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    • 专利摘要:
    To 100 parts by weight of polyacetal resin, about 0.01 to 10 parts by weight of the glyoxydiuraide compound is added. Glyoxydiurade compounds include glyoxydiuraide or derivatives thereof (metal salts, etc.). Moreover, you may add about 0.01-10 weight part of basic nitrogen containing compounds. Basic nitrogen-containing compounds include melamine, melamine resins, polyamide resins, and the like. Moreover, you may add antioxidant. Such a composition improves the stability, in particular the thermal stability, of the polyacetal resin and suppresses the generation of formaldehyde.
    公开号:KR20000062354A
    申请号:KR1019997005837
    申请日:1997-12-22
    公开日:2000-10-25
    发明作者:하쯔히꼬 하라시나；하야또 구리따；다쯔야 야마다
    申请人:가스가 다쿠조우；폴리플라스틱스 가부시키가이샤；
    IPC主号:
    专利说明:

    Polyacetal Resin Composition and Moldings
    Polyacetal resins are excellent in mechanical properties, fatigue resistance, friction resistance, abrasion resistance, chemical resistance and formability, so that they can be used in automobile parts, electrical and electronic device parts, other precision mechanical parts, construction materials and piping members, life and cosmetics, It is widely used in the field of medical components. However, as the use expands and diversifies, the demand for quality tends to be more advanced. As characteristics required for polyacetal resins, mechanical strength should not be reduced in processing processes such as extrusion or molding processes, no deposits (molding deposits) on molds will be generated, and under long-term heating conditions (heat aging). In this regard, the mechanical properties may not be deteriorated, molding defects such as silver streak or gap of the molded article may not occur, and the formaldehyde generated in the molded article may be suppressed. One of the important factors of these phenomena is decomposition of the polymer during heating. In particular, polyacetal resins are liable to decompose under the heat and oxidizing atmosphere essentially under acidic or alkaline conditions in their chemical structure. For this reason, as an intrinsic subject of a polyacetal resin, thermal stability is high and it suppresses generation | occurrence | production of formaldehyde in a molding process or a molded article. Formaldehyde is chemically active, becomes formic acid by oxidation, adversely affects heat resistance, or when used in parts of electrical and electronic equipment, metal contact parts are corroded or discolored by adhesion of organic compounds, resulting in poor contact. . Formaldehyde itself also contaminates the working environment in the parts assembly process or the living environment around the use of the final product.
    In order to stabilize the chemically active terminal, a method of esterifying the terminal of the polymer by acetylation or the like for the homopolymer, and having a adjacent carbon bond such as trioxane, cyclic ether, or cyclic formal at the time of polymerization for the copolymer The method of decomposing and removing an unstable terminal part after copolymerizing with a monomer to make it an inert stable terminal, etc. are known. However, during heating, decomposition also occurs in the main chain portion of the polymer, and in order to prevent li, it is impossible to cope with the above treatment alone, and practically, addition of antioxidants and other stabilizers is essential.
    As a method of suppressing the generation of formaldehyde of a polyacetal resin, an antioxidant, for example, a phenol compound (shielded phenol) having steric hindrance, an amine compound (shielded amine) or other stabilizer having a steric hindrance, For example, nitrogen-containing compounds such as urea derivatives, guanidine derivatives, melamine derivatives, amidine compounds, polyamides, and polyacrylamides, methods of adding alkali metal hydroxides or alkaline earth metal hydroxides, organic acids or inorganic acid salts, and the like are known. Of these stabilizers, melamine derivatives are relatively effective. In addition, antioxidants are typically used in combination with other stabilizers.
    However, even when blended with these additives, it is difficult to completely inhibit decomposition of the polyacetal resin, to impart high thermal stability, and to greatly reduce the generation of formaldehyde. For this reason, during melt processing in the extrusion or molding process for producing the composition, under the action of heat and oxygen in the cylinder of the extruder or the molding machine, formaldehyde is generated at the end of decomposition of the main chain or not sufficiently stabilized. Deteriorates the working environment during extrusion molding. Moreover, when shaping | molding for a long time, it becomes one of the largest factors which adhere | attach fine powder and a tar-like thing to a metal mold (molding deposition), reduce work efficiency, and reduce the surface state of a molded article. In addition, molding deposits and blooming tend to occur in the molding process, and cannot be added in large amounts. In addition, degradation of the mechanical strength and discoloration of the resin occur due to decomposition of the polymer. In addition, the above-described method is still not sufficient to suppress the generation of formaldehyde in the molded article as well as the processing step of the polyacetal resin composition. Therefore, in the automobile field, electric / electronic field, building materials and piping field, living / cosmetic field, and medical field, which are in close contact with human life and activity, it is required to further reduce the amount of aldehyde generated in the molded product which is the final product. In this regard, many efforts have been continued for polyacetal resins, requiring more effective stabilization prescriptions.
    Japanese Patent Publication No. 80-50502 and Japanese Patent Publication No. 94-73267 use high molecular weight melamine derivatives by polycondensation of melamine and formaldehyde to improve thermal stability, thereby improving molding deposition and blooming properties. What to do is suggested. However, even with the use of high molecular weight melamine derivatives, it is still difficult to remarkably suppress the formation of formaldehyde.
    Japanese Patent Application Laid-Open No. 73-88136 discloses a polyacetal composition containing a stabilizer composed of a phenol compound and a nitrogen-containing compound such as hydantoin and its derivatives in order to improve the thermal stability and the antioxidant properties of the polyacetal. . However, even if the hydantoin compound is added, it is difficult to maintain the amount of formaldehyde generated in the polyacetal resin at a very low level.
    It is an object of the present invention to provide a resin composition which improves the thermal stability of a polyacetal resin, in particular, the melt stability during molding processing, and a method for producing the same.
    It is another object of the present invention to provide a polyacetal resin composition, a method for producing the same, and a molded article which can significantly suppress the production of formaldehyde with a small amount of addition and improve the working environment and living environment.
