JP2003113289A - Polyacetal resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress generation of formaldehyde by improving processing stability of an acetal resin without reducing appearance of a mold. SOLUTION: This polyacetal resin composition is produced by adding about 0.001-5 hindered phenol-based compound, about 0.001-20 pts.wt. triazine ring- having spiro compound, about 0.01-10 pts.wt. processing stabilizer and about 0.001-10 pts.wt. heat stabilizer to 100 pts.wt. polyacetal resin. The spiro compound may be a compound expressed by formula (1) (wherein R<1> and R<2> are the same or different and express each an alkylene, an arylene or an alarkylene). The polyacetal resin composition may contain a colorant and the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyacetal resin composition having excellent processability and stability, and in which the amount of formaldehyde generated is remarkably suppressed, a method for producing the same, and a polyacetal formed from the resin composition. Regarding resin molded products.

[0002]

2. Description of the Related Art A polyacetal resin is essentially liable to be easily decomposed under a heating and oxidizing atmosphere under acidic or alkaline conditions due to its chemical structure. Therefore, an essential problem of the polyacetal resin is that it has high thermal stability and suppresses the generation of formaldehyde from the molding process or the molded product. When the thermal stability is low, the polymer is decomposed by being heated in a processing step such as an extrusion or molding step, and a deposit (mold deposit) on a mold is generated, and moldability and mechanical properties are deteriorated. Formaldehyde generated by decomposition is chemically active, and becomes formic acid by oxidation, adversely affecting heat resistance, and
When used as a component of electronic equipment, metal contact components are corroded or discolored due to adhesion of organic compounds, resulting in contact defects. Further, formaldehyde itself pollutes the working environment in the component assembly process and the use environment of the final product.

Therefore, in order to stabilize the polyacetal resin, antioxidants and other stabilizers are used. As the antioxidant added to the polyacetal resin, sterically hindered phenol compounds (hindered phenols), sterically hindered amine compounds (hindered amines) and the like are known, and as other stabilizers, melamine, polyamide, Alkali metal hydroxides and alkaline earth metal hydroxides are used. Also,
Antioxidants are usually used in combination with other stabilizers. However, even if such an additive is used, it is difficult to impart high stability to the polyacetal resin.

In Japanese Patent Publication No. 14709/1992, a polyacetal resin, a hindered amine antioxidant, an antistatic agent and a guanamine derivative 3,9-bis [2-] are used.
(3,5-diamino-2,4,6-triazaphenyl)
Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (CTU guanamine) was added,
Disclosed is a polyacetal resin composition having improved thermal stability and improved discoloration tendency due to a magnetic tape. In this document, in order to reduce the discoloration of the polyacetal resin, a hindered amine antioxidant is used in place of the conventionally used hindered phenol antioxidant. However, even with this composition, the tendency of discoloration is improved, but the effect of improving thermal stability is insufficient.

JP-A-62-190248 discloses a stabilized polyacetal resin composition having less formaldehyde odor and improved moldability by blending a polyacetal resin with a guanamine derivative such as benzoguanamine as a stabilizer. Has been done. However, even with this resin composition, the amount of formaldehyde generated is large and the stability is insufficient.

Further, with benzoguanamine used in these resin compositions, a mold deposit is generated during molding, and the exuding property of the molded product is not sufficient.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a polyacetal resin with excellent stability, and particularly to improve the deterioration due to heat in the molding (processing) step, and a method for producing the same. Another object is to provide molded products.

Another object of the present invention is to provide a polyacetal resin composition capable of remarkably suppressing the formation of formaldehyde with a small amount of addition and improving the surrounding environment, a method for producing the same, and a molded article.

Still another object of the present invention is to suppress the formation of formaldehyde even under harsh conditions so that decomposition products and additives adhere to the mold and resin decomposition products and additions from molded products. It is to provide a polyacetal resin composition capable of suppressing leaching of a substance and thermal deterioration of a molded product, improving the quality of the molded product, and improving moldability, a method for producing the same, and a molded product.

[0010]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventors have conducted a series of searches for a nitrogen-containing compound for a stabilizer of a polyacetal resin, and as a result, identified a hindered phenol compound and a specific compound. It was found that when a spiro compound is used in combination with a processing stabilizer and / or heat resistance stabilizer, it has a remarkable effect as a stabilizer for polyacetal resin and significantly improves the generation of formaldehyde from the polyacetal resin. The present invention has been completed.

That is, the polyacetal resin composition of the present invention comprises a polyacetal resin, a hindered phenolic compound, a spiro compound having a triazine ring, and at least one selected from a processing stabilizer and a heat resistance stabilizer. ing. The spiro compound may have a guanamine ring at both ends, and may be, for example, a compound represented by the following formula (1).

[0012]

[Chemical 2]

(In the formula, R ¹ and R ² are the same or different and each represents an alkylene group, an arylene group, or an aralkylene group.) The polyacetal resin composition contains 100 parts by weight of a polyacetal resin and 100 parts by weight of a hindered phenol. 0.001 to 5 parts by weight of the compound, 0.001 to the spiro compound
About 20 parts by weight, about 0.01 to 10 parts by weight of the processing stabilizer, and about 0.001 to 10 parts by weight of the heat resistance stabilizer may be included. The polyacetal resin composition further,
A colorant or the like may be included.

In the method of the present invention, a polyacetal resin composition is produced by mixing a polyacetal resin, a hindered phenol compound, a spiro compound having a triazine ring, a processing stabilizer and a heat resistance stabilizer. Furthermore, the present invention also includes a molded article composed of the polyacetal resin composition.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention comprises a polyacetal resin, a hindered phenolic compound, a spiro compound having a triazine ring, and at least one selected from a processing stabilizer and a heat resistance stabilizer (particularly a processing stabilizer). Stabilizer and heat-resistant stabilizer).

(Polyacetal resin) The polyacetal resin is a polymer compound having an oxymethylene group (-CH ₂ O-) as a main constituent unit, and is a polyacetal homopolymer (for example, trade name "Delrin" manufactured by DuPont, USA). ; Asahi Kasei Co., Ltd., trade name "Tenac 4010", etc.), and polyacetal copolymers containing other comonomer units in addition to the oxymethylene group (for example, Polyplastics Co., Ltd., trade name "Duracon") Be done. In the copolymer, the comonomer unit has an oxyalkylene unit having about 2 to 6 carbon atoms (preferably about 2 to 4 carbon atoms) (for example, an oxyethylene group (—CH ₂
CH ₂ O-), oxypropylene group, and oxytetramethylene group) include. The content of comonomer units is
A small amount, for example, 0.
01 to 20 mol%, preferably 0.03 to 10 mol%
(For example, 0.05 to 9 mol%), and more preferably, it can be selected from the range of about 0.1 to 8 mol%.

The polyacetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like. Polyacetal copolymers include random copolymers and block copolymers (for example,
It is also possible to use Japanese Patent Publication No. 2-24307, Asahi Kasei Kogyo Co., Ltd., trade names “Tenac LA”, “Tenac LM”, etc.) and graft copolymers. Further, the polyacetal resin may have not only a linear structure but also a branched structure and may have a crosslinked structure. Furthermore, the terminal of the polyacetal resin may be stabilized by, for example, esterification with a carboxylic acid such as acetic acid or propionic acid, or an anhydride thereof. The degree of polymerization, the degree of branching and the degree of crosslinking of the polyacetal are not particularly limited as long as they can be melt-molded. The molecular weight of the polyacetal resin is not particularly limited, for example,
The weight average molecular weight is 5,000 to 500,000, preferably about 10,000 to 400,000.

Examples of the polyacetal resin include aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, trioxane, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, 1,3-dioxolane, diethylene glycol formal, 1,4. −
It can be produced by polymerizing a cyclic ether such as butanediol formal or a cyclic formal. Moreover,
As a copolymerization component, an alkyl or aryl glycidyl ether (for example, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, naphthyl glycidyl ether, etc.), alkylene or polyoxyalkylene glycol diglycidyl ether (for example, ethylene glycol diglycidyl ether, triglyceride). It is also possible to use ethylene glycol diglycidyl ether, butanediol diglycidyl ether, etc.), alkyl or aryl glycidyl alcohols, cyclic esters (eg β-propiolactone etc.) and vinyl compounds (eg styrene, vinyl ether etc.).

