ethylenediamine-dioleic acid amide, ethylenediamine-dierucic acid amide, etc., and ethylenediamine- (stearic acid amide). Bisamide having a structure in which different acyl groups are bonded to the amine moiety of alkylenediamine such as oleic acid amide can also be used. A preferred fatty acid amide is bisamide.

  As the colorant, various dyes, organic pigments, and inorganic pigments can also be added within a range that does not impair the weather resistance (light) properties and the ability to inhibit HCHO release from the molded piece, which are the objects of the present invention.

<Method for producing polyacetal resin composition>
The manufacturing method of the polyacetal resin composition of this invention is not specifically limited, It can prepare by the various methods conventionally known as a preparation method of a resin composition. For example, (1) a method in which all components constituting the composition are mixed, and this is supplied to an extruder and melt-kneaded to obtain a pellet-like composition; (2) a part of the components constituting the composition The remaining components are fed from the main feed port of the extruder through the side feed port and melt-kneaded to obtain a pellet-like composition. (3) Once the pellets having different compositions are prepared by extrusion or the like, the pellets are mixed Thus, a method of adjusting to a predetermined composition can be employed.

  In the preparation of the composition using an extruder, it is preferable to use an extruder having one or more devolatilization vent ports, and further, water or a low boiling point at any location from the main feed port to the devolatilization vent port. It is preferable to supply about 0.1 to 10 parts by weight of alcohol with respect to 100 parts by weight of the polyacetal resin, and devolatilize and remove formaldehyde and the like generated in the extrusion process together with water and low-boiling alcohols from the devolatilization vent port. Thereby, the amount of formaldehyde generated from the polyacetal resin composition and its molded product can be further reduced.

  The molded product formed with the polyacetal resin composition of the present invention can keep the amount of formaldehyde generated low. Specifically, the amount of formaldehyde generated by the measurement method described in the Examples section can be 4.0 μg / g or less per unit weight of the molded article, and preferably 2.0 μg / g or less. This is an extremely low level compared to the amount of formaldehyde generated from a molded product made of a commercially available polyacetal resin being about 10 to 20 μg / g per unit weight. Further, a molded product made of a recycled resin composition prepared by recovering these molded products or a pulverized product thereof and melt-kneaded, or a molded product obtained by melt-kneading and directly molding the recovered molded product or a pulverized product thereof. The product has a very small amount of formaldehyde generated as described above, and the amount of formaldehyde generated is close to the above level.

  The polyacetal resin composition of the present invention can remarkably suppress the formation of formaldehyde due to oxidation or thermal decomposition of the polyacetal copolymer in a molding process or the like, and can improve the working environment. Moreover, adhesion of decomposition products and additives to the mold (mold deposit) and leaching of decomposition products and additives from the molded product can be remarkably suppressed, and various problems during molding can be improved. For this reason, the resin composition of the present invention can be produced by various methods such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, and gas injection molding. Is useful for molding.

  Moreover, the polyacetal resin composition of this invention is excellent also in weather resistance (light) property by setting it as a specific compounding component, and can be used also for the use for which weather resistance (light) property is requested | required.

  The polyacetal resin composition of the present invention is not limited in the field of use as a molded product, but is used in applications where reduction of formaldehyde generation is strongly required, such as automobile parts, electrical / electronic parts, precision machine parts, building materials, piping parts It can be suitably used for daily necessities, cosmetic parts, medical equipment parts and the like.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

<Synthesis of (A) polyacetal copolymer>
Using a biaxial paddle type continuous polymerization machine, 0.04% by weight of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4) with respect to the total monomer (trioxane + 1,3-dioxolane) -Hydroxyphenyl) propionate] and trioxane added with 2.5% of 1,3-dioxolane (in all monomers) was continuously fed, and at the same time boron trifluoride was catalyst (catalyst concentration 2 × 10 ⁻³ mol%). Note that the impurity concentration in the monomer used at this time, the water 3 × ¹⁰ -3 mol%, methanol was ^{1 × 10 -3 mol%, 1} × 10 -3 mol% formic acid.

  About the polymer discharged | emitted from the polymerization machine discharge port, the aqueous solution containing 1000 ppm of triethylamine was added and mixed and ground immediately after discharge | emission, and the stirring process was performed. Thereafter, centrifugation and drying were performed to obtain a polymer in which the catalyst was deactivated.