    Still another object of the present invention is to suppress the formation of formaldehyde even under severe conditions, to prevent adhesion of decomposition products to a mold, leaching of decomposition products from molded products, and thermal degradation of molded products. It is to provide a polyacetal resin composition and a method for producing the same that can improve the quality of a molded article.
    Still another object of the present invention is to provide a polyacetal resin molded article in which the amount of formaldehyde is significantly suppressed.
    It is still another object of the present invention to provide a polyacetal resin molded article suitable for the automobile field, the electric / electronic field, the construction materials, the piping field, the living / cosmetic field, the medical field, etc., in which the generation of formaldehyde is strictly limited.
    <Start of invention>
    MEANS TO SOLVE THE PROBLEM In order to achieve the said objective, the present inventors examined a series of urea derivatives regarding the stability (particularly, thermal stability) of polyacetal resins. As a result, (1) the glycoxydiurade compound having a specific chemical structure It has a remarkable effect as a stabilizer (or heat stabilizer) of acetal resins, in particular, a stabilizer during molding processing, and (2) a combination of the above glycoxydiurade compound and a basic nitrogen-containing compound results in remarkable thermal stability, in particular molding processability. The present invention has been accomplished by finding that it is possible to improve and maintain the amount of formaldehyde produced at an extremely low level even under severe conditions.
    That is, the polyacetal resin composition of this invention consists of a polyacetal resin and a glyoxydiurade compound. Glyoxydiurade compound, the metal salt of glyoxydiurade, etc. are contained in the said glyoxydiurade compound. The usage-amount of a glyoxydiurade compound is about 0.01-10 weight part with respect to 100 weight part of polyacetal resins, for example. The polyacetal resin composition of the present invention may further comprise a basic nitrogen-containing compound. Basic nitrogen-containing compounds include various compounds such as melamine, melamine resins, polyamide resins, and the like. The usage-amount of a basic nitrogen containing compound is about 0.01-10 weight part with respect to 100 weight part of polyacetal resins, for example. The composition may further comprise an antioxidant.
    In the method of the present invention, a polyacetal resin composition having improved processing stability is prepared by mixing a polyacetal resin and a glyoxydiurade compound with a basic nitrogen-containing compound as necessary.
    Moreover, the molded article comprised from the said polyacetal resin composition is also contained in this invention.
    In addition, in this specification, a "glyoxydiurade compound" is used by the meaning containing not only glyoxydiurade but the derivative derived from glyoxydiurade.
    <Best form for carrying out invention>
    The resin composition of this invention consists of a polyacetal resin and a glyoxydiurade compound. In addition, the composition of the present invention may contain a basic nitrogen-containing compound.
    A polyacetal resin is an oxymethylene group (-CH 2 O-) is a polymer compound as a main constituent unit, a polyacetal homopolymers (e.g., Lin U.S. DuPont (DuPont) K.K., trade name "having, Asahi Kasei ( Polyacetal copolymers (e.g., Polyplastics Co., Ltd. product, "Juracon", etc.) containing other comonomer units other than an oxymethylene group. In the copolymer, in the comonomer unit, 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-) and an oxypropylene group) And oxytetramethylene group). The content of the comonomer unit is in a small amount, for example, 0.01 to 20 mol%, preferably 0.03 to 10 mol% (for example, 0.05 to 5 mol%), more preferably 0.1 to 5, based on the entire polyacetal resin. It can be selected in the range of mole%.
    The polyacetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like. The polyacetal copolymer may be a block copolymer, a graft copolymer, or the like in addition to the random copolymer. In addition, the polyacetal resin may have a linear structure as well as a branched structure, and may have a crosslinked structure. In addition, you may stabilize the terminal of polyacetal resin by esterification with carboxylic acids, such as an acetic acid and a propionic acid, etc., for example. The degree of polymerization, branching degree or crosslinking degree of the polyacetal is not particularly limited, but may be melt-molded.
    The polyacetal resin may be polymerized by polymerizing at least one selected from aldehydes (e.g., formaldehyde, paraformaldehyde, etc.) and trioxane, or at least one selected from the aldehydes and trioxanes and a cyclic ether (e.g., For example, it can manufacture by copolymerizing ethylene oxide, a propylene oxide etc.) or cyclic formal (for example, 1, 3- dioxolane etc.).
    A feature of the present invention lies in that the addition of a specific urea derivative, a glycoxydiurade compound, significantly improves the processing stability of the polyacetal resin and significantly suppresses the generation of formaldehyde. When the said glyoxydiurade compound is used, the stabilizing effect much more than the conventional stabilizer appears, and the polyacetal resin composition excellent in workability can be obtained.
    Glyoxydiurade compounds contain glyoxydiurade (ie allantoin) and glyoxydiurade derivatives, and the glyoxydiuraide derivatives are described in the DICTIONARY OF ORGANIC COMPOUND Vol. 1, p60. (1965 EYRE & SPOTTISWOODE-PUBLISHERS-LTD). The glyoxydiurade derivatives include, for example, substituted glyoxydiurade derivatives substituted with various substituents such as alkyl groups, cycloalkyl groups, and aryl groups (for example, 1-methyl body, 3-methyl body, and 3-ethyl system). , 5-methyl body, 1,3-dimethyl body, 1,6-dimethyl body, 1,8-dimethyl body, 3,8-dimethyl body, 1,3,6-trimethyl body, 1,3,8-trimethyl Mono, di or tri-C 1-4 alkyl substituents such as sieves, aryl substituents such as 5-phenyls, etc.), and glycoxydiurades and salts of metals [alkali metal salts such as Li, Na, K (periodic table) Metal salts of Group 1A), alkaline earth metal salts such as Mg, Ca, Sr, and Ba (group 2A metal salts of the periodic table), salts of group 1B metals of the periodic table such as Cu and Ag, and salts of group 2B metals of the periodic table such as Zn. Salts with periodic table Group 3B metals such as Al, Ga, In, salts with periodic table Group 4B metals such as Sn, Pb, salts with periodic table Group 8 metals such as Fe, Co, Ni, Pd, Pt, etc. ], Glyoxydiuraide and nitrogen-containing compounds (containing amino or imino groups) Compound (salt), a compound (salt, molecular compound (complex) etc.) with a basic amino acid (arginine, lysine, ornithine, etc.) , Molecular compounds (complexes) and the like, compounds (salts, molecular compounds (complexes), etc.) of glyoxydiurade and imidazole compounds, and organic acid salts.