(Hindered Phenolic Compounds) The hindered phenolic compounds include conventional phenolic antioxidants such as monocyclic hindered phenolic compounds (2,6-di-t-butyl-p-cresol). ), A polycyclic hindered phenol compound linked with a hydrocarbon group or a group containing a sulfur atom [2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4 ′
- methylenebis (2,6-di -t- butylphenol), 1,1,3-tris (2-methyl-4-hydroxy -5-t-butylphenyl) C _1-10 alkylene bis to tetrakis butane (t -Butylphenol)
Kinds; 4,4′-butylidene bis (3-methyl-6-t-
Butylphenol) C _2-10 alkenylene or Jienirenbisu or tetrakis such (t-butylphenol)
Kinds; 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
C _6-20 arylene such as benzene or aralkylene bis to tetrakis (t-butylphenol) s; 4,4 ′
-Thiobis (3-methyl-6-t-butylphenol)
Such as bis (t-butylphenol) linked with a group having a sulfur atom], a hindered phenol compound having an ester group or an amide group [n-octadecyl-3- (4′-hydroxy-3 ′, 5 ′] -Di-t-butylphenyl) propionate, n-octadecyl-2-
T-Butylphenol having a C _2-10 alkylenecarbonyloxy group such as (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate; 1,6-hexanediol-bis [3- (3,3 5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-
Methyl-4-hydroxyphenyl) propionate],
Pentaerythritol tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] and the like, bis or tetrakis (t-butylphenol) s linked by a polyol ester of a fatty acid;
-Bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1
-Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and other heterocyclic groups and C _2-10
Bis or tetrakis (t-butylphenol) s having an alkylenecarbonyloxy group; 2-t-butyl-
6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2
T-alkylphenol (s) having a _C3-10 alkenylcarbonyloxy group such as-[1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenylacrylate. For example, t-butylphenol and t-pentylphenol); hindered phenol compounds having a phosphonate group such as di-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate; N, N ′-
Hindered phenol compounds having an amide group such as hexamethylene bis (3,5-di-t-butyl-4-hydroxy-dihydrocinnamamide)] and the like. Above all, a phenol compound having a t-butyl (particularly a plurality of t-butyl) groups (particularly a compound having a plurality of t-butylphenol moieties) is preferable. In particular, bis to tetrakis (mono to tetra t-butylphenol) linked by a polyol ester of the above fatty acid, particularly,
Bis or tetrakis (mono- or di-t-butylphenol) linked by a di- or tetraol ester group of a C _2-10 fatty acid (particularly a C _2-6 fatty acid) is preferable.

The hindered phenol compound is 1
They may be used alone or in combination of two or more.

(Spiro Compound Having Triazine Ring) The spiro compound having a triazine ring may be any compound having a triazine ring in the side chain of the spiro compound,
The number of triazine rings is not particularly limited and is about 1 to 4, preferably 1 to 2 (particularly 2). In particular, a compound having a structure in which two triazine rings are linked by a spiro compound (that is, a compound having a triazine ring at both ends of the spiro compound) is preferable.

The triazine ring includes 1,2,3-triazine, 1,2,4-triazine and 1,3,5-triazine. Of these, 1,3,5-triazine is preferable. The triazine ring has an alkyl group (C _1-4
It may have a substituent such as an alkyl group), an aryl group, an amino group or a substituted amino group. As the triazine ring, 1,3,5-triazine having an amino group or a substituted amino group as a substituent, particularly a guanamine ring is preferable.

The spiro ring part may be a spiro ring composed only of carbon, but is preferably a spiro ring having a hetero atom (particularly an oxygen atom) as a constituent atom of the ring. Examples of such a spiro compound include a spiro compound represented by the following formula (1) and having a guanamine ring at both ends.

[0024]

[Chemical 3]

(In the formula, R ¹ and R ² are the same or different and each represents an alkylene group, an arylene group or an aralkylene group.) In the above formula (1), an alkylene group represented by R ¹ and R ² Examples thereof include linear or branched C _1-10 alkylene groups such as methylene, ethylene, propylene, isopropylene, butylene, and isobutylene groups. The arylene group is C such as phenylene or naphthylene group.
_6-10 arylene groups can be mentioned. Examples of the aralkylene group include groups in which the alkylene group and the arylene group are linked. Preferred R ¹ and R ² are alkylene groups (such as C _1-6 alkylene groups), especially C _1-3 alkylene groups (such as ethylene group). In addition, the above R ¹ and R ²
_May further have a substituent such as C _1-4 alkyl group such as methyl group, phenyl group, amino group, N-substituted amino group and the like.

Examples of such spiro compounds include, for example, 3,9-bis [2- (3,5-diamino-2,4,4).
6-Triazaphenyl) ethyl] -2,4,8,10-
Tetraoxaspiro [5.5] undecane (CTU guanamine), 3,9-bis [1- (3,5-diamino-
2,4,6-Triazaphenyl) methyl] -2,4
8,10-Tetraoxaspiro [5.5] undecane (CMTU guanamine), 3,9-bis [2- (3,5)
-Diamino-2,4,6-triazaphenyl) -2-methylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1- (3,5) −
Diamino-2,4,6-triazaphenyl) -1,1-
Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [3- (3,3
5-diamino-2,4,6-triazaphenyl) -1,
1-Dimethylpropyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [3-
(3,5-diamino-2,4,6-triazaphenyl)
-3,9- such as -2,2-dimethylpropyl] -2,4,8,10-tetraoxaspiro [5.5] undecane
Examples thereof include bis [(3,5-diamino-2,4,6-triazaphenyl) C _1-6 alkyl] -2,4,8,10-tetraoxaspiro [5.5] undecane. Of these spiro compounds, 3,9-bis [(3,5-
Diamino-2,4,6-triazaphenyl) linear or branched C _1-5 alkyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, eg CTU guanamine, CMTU guanamine, 3 , 9-bis [3- (3,5
-Diamino-2,4,6-triazaphenyl) -1,1
-Dimethylpropyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like are preferable, and particularly CT
U guanamine is preferred.

These spiro compounds may be water-containing compounds of crystallization, hydrated compounds or anhydrous compounds, but in view of dispersibility of the spiro compounds in the polyacetal resin, water of crystallization is particularly preferable. The spiro compound contained is preferably used. Usually, 0.1 in one molecule of spiro compound
Contains ~ 3 molecules of water of crystallization.

Such a spiro compound is obtained, for example, by reacting a dioxonitrile having a tetraoxospiro ring with dicyandiamide in an alcoholic organic solvent at high pressure in the presence of a basic catalyst (JP-A-5-32664). ), In an ether organic solvent in the presence of a basic catalyst (JP-B-44-8676).