  This polymer is supplied to a twin screw extruder having a vent port, melted and kneaded at a resin temperature of about 220 ° C., and the unstable end is removed while performing devolatilization under reduced pressure at the vent port, thereby forming a pellet polymer. Got. Next, using a cylindrical pressure-resistant container capable of keeping heat, the above pellet-shaped polymer was continuously supplied from the upper part, and the treatment was performed for 8 hours while supplying a 500 ppm triethylamine aqueous solution at 135 ° C. from the lower part. . Thereafter, centrifugation and drying were performed to obtain a polyacetal copolymer.

  The polyacetal copolymer contains 0.04% by weight of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and has a hemi-formal terminal group amount of 0.38 mmol / kg. The amount of formyl end groups was 0.03 mmol / kg, the amount of unstable end groups was 0.15 wt%, and the melt index was 9 g / 10 min.

  In the present invention, the amount of hemi-formal end group and formyl group end group of the polyacetal copolymer is in accordance with the method described in JP-A No. 2001-11143 using an AVANCE400 type FT-NMR apparatus manufactured by Bruker Co., Ltd. It is assumed that the value (mmol / kg) obtained by performing the measurement.

  The amount of unstable terminal groups was determined by adding 1 g of a polyacetal copolymer together with 100 ml of a 50% (volume%) aqueous methanol solution containing 0.5% (volume%) ammonium hydroxide in a pressure-resistant sealed container. The amount of formaldehyde decomposed and dissolved in the solution obtained by heat-treating for minutes and then cooling and opening is quantified and expressed in weight% with respect to the polyacetal copolymer.

  Moreover, the said melt index shall be the value (g / 10min) calculated | required on condition of 190 degreeC and 2160g according to ASTM-D1238.

<Preparation of amino-substituted triazine compound>

[Amino-substituted triazine compound 1]
Cyclohexylguanamine was synthesized by the following method.
A thermometer and a reflux condenser were attached to a 200 mL four-necked flask equipped with a Dimroth condenser, and the system was purged with nitrogen. To this was charged 49.3 g of ethylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries) and 16.3 g (19.4 mmol) of dicyandiamide (manufactured by Tokyo Chemical Industry), and the mixture was completely dissolved by heating and stirring at a bath temperature of 80 ° C., and then cyclohexylcarbonitrile. 17.7 g (16.2 mmol) (manufactured by Tokyo Chemical Industry) was added dropwise. After stirring for 10 minutes, a separately prepared solution consisting of 1.81 g (3.2 mmol) of potassium hydroxide and 16.4 g of ethylene glycol monomethyl ether was added dropwise and refluxed at a reaction solution temperature of 122 ° C. to 123 ° C. for 8 hours. When the reaction solution at the 8th hour of the reaction was analyzed by gas chromatography, the conversion of nitrile was 99.0%.

  The reaction solution was cooled to room temperature, transferred to an eggplant flask, distilled water was added to the slurry obtained by distilling off the solvent with an evaporator, and the mixture was further stirred at 90 ° C. for 1 hour. Thereafter, the slurry was filtered while hot, and the obtained filter cake was rinsed successively with distilled water and 2-propanol, and then dried under reduced pressure at 40 ° C. and 10 mmHg for 8 hours to obtain cyclohexylguanamine. The yield of cyclohexylguanamine was 20.3 g (10.5 mmol), and the yield was 64.7%.

[Amino-substituted triazine compound 2]
Commercially available melamine (manufactured by Mitsui Chemicals) was used as amino-substituted triazine compound 2.

[Amino-substituted triazine compound 3]
Commercially available benzoguanamine (manufactured by Nippon Shokubai Co., Ltd.) was used as amino-substituted triazine compound 3.

[Amino-substituted triazine compound 4]
2-methoxybenzoguanamine was synthesized by the following method.
A thermometer and a reflux condenser were attached to a 200 mL four-necked flask equipped with a Dimroth condenser, and the system was purged with nitrogen. This was charged with 49.3 g of ethylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries) and 14.5 g (17.2 mmol) of dicyandiamide (manufactured by Tokyo Chemical Industry), heated and stirred at a bath temperature of 80 ° C., and completely dissolved. 19.2 g (14.4 mmol) of benzonitrile (manufactured by Tokyo Chemical Industry) was added dropwise. After stirring for 10 minutes, a separately prepared solution consisting of 0.54 g of potassium hydroxide and 16.4 g of ethylene glycol monomethyl ether was added dropwise, and the mixture was refluxed at a reaction solution temperature of 122 ° C. to 123 ° C. for 8 hours. When the reaction solution at the 8th hour of the reaction was analyzed by gas chromatography, the conversion rate of nitrile was 76.8%.