    For a compound of glyoxydiurade and 2-pyrrolidone-5-carboxylate, reference can be made to Japanese Patent Application Laid-Open No. 76-36453. For the reaction product of glyoxydiurade and basic amino acid, See Patent Publications Nos. 77-102412, 77-25771, 77-25772, 77-31072, 76-19771, and the like. About the compound of a glyoxydiurade and an imidazole compound, Unexamined-Japanese-Patent No. 77-118569 etc. can be referred. The steric structure of glyoxydiurade and its derivatives is not particularly limited, and any of d, l and dl may be used. Glyoxydiurade and derivatives thereof can be used alone or in combination of two or more thereof.
    Preferred glyoxydiurade compounds include glyoxydiuraide and metal salts of glyoxydiurade [alkali metal salts, alkaline earth metal salts, periodic table Group 1B metal salts, periodic table Group 2B metal salts, periodic table Group 3B metal salts, periodic tables Polyvalent metal salts such as group 4B metal salts and periodic table group 8 metal salts, in particular about 2 to 4 valent]; and reaction products of glyoxydiurade with an amino group or an imino group-containing compound. As specific examples of the metal salt of glyoxydiurade, allantoindihydroxyaluminum, allantoinchlorohydroxyaluminum (manufactured by Kawakin Fine Chemical Co., Ltd.), and the like are exemplified, and examples of the reaction product with an amino group or an imino group-containing compound include: And allantoin sodium-d1 pyrrolidone carboxylate (manufactured by Gawa Fine Fine Chemical Co., Ltd.) and the like.
    The addition amount of the glyoxydiurade compound is, for example, 0.01 to 10 parts by weight (for example, 0.01 to 5 parts by weight), preferably 0.03 to 5 parts by weight, and more preferably, based on 100 parts by weight of polyacetal resin. It is about 0.05 to 2.5 parts by weight (particularly 0.05 to 2 parts by weight), and even about 0.05 to 1.5 parts by weight (for example, 0.1 to 1.5 parts by weight) can significantly suppress the formation of formaldehyde. When the amount of the glyoxydiurade compound added is less than 0.01 part by weight, it is difficult to effectively reduce the amount of formaldehyde generated, and when it exceeds 10 parts by weight, moldability and color decrease or the bleeding phenomenon is likely to occur.
    The glyoxydiurade compound alone may impart remarkable stability to the polyacetal resin, but when used in combination with a basic nitrogen-containing compound, it is possible to remarkably suppress the generation of formaldehyde. That is, by adding a combination of a specific urea derivative, a glycoxydiuraide compound and a basic nitrogen-containing compound, the formation of formaldehyde can be suppressed to a very low level even under severe conditions, and the thermal and processing stability of the polyacetal resin can be reduced. It can be significantly improved. By combination of the said glycoxydiurade compound and a basic nitrogen containing compound, the very high stability unexpected with the conventional stabilizer appears, and the polyacetal resin composition excellent in workability is obtained.
    The basic nitrogen-containing compound may be a low molecular compound or a high molecular compound (nitrogen-containing resin). As a nitrogen-containing low molecular weight compound, For example, aliphatic amines, such as monoethanolamine and diethanolamine, aromatic amines (aromatic secondary amines or tertiary amines, such as o-toluidine, p-toluidine, and p-phenylenediamine) , Amide compounds (polyhydric carboxylic acid amides such as malonamide, isophthalic acid diamide, p-aminobenzamide, etc.), hydrazine or derivatives thereof (hydrazides such as hydrazine, hydrazone, polyhydric carboxylic acid hydrazide, etc.), Guanidine or derivatives thereof (3,5-diamino-1,2,4-triazole, amidine, dicyandiamide or derivatives thereof), polyaminotriazines (guanamine, acetoguanamine, benzoguanamine, etc.) Namins or derivatives thereof, melamine or derivatives thereof, uracil or derivatives thereof (uracil, urine, etc.), cytosine or derivatives thereof (cytosine, cytidine and the like) and the like.
    Examples of the nitrogen-containing resin include amino resins (condensation resins such as urea resin, thiourea resin, guanamine resin, melamine resin, guanidine resin, urea-melamine resin, and urea-benzogua) produced by reaction with formaldehyde, for example. Co-condensation resins such as namin resins, phenol-melamine resins, benzoguanamine-melamine resins, aromatic polyamine-melamine resins, and the like), aromatic amine-formaldehyde resins (such as aniline resins), polyamide resins (e.g., nylon 3, Single or copolymerized polyamides such as nylon 6, nylon 66, nylon 11, nylon 12, nylon MXD 6, nylon 4-6, nylon 6-10, nylon 6-11, nylon 6-12, nylon 6-66-610, Substituted polyamide etc. which have a methylol group and the alkoxy methyl group), polyesteramide, polyamideimide, polyacrylamide, polyaminothioether, etc. can be illustrated.
    These nitrogen-containing compounds may be used alone or in combination of two or more thereof.
    Preferred nitrogen-containing compounds include urea (urea or derivatives thereof), polyaminotriazines (melamine or derivatives thereof), nitrogen-containing resins (amino resins such as urea resins and melamine resins, polyamide resins, and the like). In particular, melamine, amino resins (such as melamine resins), and polyamide resins are preferable, and amino resins and crosslinked amino resins are particularly preferred. Also preferred are melamine resins (melamine-formaldehyde resins), especially crosslinked melamine resins. A crosslinked amino resin, especially a crosslinked melamine resin, is usually insoluble in hot water at about 40 to 100 ° C (particularly 50 to 80 ° C).