In the reaction of such a dinitrile having a tetraoxospiro ring with dicyandiamide, a spiro compound having a nitrile group at one end and a guanamine ring at the other end can be prepared. A spiro compound having a nitrile group at one end and a guanamine ring at the other end is 3
-(Cyanoalkyl) -9-[(3,5-diamino-2,
4,6-Triazaphenyl) alkyl] -2,4,8,10
-Tetraoxaspiro [5.5] undecane [eg 3
-(2-Cyanoethyl) -9- [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,
4,8,10-Tetraoxaspiro [5.5] undecane (CTU monoguanamine), 3- (1-cyanomethyl) -9- [1- (3,5-diamino-2,4,6-triazaphenyl) ) Methyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (CMTU monoguanamine), 3- (2-cyano-2-methylethyl) -9.
-[2- (3,5-Diamino-2,4,6-triazaphenyl) -2-methylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3- (1 -Cyano-1,1-dimethylmethyl) -9- [3- (3,5
-Diamino-2,4,6-triazaphenyl) -1,1
-Dimethylmethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3- (3-cyano-2,
2-Dimethylpropyl) -9- [3- (3,5-diamino-2,4,6-triazaphenyl) -2,2-dimethylpropyl] -2,4,8,10-tetraoxaspiro [5 .5] undecane and 3- (3-cyano-1,1)
-Dimethylpropyl) -9- [3- (3,5-diamino-2,4,6-triazaphenyl) -1,1-dimethylpropyl] -2,4,8,10-tetraoxaspiro [5. 5] 3- (cyano C _1-6 alkyl) -9-[(3,5-diamino-2,4,6-triazaphenyl) C _1-6 alkyl] -2,4,8,10 such as undecane -Tetraoxaspiro [5.5] undecane] and the like can be exemplified. Of these spiro compounds, 3- (cyano C
_1-5 Linear or branched alkyl) -9-[(3,5-diamino-2,4,6-triazaphenyl) linear or branched C
_1-5 alkyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, for example, CTU monoguanamine, CMTU monoguanamine, 3- (3-cyano-1,
1-Dimethylpropyl) -9- [3- (3,5-diamino-2,4,6-triazaphenyl) -1,1-dimethylpropyl] -2,4,8,10-tetraoxaspiro [5 .5] Undecane and the like are preferable, and CTU monoguanamine is particularly preferable.

Such a spiro compound having a triazine ring (guanamine ring or the like) at one end, and a mixture of a spiro compound having a triazine ring at one end and a spiro compound having a triazine ring (such as a guanamine ring) at both ends Are also included in the spiro compounds of the present invention.

Of these, it is preferable to include a spiro compound having a triazine ring at least at both ends, for example, 3,9-bis [(3,5-diamino-2,4,6-triazaphenyl) alkyl]. -2,4,8,10-Tetraoxaspiro [5.5] undecane and 3- (cyanoalkyl) -9-[(3,5-diamino-2,4,6-triazaphenyl) alkyl]- Spiro compounds composed of 2,4,8,10-tetraoxaspiro [5.5] undecane, especially 3,9-bis [(3,5-diamino-2,4,6-triazaphenyl) C _1-6 alkyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and 3- (cyano C
_1-6 alkyl) -9-[(3,5-diamino-2,4,6-
Triazaphenyl) C _1-6 alkyl] -2,4,8,10-
It may be a spiro compound composed of tetraoxaspiro [5.5] undecane and the like.

(Processing Stabilizer) As the processing stabilizer, (a)
At least one selected from long-chain fatty acids or derivatives thereof, (b) polyoxyalkylene glycol, (c) silicone compound, and the like.

(A) Long chain fatty acid or derivative thereof The long chain fatty acid may be a saturated fatty acid or an unsaturated fatty acid. Further, those in which a part of hydrogen atoms are substituted with a substituent such as a hydroxyl group can also be used.
As such a long-chain fatty acid, a monovalent or divalent fatty acid having 10 or more carbon atoms, for example, a monovalent saturated fatty acid having 10 or more carbon atoms [capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, C _10-34 saturated fatty acids such as stearic acid, arachidic acid, behenic acid, and montanic acid (preferably C _10-30 saturated fatty acids)], carbon number 10
The above monovalent unsaturated fatty acids [oleic acid, linoleic acid,
C _10-34 unsaturated fatty acids (preferably C _10-30 unsaturated fatty acids) such as linolenic acid, arachidonic acid and erucic acid], divalent fatty acids having 10 or more carbon atoms (dibasic fatty acids) [sebacic acid, Dodecanedioic acid, tetradecanedioic acid,
Divalent C _10-30 saturated fatty acids such as Tapushia acid (preferably a divalent C _10-20 saturated fatty acids), decenoic acid, a divalent unsaturated C _10-30 fatty acids such as dodecene diacid (preferably 2
C _10-20 unsaturated fatty acid) and the like]. These fatty acids may be used alone or in combination of two or more.
The fatty acid also includes a fatty acid having one or more hydroxyl groups in the molecule (for example, a hydroxy saturated C _10-26 fatty acid such as 12-hydroxystearic acid).

Derivatives of the long-chain fatty acids include fatty acid esters and fatty acid amides. The structure of the long-chain fatty acid ester is not particularly limited, and any linear or branched fatty acid ester can be used, and esters of the long-chain fatty acid and alcohol (monoester, diester, triester, tetraester). Etc. having one or more ester bonds such as). The type of alcohol constituting the long-chain fatty acid ester is not particularly limited, but polyhydric alcohol is preferable. The polyhydric alcohol has a carbon number of about 2 to 8, preferably about 2 to 6, or a polymer thereof, for example, an alkylene glycol (for example, C _2-8 such as ethylene glycol, diethylene glycol or propylene glycol). Diols such as alkylene glycol (preferably C _2-6 alkylene glycol) and the like, triols such as glycerin, trimethylolpropane or derivatives thereof, tetraols such as pentaerythritol, sorbitan or derivatives thereof, and these Homogeneous or copolymers of polyhydric alcohols (for example, polyoxyalkylene glycol homo- or copolymers such as polyethylene glycol and polypropylene glycol, polyglycerin, dipentaerythritol, polypentaerythritol, etc.) And others. The average degree of polymerization of the polyalkylene glycol is 2 or more (for example, 2 to 500), preferably 2 to 400 (for example, 2
To about 300) and an average degree of polymerization of 16 or more (for example,
20 to 200) is preferable, and such a polyalkylene glycol is preferably used as an ester with a fatty acid having 12 or more carbon atoms. Preferred polyhydric alcohols are polyalkylene glycols having an average degree of polymerization of 2 or more. These polyhydric alcohols can be used alone or in combination of two or more.

Examples of such long-chain fatty acid ester include ethylene glycol mono-dipalmitate, ethylene glycol mono-distearate, ethylene glycol mono-dibehenate, ethylene glycol mono-dimontanate, glycerin mono. -Tripalmitic acid ester, glycerin mono-tristearic acid ester, glycerin mono-tribehenic acid ester, glycerin mono-trimontanic acid ester, pentaerythritol mono-tetrapalmitic acid ester, pentaerythritol mono-tetrastearic acid ester, pentaerythritol mono- Tetrabehenate, pentaerythritol mono-tetramontanate, polyglycerin tristearate, trimethylol B bread mono palmitate, pentaerythritol mono undecyl acid ester,
Sorbitan monostearate, polyalkylene glycol (polyethylene glycol, polypropylene glycol, etc.) monolaurate, monopalmitate, monostearate, monobehenate, monomontanate, dilaurate, dipalmitate, distearate, dibehenate, dimontanate, dioleate, dilinoleate, etc. Is mentioned.

As the fatty acid amide, an acid amide (monoamide, bisamide, etc.) of the long-chain fatty acid (monovalent or divalent long-chain fatty acid) and amines (monoamine, diamine, polyamine, etc.) can be used. Examples of monoamides include primary acid amides of saturated fatty acids such as capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, and montanic acid amide, and oleic acid. Primary acid amides of unsaturated fatty acids such as amides,
Examples thereof include secondary acid amides of saturated and / or unsaturated fatty acids such as stearyl stearic acid amide and stearyl oleic acid amide, and monoamines. The preferred fatty acid amide is bisamide. The bisamide includes C
_1-6 alkylenediamine (in particular, C _1-2 alkylenediamine) and bisamide of the above fatty acid are included, and specific examples thereof include ethylenediamine-dipalmitic acid amide and ethylenediamine-distearic acid amide (ethylenebisstearylamide). , Hexamethylenediamine-
Examples thereof include distearic acid amide, ethylenediamine-dibehenic acid amide, ethylenediamine-dimontanic acid amide, ethylenediamine-dioleic acid amide, ethylenediamine-dierucic acid amide, and the like, and the amine moiety of alkylenediamine such as ethylenediamine- (stearic acid amide) oleic acid amide. It is also possible to use a bisamide having a structure in which different acyl groups are bonded to In the acid amide, the fatty acid forming the acid amide is preferably a saturated fatty acid.