  The reaction solution was cooled to room temperature, transferred to an eggplant flask, distilled water was added to the slurry obtained by distilling off the solvent with an evaporator, and the mixture was further stirred at 90 ° C. for 1 hour. Thereafter, the slurry was filtered while hot, and the obtained filter cake was rinsed with distilled water and 2-propanol successively, and then dried under reduced pressure at 40 ° C. and 10 mmHg for 8 hours to obtain 2-methoxybenzoguanamine. The yield of 2-methoxybenzoguanamine was 18.2 g (8.4 mmol), and the yield was 58.2%.

[Amino-substituted triazine compound 5]
Cyclohexenyl diaminotriazine was synthesized by the following method.
A thermometer and a reflux condenser were attached to a 200 mL four-necked flask equipped with a Dimroth condenser, and the system was purged with nitrogen. This was charged with 49.3 g of ethylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries) and 16.5 g (19.6 mmol) of dicyandiamide (manufactured by Tokyo Chemical Industry). After complete dissolution by heating and stirring at a bath temperature of 80 ° C., cyclohexenyl carbo 17.5 g (16.3 mmol) of nitrile (manufactured by Tokyo Chemical Industry) was added dropwise. After stirring for 10 minutes, a separately prepared solution consisting of 0.54 g (3.3 mmol) of potassium hydroxide and 16.4 g of ethylene glycol monomethyl ether was added dropwise, and the mixture was refluxed at a reaction solution temperature of 122 ° C. to 123 ° C. for 8 hours. When the reaction solution at the 8th hour of the reaction was analyzed by gas chromatography, the conversion of nitrile was 89.2%.

  The reaction solution was cooled to room temperature, transferred to an eggplant flask, distilled water was added to the slurry obtained by distilling off the solvent with an evaporator, and the mixture was further stirred at 90 ° C. for 1 hour. Thereafter, the slurry was filtered while hot, and the obtained filter cake was rinsed with distilled water and 2-propanol successively, and then dried under reduced pressure at 40 ° C. and 10 mmHg for 8 hours to obtain cyclohexenyl diaminotriazine. The yield of cyclohexenyl diaminotriazine was 23.4 g (12.2 mmol), and the yield was 75.0%.

[Amino-substituted triazine compound 6]
N-octylmelamine was synthesized by the following method.
A thermometer and a reflux condenser were attached to a 500 mL four-necked flask equipped with a Dimroth condenser, and the system was purged with nitrogen. Monochlorotriazine (manufactured by Wako Pure Chemical Industries, Ltd.) 16.2 g (111.3 mmol), N-octylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 42.6 g (329.5 mmol), and distilled water 156.42 g were charged into this, followed by stirring. The mixture was gradually heated in an oil bath until reflux was applied. After stirring for 1 hour under reflux, 44.70 g (335.2 mmol) of a 30% by weight aqueous sodium hydroxide solution was added dropwise over 1 hour. After completion of the addition, the mixture was further aged for 1 hour under reflux.

  Next, after leaving the oil bath, 192.2 g of toluene was slowly added dropwise, and then the reaction solution was further cooled to room temperature. The organic layer which was allowed to stand and separated into two layers was concentrated with an evaporator, and after cooling to 10 ° C. after adding 8 g of 2-propanol and 200 g of hexane, a white slurry was obtained. This was filtered, rinsed with hexane and dried at 50 mmHg and 40 ° C. for 8 hours to obtain N-octylmelamine. The yield of N-octylmelamine was 14.2 g (59.6 mmol), and the yield was 53.5%.

[Amino-substituted triazine compound 7]
N-cyclohexylmelamine was synthesized by the following method.
A thermometer and a reflux condenser were attached to a 500 mL four-necked flask equipped with a Dimroth condenser, and the system was purged with nitrogen. Monochlorotriazine (manufactured by Wako Pure Chemical Industries, Ltd.) 16.2 g (111.3 mmol), N-cyclohexylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 32.7 g (329.5 mmol), and distilled water 156.43 g were charged into this, and then stirred. The mixture was gradually heated in an oil bath until reflux was applied. Stirring was continued for 1 hour under reflux, and then 43.69 g (335.2 mmol) of a 30% by weight aqueous sodium hydroxide solution was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further aged for 1 hour under reflux.