    Melamine resin can be obtained by reaction of at least melamine with a co-condensation component (phenolic compound, urea, thiourea, guanamine, etc.) and formaldehyde as needed, and melamine resin can be obtained by initial condensation with formaldehyde. It may be water. Moreover, the methylol melamine resin which has a methylol group may be sufficient, at least one methylol group may be alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, etc.), and may be an etherified alkoxy methyl melamine resin.
    The melamine resin may be a water-soluble melamine resin, but is preferably a water-insoluble melamine resin. In the melamine resin, at least one amino group or imino group remains in one melamine skeleton.
    Particularly preferred melamine resins are crosslinked melamine resins having a high degree of condensation and having a plurality of amino groups or imino groups remaining in one melamine skeleton, for example (1) a melamine resin insoluble in hot water and soluble in dimethyl sulfoxide ( Melamine-formaldehyde condensates), (2) melamine resins (crosslinked melamine-formaldehyde condensates) insoluble in hot water and dimethyl sulfoxide. The melamine resin (1) has an average number of melamine units (average degree of polymerization or average degree of condensation) in 1 mole of melamine-formaldehyde condensate by 1 H-NMR analysis, preferably 2 to 5, more preferably Is about 2.2 to 3.8), and the average number of hydrogen atoms (average NH number) couple | bonded with three amino groups in a melamine unit is three or more (preferably 3.5 or more).
    The melamine resin (1) is disclosed in Japanese Patent Application Laid-Open No. 94-73267, and it contains 0.8 to 10 moles (preferably 0.8 to 5 moles, more preferably 1 to 3 moles) of formaldehyde with respect to 1 mole of melamine, It can be obtained by reacting in an aqueous solution or an aqueous dispersion, in particular using about 1 to 2 moles). For example, when a mixture of melamine and formaldehyde aqueous solution is reacted at a pH of about 8 to 9 and a temperature of about 50 to 90 ° C, and the solution becomes cloudy as the condensation reaction proceeds, the condensation reaction is stopped by cooling or the like at an appropriate stage. . The reaction mixture is dried by a method such as spray drying to obtain an aliquot of the crude melamine-formaldehyde condensate. Preparative crude melamine-formaldehyde condensate was washed with warm water (about 50 to 70 DEG C) at a suitable time (for example, 10 minutes to 3 hours, preferably 30 minutes to 1 hour), filtered, and the residue Is dissolved in dimethylsulfoxide. After filtering off the insoluble content in the dimethyl sulfoxide mixed solution, the dimethyl sulfoxide soluble component is injected into a large excess of acetone, and the precipitate is filtered and dried to obtain a white melamine-formaldehyde polycondensate.
    The melamine resin (2) is disclosed in Japanese Patent Application Laid-Open No. 80-50502, with respect to 1 mole of melamine, 0.8 to 10 moles (preferably 1 to 5 moles, more preferably 1 to 3 moles) of formaldehyde, 1 to 2 moles), in an aqueous solution or an aqueous dispersion, and reacting in the alkaline region in the same manner as above, to prepare a precondensate (soluble condensate), and under acidic conditions of pH 5 to 6.9, for example It can obtain by stirring at a temperature of about 70-100 degreeC, condensing again, and bridge | crosslinking. The melamine resin (2) is washed with an aqueous hot water of the melamine resin produced in the same manner as above, and filtered, the residue is mixed with dimethyl sulfoxide, the dimethyl sulfoxide insoluble component is washed with a solvent such as acetone and dried Obtained by
    The basic nitrogen-containing compound is usually used as an aliquot.
    The amount of the basic nitrogen-containing compound may be selected according to the amount of the glyoxydiurade compound, etc., for example, 0.01 to 10 parts by weight (for example, 0.01 to 5 parts by weight), preferably 100 parts by weight of the polyacetal resin. Preferably it is about 0.03-5 weight part, More preferably, it is about 0.05-2.5 weight part (especially 0.1-1 weight part), and even about 0.1-0.5 weight part can form remarkably suppress formation of formaldehyde.
    The ratio of the glyoxydiurade compound and the basic nitrogen-containing compound can be selected in a wide range, usually the former / the latter = 5/95 to 95/5 (weight ratio), preferably 10/90 to 90/10 (Weight ratio), More preferably, it can select from the range of about 20/80-80/20 (weight ratio). In particular, when the ratio of the glycoxydiuraide compound increases, the amount of formaldehyde produced can be greatly improved. For this reason, a preferable ratio (weight ratio) of both is former / the latter = 0.5-10, Preferably it is 0.7-8, More preferably, it is about 1-5.
    The total amount of the glyoxydiurade compound and the basic nitrogen-containing compound can be generally selected in the range of 0.02 to 10 parts by weight based on 100 parts by weight of the polyacetal resin, and 0.02 to 5 parts by weight (for example, 0.1 to 5 parts). Parts by weight), preferably 0.05 to 3 parts by weight (for example 0.2 to 3 parts by weight), more preferably 0.1 to 2 parts by weight, especially 0.1 to 1.5 parts by weight (for example 0.3 to 1.5 parts by weight). to be.
    The stabilizer composed of the glyoxydiurade compound and the basic nitrogen-containing compound, if necessary, can provide remarkable stability to the polyacetal resin even in a small amount, and can be used in combination with an antioxidant.
    Antioxidants include, for example, phenol-based (shielded phenols, etc.), amine-based, phosphorus-based, sulfur-based, hydroquinone-based, quinoline-based antioxidants and the like.