These long-chain fatty acids or their derivatives can be used alone or in combination of two or more.

(B) Polyoxyalkylene glycol The polyoxyalkylene glycol includes alkylene glycol (for example, C _2-6 alkylene glycol (preferably C _2-4 alkylene glycol) such as ethylene glycol, propylene glycol and tetramethylene glycol). Etc.) homopolymers, copolymers, and derivatives thereof. Specific examples thereof include poly C _2-6 oxyalkylene glycol (preferably poly C _2-4 oxyalkylene glycol) such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, polyoxyethylene-polyoxypropylene copolymer (random Or block copolymers), polyoxyethylene polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene monobutyl ether, and other copolymers. Preferred polyoxyalkylene glycols are polymers having oxyethylene units, such as polyethylene glycol, polyoxyethylene polyoxypropylene copolymers and their derivatives. The number average molecular weight of the polyoxyalkylene glycol is 3 × 10 ² to 1 × 1.
0 ⁶ (for example, 5 × 10 ^{2 to} 5 × 10 ⁵ ), preferably 1
× 10 ³ to 1 × 10 ⁵ (for example, 1 × 10 ^{3 to} 5 × 10 ⁴ )
It is a degree.

The polyoxyalkylene glycol can be used alone or in combination of two or more kinds.

(C) Silicone Compound The silicone compound includes polyorganosiloxane and the like. Examples of the polyorganosiloxane include dialkyl siloxane (eg, dimethyl siloxane),
Examples thereof include homopolymers (eg, polydimethylsiloxane, polyphenylmethylsiloxane, etc.) and copolymers of alkylaryl siloxanes (eg, methylphenylsiloxane, etc.) and diarylsiloxanes (eg, diphenylsiloxane, etc.). The polyorganosiloxane may be an oligomer. In addition, polyorganosiloxane includes epoxy group, hydroxyl group, alkoxy group, carboxyl group, amino group or substituted amino group (dialkylamino group, etc.), ether group, vinyl group, (meth) acryloyl at the molecular end or main chain. A modified polyorganosiloxane having a substituent such as a group (eg, modified silicone) and the like are also included. These silicone compounds can be used alone or in combination of two or more.

(Heat resistance stabilizer) The heat resistance stabilizer includes (a)
Basic nitrogen compounds, (b) phosphine compounds, (c) organic carboxylic acid metal salts, (d) alkali or alkaline earth metal compounds, (e) hydrotalcite and (f) zeolite are included.

(A) Basic Nitrogen Compound The basic nitrogen-containing compound includes a low molecular weight compound and a high molecular weight compound (nitrogen-containing resin). Examples of the nitrogen-containing low molecular weight compound include aliphatic amines (monoethanolamine, diethanolamine, etc.), aromatic amines (o
-Aromatic secondary amines or tertiary amines such as toluidine, p-toluidine, p-phenylenediamine), amide compounds (polyvalent carboxylic acid amides such as malonamide and isophthalic acid diamide, p-aminobenzamide), hydrazine Or derivatives thereof (hydrazine, hydrazone, hydrazides such as polyhydric carboxylic acid hydrazide), polyaminotriazines [guanamine, acetoguanamine, benzoguanamine, succinoguanamine, adipoguanamine, 1,3,6-tris (3,5- Diamino-2,4,6-triazinyl) hexane, guanamines such as phthaloguanamine or their derivatives, melamine or its derivatives (melamine; melamine condensates such as melam, melem, melon, etc.)], uracil or its derivatives (uracil) , Uridine Etc.), cytosine or a derivative thereof (cytosine, cytidine, etc.), guanidine or a derivative thereof (acyclic guanidine such as guanidine, cyanoguanidine; cyclic guanidine such as creatinine), urea or a derivative thereof [biuret, biurea, ethyleneurea, acetylene]. Urea, isobutylidene diurea, crotylidene diurea, a condensation product of urea and formaldehyde,
Hydantoin, substituted hydantoin derivatives (mono- or di-C _1-4 alkyl substitution products such as 1-methylhydantoin, 5-propylhydantoin, and 5,5-dimethylhydantoin; aryl substitutions such as 5-phenylhydantoin and 5,5-diphenylhydantoin Body; alkylaryl substituents such as 5-methyl-5-phenylhydantoin), allantoin, substituted allantoin derivatives (eg, mono-, di- or tri-C _1-4 alkyl substituents, aryl substituents, etc.), metal salts of allantoin (Salts such as allantoin dihydroxyaluminum, allantoin monohydroxyaluminum, and allantoin aluminum with metal of Group 3B of the periodic table), reaction products of allantoin and aldehyde compounds (allantoin formaldehyde adduct, etc.), allanto The compounds of the emission and the imidazole compound (allantoin sodium -dl pyrrolidone carboxylate, etc.), organic acid salts], and others.

Examples of the nitrogen-containing resin include amino resins (condensation resins such as guanamine resin, melamine resin and guanidine resin, phenol-melamine resin, benzoguanamine-melamine resin, aromatic polyamine-melamine resin) formed by reaction with formaldehyde. Such as co-condensation resin), aromatic amine-formaldehyde resin (aniline resin, etc.), polyamide resin (for example, nylon 3 (poly β-alanine), nylon 46, nylon 6, nylon 66, nylon 11, nylon 12, nylon). MXD6, nylon 6-10, nylon 6-11,
Nylon 6-12, nylon 6-66-610 and other homo- or copolymer polyamides, substituted polyamides having a methylol group or an alkoxymethyl group), polyester amides, polyamide imides, polyurethanes, poly (meth)
Acrylamide, copolymer of (meth) acrylamide with other vinyl monomer, poly (vinyl lactam), copolymer of vinyl lactam with other vinyl monomer (for example, JP-A-55-52338, U.S. Pat. 320
No. 4014 homopolymer or copolymer), poly (N-vinylcarboxylic acid amide), a copolymer of N-vinylcarboxylic acid amide and another vinyl monomer (for example, JP 2001-247745 A). Publication, JP 2001
-131386, JP-A-8-311302, JP-A-59-86614, and U.S. Pat. No. 545.
5042, U.S. Pat. No. 5,407,996, U.S. Pat. No. 5,338,815, homopolymers or copolymers, manufactured by Showa Denko KK, trade names "Noniolex", "Clastic", etc.) it can.

These basic nitrogen-containing compounds can be used alone or in combination of two or more.

Preferred nitrogen-containing compounds include guanamines (such as adipguanamine), melamine or derivatives thereof [especially melamine or melamine condensates (such as melam and melem)], guanidine derivatives (such as cyanoguanidine and creatinine), and urea derivatives. [Biurea, condensate of urea and formaldehyde, allantoin, metal salt of allantoin (allantoin dihydroxyaluminum, etc.)], nitrogen-containing resin [amino resin (amino resin such as melamine resin, melamine-formaldehyde resin; crosslinked melamine resin, etc. Amino resin), polyamide resin, poly (meth) acrylamide, poly (N-vinylcarboxylic acid amide), poly (vinyl lactam), etc.] are included.

(B) Phosphine Compound The phosphine compound is an alkylphosphine (for example,
Triethylphosphine, tripropylphosphine, tributylphosphine, and other triC _1-10 alkylphosphines, cycloalkylphosphine (eg, tricyclohexylphosphine, and other C _5-12 cycloalkylphosphines), arylphosphine (eg, triphenyl) Phosphine, p-tolyldiphenylphosphine,
Di-p-tolylphenylphosphine, tri-m-aminophenylphosphine, tri-2,4-dimethylphenylphosphine, tri-2,4,6-trimethylphenylphosphine, tri-o-tolylphosphine, tri-m-tolyl Phosphine, tri C _6-12 arylphosphine such as tri-p-tolylphosphine), aralkylphosphine (eg, tri-o-anisylphosphine, tri-p)
_-Tri C _6-12 aryl C _1-4 alkylphosphine such as anisylphosphine), arylalkenylphosphine (for example, diC _6-12 aryl C _2-10 alkenylphosphine such as diphenylvinylphosphine, allyldiphenylphosphine) , aryl aralkyl phosphines (for example, di-C _6-12 aryl C _6-12 aralkyl phosphines such as p- anisyl diphenylphosphine, di -p
-C _6-12 aryldi C _6-12 aryl C _1-4 alkylphosphine such as anisylphenylphosphine), alkylaryl aralkylphosphine (eg C _1-10 alkyl C such as methylphenyl-p-anisylphosphine)
_6-12 aryl C _6-12 aryl C _1-4 alkylphosphine, etc.), bisphosphines [eg, bis (diC _6-12 arylphosphino) C ₁ such as 1,4-bis (diphenylphosphino) butane] _-10 alkane] and the like. These phosphine compounds can be used alone or in combination of two or more.