  Next, after removing from the oil bath, 192.4 g of toluene was slowly added dropwise, and then the reaction solution was further cooled to 10 ° C. in an ice bath. The precipitated crystals were filtered, rinsed with toluene and water, and then dried at 50 mmHg and 50 ° C. for 8 hours to obtain N-cyclohexylmelamine. The yield of N-cyclohexylmelamine was 20.3 g (105.0 mmol), and the yield was 93.0%.

<Preparation of polyacetal resin composition>

In Table 1, various materials are as follows.
(A) Specific polyacetal copolymer Polyacetal copolymer obtained by the above <(A) Synthesis of polyacetal copolymer> (B) Cyclohexylguanamine Cyclohexylguanamine obtained by the above <Preparation of amino-substituted triazine compound> (B ′ ) Other amino-substituted triazine compounds Various compounds obtained by the above <Preparation of amino-substituted triazine compound> (C) Specific piperidine derivatives 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6 , -Pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) -diethanol (Product name: ADK STAB LA-63P, manufactured by ADEKA)
(D) Benzotrial compounds, etc. 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (product name: TINUVIN234, manufactured by BASF Japan)
(E) Hindered phenol antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Product name: IRGANOX1010, manufactured by BASF Japan)
(F) Fatty acid ester consisting of fatty acid and polyalkylene glycol Polyethylene glycol monostearate (average degree of polymerization of polyethylene glycol: 90) (Product name: Nonion S-40, manufactured by NOF Corporation)
(G) Others 12-hydroxy calcium stearate (Product name: CS-6, manufactured by Nitto Kasei Kogyo Co., Ltd.)
Ethylene bisstearylamide (Product name: Armo wax EBS (B), manufactured by Lion Akzo)

  The materials shown in Table 1 were pre-blended in the proportions shown in Table 1 (units are parts by weight), then charged into the main feed port of a 30 mm diameter twin screw extruder having one vent port and melt mixed (extruded) Conditions: L / D = 35, extrusion temperature = 200 ° C., screw rotation speed = 120 rpm, vent vacuum = −700 mmHg, discharge amount = 15 kg / hr) to prepare a pellet-shaped composition.

<Evaluation>
[Preparation of test piece]
After the pellets of the polyacetal resin composition prepared in Examples and Comparative Examples were dried at 140 ° C. for 3 hours in an air dryer, the above polyoxymethylene resin composition was used using an injection molding machine set at a cylinder temperature of 190 ° C. The product was injection-molded to obtain 100 mm × 40 mm × 2 mm flat test pieces and 70 mm × 40 mm × 3 mm flat test pieces.

  And using the said test piece, the generation amount of formaldehyde from a molded article, a weather resistance (light) property, and the oozing-out property from a molded piece were evaluated.

[Amount of formaldehyde generated from molded products]
Two flat test pieces of 100 mm × 40 mm × 2 mm (total weight of about 22 g are precisely weighed) are sealed by hanging on a lid of a polyethylene bottle (capacity 1 L) containing 50 ml of distilled water, and a temperature of 60 in a thermostat. The mixture was allowed to stand at 3 ° C. for 3 hours and then allowed to stand at room temperature for 1 hour. The amount of formaldehyde generated from a flat test piece and absorbed in distilled water in a polyethylene bottle was determined according to JIS K0102, 29 (formaldehyde term), and the amount of formaldehyde generated per unit weight (μg / g) was determined. Calculated. The case where the amount of formaldehyde generated is 2.0 μg / g or less is “◎”, exceeds 2.0 μg / g, the case where it is 3.0 μg / g or less is “◯”, exceeds 3.0 μg / g, The case where it was 4.0 μg / g or less was designated as “Δ”, and the case where it was over 4.0 μg / g was designated as “x”. The results are shown in Table 3.