    Phenolic antioxidants include masked phenols such as 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol ), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,6-di-t-butyl-p-cresol, 1,3,5-trimethyl-2,4, 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3-t-butyl-5- Methyl-4-hydroxyphenyl) propionate], n-octadiyl-3- (4 ', 5'-di-t-butylphenol) propionate, n-octadisil-3- (4'-hydroxy Hydroxy-3 ', 5'-di-t-butylphenol) propionate, stearyl-2- (3,5-di-t-butyl-4-hydroxyphenol) propionate, distearyl-3 , 5-di-t-butyl-4-hydroxybenzylphosphonate, 2-t-butyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenylacrylate , N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnaamide), 3,9-bis {2- [3- (3-t-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (3- Methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) butane and the like.
    For amine antioxidants, masked amines such as 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperi Dean, 4-phenoxy-2,2,6,6tetramethylpiperidine, bis- (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis- (2, 2, 6,6-tetramethyl-4-piperidyl) malonate, bis- (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis- (2,2,6,6- Tetramethyl-4-piperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl- 4-piperidyl) terephthalate, 1,2-bis- (2,2,6,6-tetramethyl-4-piperidyloxy) ethane, phenyl-1-naphthylamine, phenyl-2-naphthyl Amines, N, N'-diphenyl-1,4-phenylenediamine, N-phenyl-N'-cyclohexyl-1,4-phenylenediamine and the like.
    Examples of the phosphorus antioxidant include triisodecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, diphenylisodisyl phosphite, phenyl diisodisyl phosphite, 2,2-methylene bis (4, 6-di-t-butylphenyl) octylphosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) ditridisylphosphite, tris (2, 4-di-t- Butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (2,4-di-t-amylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, bis (2-t-butylphenyl) phenylphosphite, tris [2- (1,1-dimethylpropyl) -phenyl] phosphite, tris [2,4-di (1,1-dimethylpropyl) -phenyl] phosphite , Tris (2-cyclohexylphenyl) phosphite, tris (2-t-butyl-4-phenylphenyl) phosphite and the like.
    Hydroquinone antioxidants include, for example, 2,5-di-t-butylhydroquinone, and the like, and quinoline antioxidants include, for example, 6-ethoxy-2,2,4-trimethyl-1,2-dihydro. Quinoline and the like, and sulfuric acid-based antioxidants include, for example, dilaurylthiodipropionate, distearylthiodipropionate, and the like.
    These antioxidants can be used alone or in combination of two or more. Preferred antioxidants include phenolic antioxidants (particularly masked phenols) and the like. Especially among the masked phenols, for example, C 2-10 alkylenediol such as 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] -Bis [3- (3,5-di-branch-C 3-6 alkyl-4-hydroxyphenyl) propionate]; For example, di or trioxy C 2-4 alkylenediol-bis [3- such as triethylene glycol-bis [3- (3-tbutyl-5-methyl-4-hydroxyphenyl) propionate]; (3,5-di-branched C 3-6 alkyl-4-hydroxyphenyl) propionate]; For example, C 3-8 alkylenetriol-bis [3- (3,5-di) such as glycerine tris [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] -Branched C 3-6 alkyl-4-hydroxyphenyl) propionate]; For example, C 4-8 alkylenetetraol tetrakis [3- (3, 5) such as pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] -Di-branched C 3-6 alkyl-4-hydroxyphenyl) propionate] and the like.
    These antioxidants can be used alone or in combination of two or more. The content of the antioxidant can be selected in the range of, for example, 0.01 to 5 parts by weight, preferably 0.05 to 2.5 parts by weight, especially 0.1 to 1 part by weight, based on 100 parts by weight of the polyacetal resin.
    Further, the ratio (weight ratio) of the glyoxydiurade compound to the antioxidant is, for example, the former / the latter = 0.1 to 10, preferably 0.2 to 10, more preferably 0.5 to 7 (particularly 1 to 7). You can choose from a range of degrees. In particular, when the ratio of the glycoxydiuraide compound increases, the amount of formaldehyde produced can be greatly improved. For this reason, the preferable ratio (weight ratio) of both is former / the latter = 1.0-10, Preferably it is 1.2-10, More preferably, it is 1.5-5, Especially about 1.7-5 (for example, 2-5). .
    The total amount of the component glyoxydiuraide compound and the antioxidant in such a ratio can usually be selected in the range of about 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyacetal resin, preferably about 0.1 to 5 parts by weight, More preferably, about 0.1 to 3 parts by weight (eg about 0.2 to 3 parts by weight) More preferably about 0.1 to 2 parts by weight (particularly about 0.1 to 1.5 parts by weight (eg about 0.5 to 1.5 parts by weight) )to be.
    You may use combining the said antioxidant and basic nitrogen containing compound, respectively.
    Other stabilizers such as alkali metal hydroxides, alkaline earth metal hydroxides, metal oxides, organic carboxylic acid salts, long chain fatty acids or salts thereof, polyhydric alcohol fatty acid esters, and the like may be added to the resin composition of the present invention.
    In the resin composition of the present invention, one or more combinations of various additives, for example, a colorant, a release agent, a nucleating agent, an antistatic agent, a flame retardant, a surfactant, various polymers, fillers and the like, including dyes and pigments, may be used. May be added.
    The polyacetal resin composition of the present invention may be a granular mixture or a melt mixture (such as pellets). The said resin composition can be manufactured by mixing a polyacetal resin, a glyoxydiurade compound, and another additive as needed by a conventional method. Moreover, you may mix at least 1 sort (s) chosen from a basic nitrogen containing compound and antioxidant. In the molding of the polyacetal resin composition, for example, 1) each component is mixed, kneaded and extruded by a single screw or twin screw extruder to produce pellets, and 2) pellets having different compositions (master batches) ), The pellets are mixed (diluted) in a predetermined amount to be used for molding, and a molded article having a predetermined composition is obtained. (3) Glyoxydiurade compound or basic nitrogen-containing compound is sprayed onto pellets of polyacetal resin. A method of forming a molded article having a predetermined composition by molding after adhering is employed. Moreover, in the manufacture of the composition used for a molded article, the particle | grain of a polyacetal resin which is gas (for example, the granule which grind | pulverized one part or all of polyacetal resin) and another component (glyoxydiurade compound and basic nitrogen) Mixing and melt kneading the containing compound) is advantageous for improving the dispersion of the additive.