(C) Organic Carboxylic Acid Metal Salt Examples of the organic carboxylic acid metal salt include organic carboxylic acids and metals (alkali metals such as Na and K; alkaline earth metals such as Mg and Ca; transition metals such as Zn). And salt.

The organic carboxylic acid may be either a low molecular weight compound or a high molecular weight compound. In addition to the long chain saturated or unsaturated aliphatic carboxylic acid exemplified in the section of the long chain fatty acid, it has less than 10 carbon atoms. Lower saturated or unsaturated aliphatic carboxylic acid,
Polymers of unsaturated aliphatic carboxylic acids can also be used. Moreover, these aliphatic carboxylic acids may have a hydroxyl group. Examples of the lower saturated aliphatic carboxylic acid include saturated C _1-9 monocarboxylic acid (acetic acid, propionic acid,
Butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, caprylic acid, etc., saturated C _2-9 dicarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cork) Acid, azelaic acid, etc.) and these oxy acids (glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, citric acid, etc.) and the like.

As the lower unsaturated aliphatic carboxylic acid,
Unsaturated C _3-9 monocarboxylic acid [(meth) acrylic acid, crotonic acid, isocrotonic acid, etc.], unsaturated C _4-9 dicarboxylic acid (maleic acid, fumaric acid, etc.), and these oxy acids (propiolic acid, etc.) ) Etc. can be illustrated.

The unsaturated aliphatic carboxylic acid polymer may be a polymerizable unsaturated carboxylic acid [α, β-ethylenically unsaturated carboxylic acid, for example, a polymerizable unsaturated monocarboxylic acid such as (meth) acrylic acid. Acid, polymerizable unsaturated polycarboxylic acid (itaconic acid, maleic acid, fumaric acid, etc.), acid anhydride or monoester of said polycarboxylic acid (mono C _1-10 alkyl ester such as monoethyl maleate, etc.)
Etc.] and olefins (alpha, such as ethylene and propylene
C _2-10 olefin, etc.) and the like.

These organic carboxylic acid metal salts can be used alone or in combination of two or more kinds.

Preferred organic carboxylic acid metal salts include alkaline earth metal organic carboxylic acid salts (calcium acetate, calcium citrate, calcium stearate, magnesium stearate, calcium 12-hydroxystearate, etc.), ionomer resins (the aforementioned polymerizable unsaturated). Resins in which at least a part of the carboxyl groups contained in the copolymer of a polyvalent carboxylic acid and an olefin are neutralized by the ions of the metal). The ionomer resin is, for example, ACLYN (manufactured by Allied Signal Co., Ltd.),
It is commercially available as Himilan (manufactured by Mitsui DuPont Polychemical Co., Ltd.) and Surlyn (manufactured by DuPont Co., Ltd.).

(D) Alkali or alkaline earth metal compounds Alkali or alkaline earth metal compounds include CaO and M
Metal oxide such as gO, metal hydroxide such as Ca (OH) ₂ and Mg (OH) ₂ , metal inorganic acid salt (Na ₂ CO ₃ , K ₂ C)
Inorganic compounds such as metal carbonates such as O ₃ , CaCO ₃ and MgCO ₃ and inorganic acid salts such as borate and phosphate are included, and metal oxides and metal hydroxides are particularly preferable. Of the above compounds, alkaline earth metal compounds are preferred.

These alkali or alkaline earth metal compounds can be used alone or in combination of two or more kinds.

(E) Hydrotalcite As hydrotalcite, hydrotalcites described in JP-A-60-1241 and JP-A-9-59475, for example, are represented by the following formula. A hydrotalcite compound or the like can be used.

[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] ^{x +} [A ^n- _{x / n} · mH ₂ O] ^x- (wherein M ²⁺ is Mg ²⁺ , Mn ²⁺ , It shows divalent metal ions such as Fe ²⁺ and Co ²⁺ , and M ³⁺ is Al ³⁺ , Fe ³⁺ , Cr ³⁺
And trivalent metal ions. A ^n- is CO ₃ ^2-, OH ^-,
An n-valent (particularly monovalent or divalent) anion such as HPO ₄ ²⁻ or SO ₄ ²⁻ is shown. x is 0 <x <0.5, and m is
0 ≦ m <1. ) These hydrotalcites are
They can be used alone or in combination of two or more.

The hydrotalcite is "DHT-
4A ”,“ DHT-4A-2 ”,“ Alcamizer ”and the like are available from Kyowa Chemical Industry Co., Ltd.

(F) Zeolite Zeolite is not particularly limited, but zeolites other than H-type zeolite, for example, zeolites described in JP-A-7-62142 [minimum unit cell is alkali and / or alkaline earth metal] , Which is a crystalline aluminosilicate of A (type A, type X, type Y, type L and ZSM type zeolite, mordenite type zeolite; chabazite,
Morden-zeolite, natural zeolite such as faujasite, etc.)] etc. can be used.

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

The A-type zeolite is "zeolum A-
3 ”,“ Zeolam A-4 ”,“ Zeolam A-5 ”, etc., and the X-type zeolite is“ Zeolam F-9 ”, Y
Type zeolite is available from Tosoh Corporation as "HSZ-320NAA".

The heat resistance stabilizer may be used alone or in combination of two or more kinds. When a basic nitrogen-containing compound is used in combination with at least one selected from a phosphine compound, an organic carboxylic acid metal salt, an alkali or alkaline earth metal compound, hydrotalcite, and zeolite, heat resistance stability is imparted in a small amount. You can also do it.

(Ratio of Each Component) In the resin composition of the present invention, the ratio of the hindered phenol compound is 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, based on 100 parts by weight of the polyacetal resin. Parts by weight, more preferably about 0.01 to 1 part by weight.

The proportion of the spiro compound is 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight, and more preferably 0.001 to 100 parts by weight of the polyacetal resin.
It is about 03 to 5 parts by weight.

The proportion of the processing stabilizer is 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight (for example, 0.05 to 3 parts by weight), and particularly about 100 parts by weight of the polyacetal resin. It is about 0.05 to 2 parts by weight.

The ratio of the heat resistance stabilizer is, for example, 0.001 to 10 parts by weight, preferably 0.001 to 5 parts by weight (particularly 0.01 to 10 parts by weight) based on 100 parts by weight of the polyacetal resin.
2 parts by weight). In particular, when a basic nitrogen compound is used as the heat resistance stabilizer, the ratio of the basic nitrogen compound is 0.001 to 1 part by weight, preferably 0.005 to 100 parts by weight with respect to 100 parts by weight of the polyacetal resin.
It can be selected from the range of about 0.5 parts by weight (particularly 0.01 to 0.15 parts by weight).

(Colorant) The polyacetal resin composition of the present invention may further contain a colorant. As the colorant, various dyes or pigments can be used. The dye is preferably a solvent dye, and examples thereof include azo dyes, anthraquinone dyes, phthalocyanine dyes, and naphthoquinone dyes. As the pigment, both an inorganic pigment and an organic pigment can be used.

As the inorganic pigments, titanium pigments, zinc pigments, carbon blacks (furnace black, channel black, acetylene black, Ketjen black, etc.), iron pigments, molybdenum pigments, cadmium pigments, lead pigments, Examples include cobalt-based pigments and aluminum-based pigments.