[Weather resistance (light)]
Using a sunshine weather meter S80HB / BR (manufactured by Suga Test Instruments Co., Ltd.), sample surface irradiance: 255 w / m ² (300 to 700 nm), glass filter: cut below 255 nm, black panel temperature: 83 ° C., test chamber humidity: The surface of a flat molded product (70 mm x 40 mm x 3 mm) is observed every 24 hours up to 120 hours up to 120 hours and every 72 hours thereafter until the processing time is 480 hours, under the conditions of 50% and no light / dark cycle. The time when the crack was observed was measured. The case where the time until the crack was observed was 300 hours or more was indicated as “◯”, the case where it was 200 hours or more and less than 300 hours was indicated as “Δ”, and the case where it was less than 200 hours was indicated as “x”. The results are shown in Table 3.

[Exuding property]
The surface of the test piece after the above-mentioned measurement of the amount of formaldehyde generated from the molded product was observed, and the presence or absence of seepage on the surface of the molded piece was confirmed. The case where no seepage was observed was indicated by “◯”, the case where slight seepage was observed was indicated by “△”, and the case where exudation was observed was indicated by “X”. The results are shown in Table 3.

  (A) a specific polyacetal copolymer, (B) cyclohexylguanamine, (C) a piperidine derivative having a sterically hindering group, and the nitrogen forming the cyclic amine is tertiary nitrogen, and (D) benzo When a polyacetal resin composition containing a triazole-based compound and (E) a hindered phenol-based antioxidant is used, the amount of formaldehyde generated from the resin molded product can be suppressed to an extremely low level. Moreover, this resin composition has extremely high weather resistance (light). Furthermore, no seepage from the molding surface is observed (Example 1). Therefore, the polyacetal resin compositions according to the examples are various resin molded products that are required to have both low VOC properties and high weather resistance (light) properties, for example, portable terminal equipment or car navigation cases, or automobiles. It can use suitably as a material which comprises the resin composition for forming resin molded articles, such as a component material of interior parts or building materials.

  Further, when the amino-substituted triazine compound is melamine, it is not preferable because the amount of formaldehyde generated from the resin molded product is high (Comparative Example 1). Similarly, when the amino-substituted triazine compound is 2-methoxybenzoguanamine, N-octylmelamine or N-cyclohexylmelamine, the amount of formaldehyde generated from the resin molded product is suppressed to an extremely low level, although not as much as melamine. It is not preferable in that it cannot be said (Comparative Examples 3, 5 and 6). In addition, when the amino-substituted triazine compound is benzoguanamine or cyclohexenylaminotriazine, the amount of formaldehyde generated from the resin molded product can be suitably suppressed, but it cannot be said to have high weather resistance (light), so low VOC properties In addition, it cannot be suitably used as a resin composition for forming various resin molded products that require both high weather resistance (light) resistance (Comparative Examples 2 and 4). In addition, when the amino-substituted triazine compound is 2-methoxybenzoguanamine or cyclohexenyl diaminotriazine, since it can ooze out from the surface of the molded product, the structure for a portable terminal device or a car navigation case, or an automobile interior part or building material If it is used as a material constituting a resin composition for forming a resin molded product such as a material, an appearance defect may occur, which is not preferable (Comparative Examples 3 and 4).

Claims (6)

(A) a polyacetal copolymer having a hemi-formal terminal group amount of 1.0 mmol / kg or less, a formyl terminal group amount of 2.0 mmol / kg or less, and an unstable terminal group amount of 0.5% by weight or less; ,
(B) cyclohexylguanamine;
(C) a piperidine derivative having a sterically hindering group, wherein the nitrogen forming the cyclic amine is a tertiary nitrogen;
(D) a benzotriazole compound,
(E) a hindered phenolic antioxidant,
A polyacetal resin composition containing The component (C) is
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate,
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] undecane) -diethanol and / or dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol The polyacetal resin composition according to claim 1, which is a polymer.   The polyacetal resin composition according to claim 1 or 2, wherein the component (D) is 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol. object.   The polyacetal resin composition according to any one of claims 1 to 3, further comprising (F) a fatty acid ester and / or a polyalkylene glycol. For 100 parts by weight of the component (A),
The component (B) is 0.01 part by weight or more and 1 part by weight or less,
The component (C) is 0.2 parts by weight or more and 1 part by weight or less,
The component (D) is 0.1 part by weight or more and 1 part by weight or less,
The polyacetal resin composition according to any one of claims 1 to 4, wherein the component (E) is 0.03 parts by weight or more and 0.3 parts by weight or less.   A polyacetal resin molded article which is composed of a molded product of the polyacetal resin composition according to any one of claims 1 to 5, and is a constituent material for a portable terminal device or a car navigation casing, or an automobile interior part or building material.