    In the molding process (especially melt molding process) process, the resin composition of this invention can suppress generation | occurrence | production of formaldehyde by the oxidation or thermal decomposition of a polyacetal resin, and can improve a working environment. In addition, adhesion of the decomposed product to the mold (molding deposition), leaching of the decomposed product from the molded article, significantly suppressing thermal deterioration of the molded article, greatly improving the heat aging characteristics, and improving various problems during the molding process. Therefore, the resin composition of this invention is useful for shape | molding various molded articles by the conventional shaping | molding method, for example, injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, etc.
    The polyacetal resin molded article of the present invention composed of the polyacetal resin composition contains at least a glyoxydiurade compound and has a very low amount of formaldehyde. That is, a molded article made of the conventional polyacetal resin containing a stabilizer such as an antioxidant produces a relatively large amount of formaldehyde and contaminates a living environment or a work environment in addition to corrosion and discoloration. For example, the amount of formaldehyde generated in a commercially available polyacetal resin molded article is about 2 to 5 μg (typically 2 μg) per cm 2 of surface area in dry (in constant temperature dry atmosphere), and wet (in constant temperature and humid atmosphere). It is on the order of 3-6 µg per cm 2 of surface area. In addition, even when the molding conditions are controlled, it is difficult to obtain molded articles having a dry content of 1.5 µg or less per square centimeter in dry form and 2.5 µg or less per square centimeter in wet form.
    In contrast, in the polyacetal resin molded article of the present invention, the amount of formaldehyde generated in the dry type is 1.5 µg or less (about 0 to 1.5 µg), preferably 1.2 µg or less (about 0 to 1.2 µg), per 1 cm 2 of the molded article. Preferably it is 1 microgram or less (about 0-1 microgram), Especially preferably, it is about 0.01-1 microgram. In addition, the amount of formaldehyde generated in the wet type is 2.5 μg or less (about 0 to 2.5 μg), preferably 2 μg or less (about 0 to 2 μg), and more preferably 1.5 μg or less (0 to 1.5) per cm 2 of the molded article. Μg), and particularly preferably about 0.01 to 1.2 μg (for example, about 0.01 to 1 μg).
    The polyacetal resin molded article of the present invention may have the amount of generation of formaldehyde in at least one of dry and wet, and usually has the amount of generation of formaldehyde in both dry and wet.
    In addition, the amount of formaldehyde generation in dry can be measured as follows.
    After cutting a polyacetal resin molded article as needed and measuring a surface area, the appropriate amount (for example, about 10-50 cm <2> of surface areas) of the molded article is put into an airtight container (capacity 20 ml), and it is left to stand at the temperature of 80 degreeC for 24 hours. . Thereafter, 5 ml of water is poured into the sealed container, and the amount of formalin in the aqueous solution is quantified according to JIS K 0102,29 (term of formaldehyde) to determine the amount of formaldehyde generated (μg / cm 2) per surface area of the molded article.
    In addition, the amount of formaldehyde generation in wet can be measured as follows.
    After cutting the polyacetal resin molded article as needed and measuring the surface area, the appropriate amount of the molded article (for example, the surface area of about 10 to 100 cm 2) was sealed on a lid of a closed container (capacity 1L) containing 50 ml of distilled water. It is left to stand in a constant temperature bath at the temperature of 60 degreeC for 3 hours. Thereafter, it is left to stand at room temperature for 1 hour, the amount of formalin in the airtight container is quantitatively determined according to JIS K 0102,29 (term of formaldehyde), and the amount of formaldehyde generated (μg / cm 2) per surface area of the molded article is obtained.
    The numerical definition of the amount of formaldehyde generation according to the present invention relates to a molded article of a polyacetal resin composition containing ordinary additives (normal stabilizers, mold release agents, etc.) as long as it contains at least a polyacetal resin and a glyoxydiurade compound. In addition, in the molded article of the composition containing an inorganic filler and other polymers, the molded article (for example, a multi-color molded article or a coated molded article) where most of the surface of the molded article (for example, 50 to 100% of the total surface area) is made of polyacetal resin. And the like).
    The present invention relates to a polyacetal resin composition, a method for producing the same, and a polyacetal resin molded article molded from the resin composition, in which the amount of formaldehyde generation is remarkably suppressed in processing and the like.
    EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.
    The polyacetal resin, glyoxydiurade compound, basic nitrogen-containing compound, antioxidant, and other stabilizers used in Examples and Comparative Examples are as follows.
    1. Polyacetal Resin
    (a-1): polyacetal resin copolymer
    (Polyplastics, Inc., `` Juracon '')
    (a-2): polyacetal resin homopolymer
    (Asahi Kasei Co., Ltd., Tenak 4010)
    2. Glyoxydiurade Compound
    (b-1): Glyoxydiurade
    (b-2): allantoindihydroxyaluminum
    (Kawa Poker Fine Chemical Co., Ltd. product)
    3. Basic Nitrogen-Containing Compounds
    (c-1)-(c-5): melamine-formaldehyde resin
    (c-1): To 1 mole of melamine, react with 1 mole of formaldehyde in an aqueous solution at pH 8.5 and a temperature of 75 ° C., and after cooling the reaction system after a predetermined time to produce a melamine resin by drying the reaction system, The solid powder of the crude melamine resin was obtained. The solid was washed with hot water at 60 ° C. for 30 minutes, filtered, and the residue was washed with acetone and dried at room temperature. The dried product was melted in dimethyl sulfoxide at a concentration of 0.5% by weight over 2 hours, the insoluble content was filtered off, and then poured into 20% by weight of acetone, the precipitate was filtered and dried at room temperature to obtain a white powder of purified melamine resin. Got. Moreover, when the average condensation degree and average NH number of this melamine resin were measured by <1> H-NMR method, it was 2.51 in average condensation degree, 4.26 in NH number, and 4.1 weight% of monomer content.