Examples of organic pigments include azo pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, dioxazine pigments, and slene pigments. .

The above colorants may be used alone or in combination of plural colorants. When a colorant having a high light shielding effect (carbon black, titanium white (titanium oxide), phthalocyanine-based pigment, especially carbon black) is used, weather resistance (light) can be improved.

The content of the colorant is, for example, 0 to 5 parts by weight (for example, 100 parts by weight of the polyacetal resin).
0.01 to 5 parts by weight), preferably 0.1 to 4 parts by weight,
More preferably, it is about 0.1 to 2 parts by weight.

The polyacetal resin composition of the present invention contains
If necessary, conventional additives such as antioxidants (amine-based, phosphorus-based, sulfur-based, hydroquinone-based, quinoline-based antioxidants, etc.), weathering (light) agents, release agents, nucleating agents, charging agents Inhibitors, slidability improvers, impact modifiers, flame retardants, surfactants, antibacterial agents, antifungal agents, fragrances, fragrances, various polymers [acrylic resins (C _1-10 such as polymethylmethacrylate, etc. Alkyl (meth) acrylate homopolymer or copolymer), acrylic-based core-shell polymer, polycarbonate-based resin, polyolefin-based resin, polyurethane-based resin, polyester-based resin, fluorine-based resin, silicone-based resin, etc.], filler, etc. Alternatively or in combination of two or more.

If necessary, in order to improve the performance of the molded article of the present invention, conventional fillers such as fibrous, plate-like, and granular materials may be blended alone or in combination of two or more kinds. Good. Examples of the fibrous filler include inorganic fibers (glass fibers, carbon fibers, boron fibers, potassium titanate fibers (whiskers), etc.), organic fibers (amide fibers, etc.) and the like. Examples of the plate-like filler include glass flakes, mica, graphite, various metal foils and the like. Examples of powdered and granular fillers include metal oxides (zinc oxide, alumina, etc.), sulfates (calcium sulfate, magnesium sulfate, etc.), carbonates (calcium carbonate, etc.), glasses (milled fiber, glass beads, glass balloons, etc.) ,
Silicates (talc, kaolin, silica, diatomaceous earth, clay, wollastonite, etc.), sulfides (molybdenum disulfide, tungsten disulfide, etc.), carbides (fluorinated graphite,
Examples thereof include silicon carbide) and boron nitride.

(Method for producing polyacetal resin composition)
The polyacetal resin composition of the present invention may be a powdery or granular mixture or a melt mixture, a polyacetal resin, a hindered phenolic compound, and the spiro compound,
It can be prepared by mixing a processing stabilizer and / or heat resistance stabilizer and, if necessary, other additives by a conventional method.
For example, (1) each component is fed from a main feeder, kneaded and extruded by a uniaxial or biaxial extruder to prepare pellets, and then molded, and (2) a spiro compound-free component is added to the main feeder. , And at least a component containing a spiro compound (as another component, a polyacetal resin, a stabilizer, other additives, etc.) is fed from a side feeder and kneaded and extruded by a uniaxial or biaxial extruder to prepare pellets. , Molding method, (3) once preparing pellets (masterbatch) having different compositions,
The pellets are mixed (diluted) in a predetermined amount and subjected to molding to obtain a molded product having a predetermined composition, (4) After the inhibitor is attached to the polyacetal resin pellets by spraying or the like,
A method of molding to obtain a molded product having a predetermined composition can be adopted. Also, in the preparation of the composition used in the molded article,
Mixing the base polyacetal resin powder (for example, powder obtained by crushing a part or all of the polyacetal resin) and other components (hindered phenol compound, processing stabilizer, heat stabilizer, spiro compound, etc.) Then, melt kneading is advantageous for improving the dispersion of the additives.

The polyacetal resin composition of the present invention can remarkably suppress the formation of formaldehyde due to the oxidation or thermal decomposition of the polyacetal resin particularly in the molding process (particularly the melt molding process), and the working environment can be improved.
Further, it is possible to remarkably suppress the adhesion of decomposed products and additives to the mold (mold deposit) and the leaching of decomposed products and additives from the molded product, and it is possible to improve various problems during the molding process. Therefore, the resin composition of the present invention, a conventional molding method, for example,
It is useful for molding various molded products by methods such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, and gas injection molding.

(Molded Product) The Polyacetal Resin Composition
The polyacetal resin molded article of the present invention composed of
A chondrophenol compound, a specific spiro compound,
Including a processing stabilizer and / or a heat stabilizer in combination
And is excellent in extrusion and / or molding processing stability.
In addition, the amount of formaldehyde generated is extremely small. Sanawa
A conventional polyacetator containing stabilizers such as antioxidants
A molded product made of resin is a relatively large amount of formaldehyde.
Dehydration, corrosion, discoloration, living environment and work
Pollute the environment. For example, commercially available polya
The amount of formaldehyde generated from a cetal resin molded product is
Surface area of 1 cm in dry type (under constant temperature and dry atmosphere)²This
2-5 μg or so, wet (under constant temperature and moist atmosphere)
At a surface area of 1 cm ²Per 3-6 μg
It

On the other hand, in the polyacetal resin molded product of the present invention, the amount of formaldehyde generated is 1.5 μg or less, preferably 0 to 1.3 μg, more preferably 0 to 1 μg per 1 cm ² of the surface area of the molded product in the dry method. It is about 0.01 to 1 μg. In the wet method, the amount of formaldehyde generated is 2.5 μg or less (about 0 to ² μg), preferably 0 to 1.7 μg, and more preferably 0 to 1.5 per 1 cm ² of the surface area of the molded product.
It is about μg, and usually about 0.01 to 1.5 μg.

The polyacetal resin molded article of the present invention may have the formaldehyde generation amount in either dry type or wet type, and usually has the formaldehyde generation amount in both dry type and wet type. There is.

The amount of formaldehyde generated in the dry method can be measured as follows.

After the polyacetal resin molded product is cut as necessary to measure the surface area, an appropriate amount (for example, a surface area of 10 to 50 cm ² ) of the molded product is placed in a closed container (capacity 20 ml) and the temperature is set to 80. Leave at 24 ° C for 24 hours. After that, 5 ml of water is injected into this closed container, the amount of formalin in this aqueous solution is quantified according to JIS K0102, 29 (formaldehyde term), and the amount of formaldehyde generated per surface area of the molded product (μg / cm ² ) is determined.

The amount of formaldehyde generated in the wet state can be measured as follows.

After the polyacetal resin molded product is cut as necessary to measure the surface area, an appropriate amount of the molded product (for example, a surface area of 10 to 100 cm ² ) is placed in a closed container (volume 1 L) containing 50 ml of distilled water. ) Suspended and sealed in the lid, and left in a constant temperature bath at a temperature of 60 ° C. for 3 hours. Then, the mixture is allowed to stand at room temperature for 1 hour, and the amount of formalin in the aqueous solution in the closed container is quantified according to JIS K0102, 29 (formaldehyde item) to determine the amount of formaldehyde generated (μg / cm ² ) per surface area of the molded product.

The numerical value of the amount of formaldehyde generated in the present invention is the conventional additive as long as it contains a polyacetal resin, a hindered phenolic compound, a specific spiro compound, a processing stabilizer and / or a heat resistance stabilizer. The surface of the molded product is not only the molded product of the polyacetal resin composition containing (normal stabilizer, release agent, etc.) but also the molded product of the composition containing the inorganic filler, other polymer, etc. Most of the
It is also applicable to a molded product (for example, a multicolor molded product or a coated molded product) in which 0%) is composed of a polyacetal resin.

The molded article of the present invention can be used for any application in which formaldehyde has a harmful effect (for example, a knob or a lever as a bicycle part), but it can be used for automobile parts or electric / electronic parts (active parts or passive parts). Parts, etc.), building materials / piping parts, daily necessities (life) / cosmetics parts, and medical (medical / treatment) parts.