    (c-2): Purified melamine resin of white powder was obtained similarly to said (c-1) except having used 2.0 mol of formaldehyde with respect to 1 mol of melamine (average condensation degree 2.71, average NH number 3.62, 1). Monomer content 3.5% by weight).
    (c-3): To 1 mol of melamine, 1.1 mol of formaldehyde was used to react at pH 8.0 in an aqueous solution at a temperature of 70 ° C. to produce a melamine resin of a water-soluble initial condensate without clouding the reaction system. Subsequently, the reaction system was adjusted to pH 6.5 while stirring, stirring was continued, the melamine resin was precipitated, and the granule of a crude melamine resin was obtained by drying. The aliquot was washed with warm water at 60 ° C. for 30 minutes, filtered, and the residue was washed with acetone and dried at room temperature. The dried product was dispersed in dimethyl sulfoxide at a concentration of 0.5% by weight over 2 hours, the soluble component was removed by filtration, and dried at room temperature to obtain a white melamine-refined melamine resin (average degree of condensation because it was insoluble and insoluble). And the average NH number was unmeasurable (monomer content 0.05 wt%).
    (c-4): The granules of crude melamine resin were obtained in the same manner as in (c-3) except that 1.2 mol of formaldehyde was used per 1 mol of melamine. The aliquot was washed with warm water at 60 ° C. for 30 minutes, filtered, and the residue was washed with acetone and dried at room temperature to obtain a white melamine-purified melamine resin (because it is insoluble and insoluble, average condensation degree and average NH number). Cannot be measured (monomer content 0.03% by weight).
    (c-5): A white powdery purified melamine resin was obtained in the same manner as in (c-4), except that 2.0 mol of formaldehyde was used per 1 mol of melamine (the average degree of condensation and average because it is insoluble and insoluble). NH number is not measurable (monomer content 0.01% by weight).
    (c-6): melamine
    (c-7): nylon 6
    (c-8): nylon 6-66-610
    4. Antioxidant
    (d-1): pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
    5. Other Stabilizers
    (e-1): ethylene urea
    (e-2): melamine
    (e-3): hydantoin
    (e-4): nylon 12
    (e-5): cyanoguanidine
    (e-6): 5,5-dimethyldimethyldanine
    Further, in Examples and Comparative Examples, the amount of formaldehyde generated in the melt, the amount of formaldehyde generated in the molded article in dry and wet form, the moldability, the odor of the molding environment (degree of odor), the odor in the molded article, and the degree of heat aging It evaluated as follows.
    Formaldehyde Generation in Melt
    5 g of pellets were accurately weighed and held in a metal container at 200 ° C. for 5 minutes, and then the atmosphere in the container was absorbed in distilled water. The amount of formaldehyde in this aqueous solution was quantified according to JIS K 0102, 29 (term of formaldehyde) and calculated as the amount of formaldehyde gas generated in the pellets (ppm).
    [Formaldehyde Generation in Molded Products at Dry]
    10 resin samples (2 mm x 2 mm x 50 mm) of resin samples (total surface area of about 40 cm 2) were placed in an airtight container (capacity 20 ml), heated at a temperature of 80 ° C. for 24 hours in a constant temperature bath, and then at room temperature. Air-cooled and 5 ml of distilled water were injected into the syringe. The formalin amount of this aqueous solution was quantified in accordance with JIS K 0102, 29 (term of formaldehyde), and was calculated as the amount of formaldehyde gas generated (μg) per 1 cm 2 surface area.
    [Formaldehyde Generation from Wet Products in Wet]
    The test piece (100 mm × 40 mm × 2 mm; total surface area of about 85.6 cm 2) is suspended from the lid of a polyethylene bottle (capacity 1 L) containing 50 ml of distilled water and sealed, and left to stand at a temperature of 60 ° C. for 3 hours. After that, the mixture was allowed to stand at room temperature for 1 hour. The amount of formalin in aqueous solution was quantified in accordance with JIS K 0102, 29 (term of formaldehyde) in a bottle made of polyethylene, and calculated as the amount of formaldehyde gas generated (μg) per 1 cm 2 of the molded article.
    [Forming (quantification of mold deposits) and environmental odor during molding]
    Using a pellet of the sample polyacetal resin composition, the molded article of a specific shape was continuously molded (24 hours) by an injection molding machine under the following conditions, and the amount of formaldehyde in the vicinity of the molding machine during continuous molding and the amount of mold deposits after 24 hours were as follows. It evaluated together.
    (Molding conditions)
    Injection molding machine: Toshiba IS30 EPN [roduct of Toshiba Kikaki Co., Ltd.]
    Cylinder temperature: 200 ℃
    Injection pressure: 750 ㎏ / ㎠
    Injection time: 4 seconds
    Cooling time: 3 seconds
    Mold temperature: 30 ℃
    (Evaluation of formaldehyde odor around the molding machine at the time of continuous molding)
    A: Almost no smell of formaldehyde
    B: It smells a little formaldehyde
    C: It smells like formaldehyde and irritates throat and eyes.
    D: The smell of formaldehyde is quite severe and can't be there.
    (Evaluation of Mold Attachment During Continuous Molding)
    A: Some attachments are accepted
    B: Small amount of deposit
    C: The amount of deposit is large, but it is not attached to the front of mold.
    D: Many deposits are attached to the front of the mold.
    [Formaldehyde intake of molded products]
    The formaldehyde odorizer was placed in a sealed container (capacity 200 ml) of 20 test specimens (2 mm x 2 mm x 50 mm) in a sealed container (capacity 200 ml), and then heated in a constant temperature chamber for 1 hour at 40 ° C. The smell was confirmed immediately.
    In addition, in order to evaluate formaldehyde odor in higher temperature conditions, the resin sample of ten test pieces (2 mm x 2 mm x 50 mm) (total surface area about 40 cm <2>) was put into an airtight container (20 ml of capacity), and the temperature is 80 degreeC 24 hours at, opened in a constant temperature bath and then opened and immediately confirmed the smell.