More specifically, as automobile parts, inner handle, FE trunk opener, seat belt buckle, assist wrap, interior parts such as various switches, knobs, levers, clips, electric system parts such as meters and connectors, Mechanisms such as in-vehicle electric / electronic parts such as audio equipment and car navigation equipment, parts that come into contact with metal typified by carrier plates of window regulators, door lock actuator parts, mirror parts, wiper motor system parts, fuel system parts, etc. Parts can be illustrated.

As electric / electronic parts (mechanical parts), parts or members of equipment which are made of polyacetal resin molding and have many metal contacts [for example, audio equipment such as cassette tape recorder, VTR (video tape recorder), etc.] ), 8mm video, video equipment such as video cameras, OA (office automation) equipment such as copiers, facsimiles, word processors, computers, as well as toys, telephones, computers, etc. that are driven by the driving force of motors, springs, etc. Attached keyboard, etc.] and the like. Specific examples include chassis (base), gears, levers, cams, pulleys and bearings. Further, optical and magnetic media parts (for example, metal thin film magnetic tape cassettes, magnetic disk cartridges, magneto-optical disk cartridges, etc.), at least a part of which is composed of a polyacetal resin molded product,
More specifically, it can be applied to a music metal tape cassette, a digital audio tape cassette, an 8 mm video tape cassette, a floppy disk cartridge, a mini disk cartridge and the like. Specific examples of optical and magnetic media parts include tape cassette parts (tape cassette body, reel, hub, guide, roller, stopper, lid, etc.), disk cartridge parts (disk cartridge body (case), shutter, clamping). Plate etc.) and the like.

Further, the polyacetal resin molded product of the present invention is a building material / piping component such as a lighting fixture, fitting, piping, cock, faucet, toilet peripheral component, fasteners (slide fastener, snap fastener, surface fastener,
Rail fasteners etc.), stationery, lip balm / lipstick container, washer, water purifier, spray nozzle, spray container, aerosol container, general container, injection needle holder, etc. It is preferably used for related parts.

[0087]

The polyacetal resin composition of the present invention is
Since it contains a hindered phenolic compound, a specific spiro compound, and a processing stabilizer and / or a heat resistance stabilizer, the thermal stability during extrusion / molding processing of the polyacetal resin is significantly improved, and By adding a small amount of components, the amount of formaldehyde generated from the polyacetal resin and molded products can be suppressed to an extremely low level, and the surrounding environment (work environment, use environment, etc.) can be greatly improved. Furthermore, it is possible to suppress the formation of formaldehyde even under harsh conditions, adhesion of decomposition products and additives to molds (mold deposit), leaching of resin decomposition products and additives from molded products, and molding products. It is possible to suppress the thermal deterioration of, and improve the quality and moldability of molded products.

[0088]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

In the examples and comparative examples, the thermal stability, moldability (amount of mold deposit), amount of formaldehyde generated from dry and wet molded products, and exudation property are as follows. And evaluated.

[Thermal Stability] The thermal stability was evaluated by the weight loss rate (% / min) per minute when the pellets were heated in air at 230 ° C. for 45 minutes.

[Moldability (amount of deposit on mold)] Molded product (diameter 20 mm x 1 mm) having a specific shape from pellets formed of the polyacetal resin composition is continuously molded (1000 shots) using an injection molding machine. The degree of adherence to the mold is 5
Graded. It should be noted that the smaller the number, the less the amount of deposits on the mold, that is, the less the mold deposit.

[Amount of Formaldehyde Emitted from Molded Product in Dry Method] Ten test pieces (2 mm × 2 mm × 50 mm) (total surface area of about 40 cm ² ) of resin sample were placed in a closed container (capacity: 20 ml), and the temperature was 80 ° C. After heating in a constant temperature bath for 24 hours, it was cooled to room temperature and 5 ml of distilled water was injected with a syringe. The formaldehyde amount of this aqueous solution was quantified according to JIS K0102, 29 (formaldehyde item), and the formaldehyde gas generation amount per surface area (μg / cm ² ) was calculated.

[Amount of Formaldehyde Emitted from Molded Article in Wet Condition] Flat test piece (100 mm × 40 mm × 2 m)
m; total surface area 85.6 cm ² ) was hung from the lid of a polyethylene bottle (volume 1 L) containing 50 ml of distilled water and sealed,
After leaving it in a constant temperature bath at a temperature of 60 ° C. for 3 hours, it was allowed to stand at room temperature for 1 hour. The amount of formalin in the aqueous solution in the polyethylene bottle was quantified in accordance with JIS K0102, 29 (formaldehyde item), and the amount of formaldehyde generated per surface area (μg / cm ² ) was calculated.

[Bleeding property] Flat molded article (70 mm x
40 mm × 3 mm) was heat-treated at 120 ° C. for a whole day and night, and the surface of the molded article was observed, and the degree of exudate was evaluated according to the following criteria.

[0095] ○: No bleeding is seen △: Slight bleeding is seen X: Marked bleeding is observed.

Examples 1 to 40 and Comparative Examples 1 to 5 After mixing 100 parts by weight of polyacetal resin with a hindered phenol compound, a spiro compound, a processing stabilizer and a heat resistance stabilizer in the proportions shown in Tables 1 to 4, , 30mm diameter 2
The composition was melted and mixed by a shaft extruder to prepare a pelletized composition. Using this pellet, the thermal stability of the resin composition in the molten state was evaluated. Also, with the injection molding machine,
A predetermined test piece was molded and the mold deposit at the time of molding was evaluated. Further, the amount of formaldehyde generated from a predetermined test piece and the exudation property were evaluated. The results are shown in Tables 1 to 4.

For comparison, an example of adding CTU guanamine to a basic system composed of a polyacetal resin and a hindered phenol compound, an example of adding benzoguanamine which is a guanamine compound having no spiro ring, and heat resistance Examples of adding melamine, which is a stabilizer, examples of adding benzoguanamine, a processing stabilizer, and a heat-resistant stabilizer, examples of adding a heat-resistant stabilizer of melamine, which is a heat-resistant stabilizer, and another heat-resistant stabilizer, as described above. It evaluated similarly.
The results are shown in Table 5.

The polyacetal resin, hindered phenolic compound, spiro compound, processing stabilizer, heat stabilizer and colorant used in the examples and comparative examples are as follows.

1. Polyacetal resin a (a-1): polyacetal resin copolymer (melt hydrolysis method stabilizing resin, melt index = 9 g / 10
Min) (a-2): polyacetal resin copolymer (solution hydrolysis stabilizing resin, melt index = 9 g / 10
Min) In addition, the melt index is ASTM-D123.
It is a value (g / 10 minutes) obtained under the conditions of 190 ° C. and 2169 g according to 8.

2. Hindered phenolic compound b (b-1): triethylene glycol bis [3- (3-
t-Butyl 5-methyl-4-hydroxyphenyl) propionate] (b-2): pentaerythritol tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate]

3. Spiro compound c (c-1): water of crystallization containing CTU guanamine [8% by weight of water containing crystallization] (c-2): anhydrous CTU guanamine [(c-1) of 20]
Heat treated under nitrogen atmosphere at 0 ° C. for 3 hours] (c-3): CTU guanamine / CTU monoguanamine mixture containing water of crystallization [5% by weight of water of crystallization and 3% by weight of CT
Mixture containing U monoguanamine] (c-4): CMTU guanamine (c-5): 3,9-bis [3- (3,5-diamino-
2,4,6-Triazaphenyl) -1,1-dimethylpropyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (c-6): benzoguanamine [Tokyo Chemical Industry Co., Ltd.]
Made].

4. Processing stabilizer d (d-1): ethylenebisstearylamide (d-2): polyethylene glycol (molecular weight 3500
0) (d-3): sorbitan mono / distearate (d-4): glycerin monostearate (d-5): ethylene glycol distearate (d-6): pentaerythritol tetrastearate (d-7): Glycerin monobehenate (d-8): polyoxyethylene-polyoxypropylene (50-50) block copolymer (molecular weight 6000) (d-9): montanic acid ester (d-10): polyethylene glycol (molecular weight 600
0).

5. Heat resistance stabilizer (organic carboxylic acid metal salt,
Alkaline earth metal salt) e (e-1): 12-hydroxycalcium stearate (e-2): ionomer [Mitsui DuPont Polychemical Co., Ltd., Himilan 1702] (e-3): magnesium oxide (e- 4): calcium citrate (e-5): calcium acetate (e-6): magnesium stearate (e-7): magnesium hydroxide (e-8): hydrotalcite [Kyowa Chemical Industry Co., Ltd.
Manufactured by DHT-4A] (e-9): Zeolite A-4 [manufactured by Tosoh Corporation, Zeorum A-4]

6. Heat-resistant stabilizer (basic nitrogen compound, phosphine compound) f (f-1): melamine (f-2): melamine formaldehyde resin 1.2 mol of formaldehyde is used with respect to 1 mol of melamine, pH 8 in aqueous solution, temperature 70 Melamine, which is a water-soluble initial condensate, without causing the reaction system to become cloudy.
Formaldehyde resin was produced. Next, the reaction system was adjusted to pH 6.5 while stirring, stirring was continued to precipitate a melamine-formaldehyde resin, and a crude melamine-formaldehyde resin powder was obtained by drying.
The powder and granules were washed with warm water at 60 ° C. for 30 minutes, filtered, and the residue was washed with acetone and dried to obtain a white powder of purified melamine-formaldehyde resin. (F-3): Melem [manufactured by Nissan Chemical Industries, Ltd.] (f-4): Nylon 6-66-610 (f-5): Allantoin [manufactured by Kawaken Fine Chemicals Co., Ltd.] (f-6): Allantoin dihydroxyaluminum [Kawaken Fine Chemicals Co., Ltd., "ALDA"] (f-7): Nylon-66 (average particle diameter 3 μm) (f-8): Biurea (f-9): Poly (N-vinylacetamide) ) (F-10): poly (vinylpyrrolidone) (f-11): triphenylphosphine.

7. Colorant g (G-1): Carbon black (acetylene black) (G-2): Phthalocyanine-based blue pigment (G-3): titanium oxide (G-4): Ultramarine blue

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

As is clear from the table, compared with the comparative example,
The resin compositions of the examples have excellent thermal stability. Also,
Since the mold deposit at the time of molding is small, the moldability can be improved, and since the amount of formaldehyde generated is extremely small, the environment can be greatly improved. Further, since the additive does not seep out from the molded product, it can be suitably used as an external component.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/3492 C08K 5/3492 C08L 71/02 C08L 71/02 83/04 83/04 F-term (reference) 4F071 AA40 AA51 AA67 AB03 AB21 AB26 AC09 AC11 AC15 AC19 AE05 AE09 AH03 AH07 AH12 BB05 4J002 CB001 CC132 CH022 CL012 CL032 CP032 DA039 DE288 DJ008 EG028 EU018 EU0 EU0 EF76 EW0 EF76 EW0 EF0 EF0 EF06 EF0 EF0 EF0 EF0 EJ060 EJ026 EJ026 EJ026E026E026 GN00 GQ00

Claims (21)

[Claims] 1. A polyacetal resin composition composed of a polyacetal resin, a hindered phenolic compound, a spiro compound having a triazine ring, and at least one selected from a processing stabilizer and a heat resistance stabilizer. 2. The polyacetal resin composition according to claim 1, wherein the spiro compound has a guanamine ring at both ends. 3. The polyacetal resin composition according to claim 1, wherein the spiro compound is a compound represented by the following formula (1). [Chemical 1] (In the formula, R ¹ and R ² are the same or different and each represents an alkylene group, an arylene group, or an aralkylene group.) 4. The polyacetal resin composition according to claim 3, wherein in the formula (1), R ¹ and R ² are linear or branched C _1-10 alkylene groups. 5. The spiro compound is 3,9-bis [(3,5
The polyacetal resin composition according to claim 1, which is -diamino-2,4,6-triazaphenyl) C _1-6 alkyl] -2,4,8,10-tetraoxaspiro [5.5] undecane. 6. The spiro compound is 3,9-bis [2-
(3,5-Diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane 3,9-bis [1- (3,5 -Diamino-2,
4,6-Triazaphenyl) methyl] -2,4,8,10-
Tetraoxaspiro [5.5] undecane, and 3,9-
Bis [3- (3,5-diamino-2,4,6-triazaphenyl) -1,1-dimethylpropyl] -2,4,8,10-
The polyacetal resin composition according to claim 1, comprising at least one selected from tetraoxaspiro [5.5] undecane. 7. The spiro compound is 3,9-bis [2-
The polyacetal resin composition according to claim 1, which is composed of (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane. object. 8. The polyacetal resin composition according to claim 1, wherein the spiro compound is an anhydrous compound or a compound containing water of crystallization. 9. The spiro compound contains water of crystallization 3,
9-Bis [(3,5-diamino-2,4,6-triazaphenyl) linear or branched C _1-5 alkyl] -2,4,8,10-
It is tetraoxaspiro [5.5] undecane.
The polyacetal resin composition described. 10. The spiro compound is 3,9-bis [(3,
5-diamino-2,4,6-triazaphenyl) alkyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and 3- (cyanoalkyl) -9-[(3,5 -Diamino-2,4,6-triazaphenyl) alkyl] -2,
The polyacetal resin composition according to claim 1, which is composed of 4,8,10-tetraoxaspiro [5.5] undecane. 11. The spiro compound is 3,9-bis [(3,
5-Diamino-2,4,6-triazaphenyl) C _1-6 alkyl] -2,4,8,10-tetraoxaspiro [5.5]
Undecane and 3- (cyano C _1-6 alkyl) -9-
[(3,5-Diamino-2,4,6-triazaphenyl) C
_1-6 alkyl] -2,4,8,10-tetraoxaspiro
[5.5] The polyacetal resin composition according to claim 1, which is composed of undecane. 12. The polyacetal resin composition according to claim 1, wherein the processing stabilizer is at least one selected from the group consisting of long chain fatty acids or their derivatives, polyoxyalkylene glycols and silicone compounds. 13. The heat resistance stabilizer is at least one selected from the group consisting of basic nitrogen compounds, phosphine compounds, organic carboxylic acid metal salts, alkali or alkaline earth metal compounds, hydrotalcites and zeolites. Item 2. The polyacetal resin composition according to item 1. 14. The polyacetal resin composition according to claim 1, wherein the heat resistance stabilizer is at least one selected from melamine or a derivative thereof, a guanidine derivative, a urea derivative, and a nitrogen-containing resin. 15. A hindered phenol compound 0.001 to 5 parts by weight, a spiro compound 0.001 to 20 parts by weight, a processing stabilizer 0.01 to 10 parts by weight, and a heat resistance stability to 100 parts by weight of a polyacetal resin. Agent 0.001 to 1
The polyacetal resin composition according to claim 1, containing 0 part by weight. 16. The polyacetal resin composition according to claim 1, further comprising a colorant. 17. The polyacetal resin composition according to claim 16, wherein the colorant is carbon black. 18. A method for producing a polyacetal resin composition, which comprises mixing a polyacetal resin, a hindered phenol compound, a spiro compound having a triazine ring, a processing stabilizer, and a heat resistance stabilizer. 19. A polyacetal resin molded article composed of the polyacetal resin composition according to claim 1. 20. (1) When stored in a closed space at a temperature of 80 ° C. for 24 hours, the amount of formaldehyde generated is 1.5 μg or less per 1 cm ² of the surface area of the molded article, and / or (2) a temperature of 60 ° C. and saturated humidity. When stored for 3 hours in a closed space, the amount of formaldehyde generated was ^2. per 1 cm ² of surface area of the molded product.
20. The polyacetal resin molded article according to claim 19, which is 5 μg or less. 21. The polyacetal resin molded article according to claim 19, wherein the molded article is at least one selected from automobile parts, electric / electronic parts, building materials / piping parts, daily life / cosmetic parts and medical parts.