    The odor of formaldehyde was organoleptically evaluated in the following five steps.
    A: Odorless
    B: Odour
    C: medicine
    D: Intrusion
    E: snatch
    [Degree of Heat Aging (Exudative Evaluation on Molded Part Surface)]
    The molded article was left for 3 days in an environment of 70 ° C. and a relative humidity of 80% RH, and then left overnight at a temperature of 120 ° C., followed by observation of the surface of the molded product. Evaluated in stages.
    A: No exudates at all
    B: exudates are partially recognized
    C: The exudate is recognized in front
    D: The exudate is leached abundantly in the front.
    [Heat aging degree (evaluation of crack occurrence on the surface of the molded article)]
    The plate-shaped molded product (120 mm x 120 mm x 2 mm) was left to age at 30 ° C. in a gear oven for 30 days, and then heated and aged. Then, the surface of the molded product was observed. Evaluated as.
    A: No crack at all
    B: The crack is partially confirmed
    C: The crack is confirmed from the front
    <Examples 1 to 7 and Comparative Examples 1 to 7>
    The antioxidant and the glyoxydiurade compound were mixed with the polyacetal resin in the ratio shown in Table 1, followed by melt mixing with a twin screw extruder to prepare a pellet-like composition. Subsequently, the test piece was produced with the injection molding machine using this pellet. The pellets and test pieces were used to evaluate formaldehyde generation in the melt, formaldehyde odor in continuous molding, formability and heat aging (exudability). The results are shown in Table 1.
    In addition, it evaluated similarly to the example of the addition of the glyoxydiurade compound and the example which added the normal stabilizer to the polyacetal resin for the comparison.
    As shown in Table 1, the amount of generation of formaldehyde was very small and the amount of exudates in the molded article and the molded article was very small in the resin composition of the example compared with the comparative example.
    <Examples 8 to 14 and Comparative Examples 8 to 13>
    After mixing an antioxidant and a glyoxydiurade compound with the polyacetal resin in the ratio shown in Table 2, it melt-mixed by the twin screw extruder and manufactured the pellet-form composition. Subsequently, a test piece was produced by the injection molding machine using this pellet, and the formaldehyde generation in the molded article and the formaldehyde odor of the molded article were evaluated. The results are shown in Table 2.
    In addition, it evaluated similarly to the example of the addition of the glyoxydiurade compound and the example which added the normal stabilizer to the polyacetal resin for the comparison.
    As shown in Table 2, the resin molded article of the comparative example has a large amount of formaldehyde generation, and the odor is very strong in the odor test. In contrast, in the resin molded article of Example, the amount of formaldehyde generated is very small and almost odorless.
    <Examples 15 to 25 and Comparative Examples 14 to 18>
    0.3 part by weight of an antioxidant [entaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 100 parts by weight of a polyacetal resin, a glyoxydiuraide compound, and basic Nitrogen containing compounds (melamine-formaldehyde resin, melamine, polyamide resin) were mixed in the ratio shown in Table 3, followed by melt mixing by a twin screw extruder to prepare a pellet-like composition. The test piece was produced by the injection molding machine using this pellet. The pellets and test pieces were used for evaluation of formaldehyde generation in the melt and the molded article, formaldehyde odor during continuous molding, and the degree of heat aging (cracking of the molded article surface). The results are shown in Table 3.
    In addition, the example of the addition of the glyoxydiurade compound addition and the example of the addition of the melamine formaldehyde resin for evaluation was evaluated similarly to the above.
    As shown in Table 3, compared with the comparative example, the resin composition of the example has a very small amount of formaldehyde and a high degree of heat aging.
    As mentioned above, the polyacetal resin composition of this invention can suppress generation | occurrence | production of formaldehyde, can improve a work environment largely, and can improve moldability. In addition, the generation of formaldehyde in the molded article can also be reduced, and the living environment can be greatly improved.
    Since the polyacetal resin composition of this invention contains the glyoxydiurade compound at least, the stability and thermal stability of polyacetal resin (especially melt stability at the time of shaping | molding process) can be improved significantly. In addition, the addition of a small amount can significantly suppress the formation of formaldehyde, can significantly reduce the smell of formaldehyde of the molded article, it can greatly improve the working environment. In particular, the stability of the polyacetal resin and the amount of formaldehyde generated can be suppressed to a very low level. The polyacetal resin composition of the present invention can also suppress the formation of formaldehyde even under severe conditions, and can suppress the attachment of degradants to a mold (molding deposition), the leaching of decomposed products from molded products and the thermal deterioration of molded products. The quality and moldability of the molded article can be improved.
    The molded article of the present invention can be used for any use (e.g. door hangers, levers, etc.) for which formaldehyde is harmful. Appropriately used as mechanical parts (active parts, passive parts, etc.), building materials and piping fields, daily necessities (life) and cosmetics fields, and parts and components of the medical and medical fields (medical and therapeutic fields). .
    More specifically, the mechanical parts of the automobile field include internal handles, pair trunk openers, seat belt buckles, assist straps, internal parts such as various switches, door hangers, levers, clips, electrical system parts such as dashboards and connectors, and audio equipment. Examples thereof include automotive electrical and electronic parts such as automobile navigation equipment, parts in contact with metals represented by carrier plates of window regulators, door lock actuator parts, mirror parts, wiper motor system parts, fuel system parts, and the like.
    As a mechanical component in the electric and electronic field, a component or member of an apparatus composed of a polyacetal resin molded article and having a large number of metal contacts [for example, an audio apparatus such as a cassette tape recorder, a VTR (video tape recorder), 8 mm Video equipment such as video and video cameras, or OA (office automation) equipment such as copiers, facsimiles, word processors, and computers, and toys, telephones, computers, etc. which are driven by driving power such as motors and springs. Is illustrated. Specifically, a chassis (gear), a gear, a lever, a cam, a pulley, a bearing, etc. are mentioned. In addition, optical and magnetic media components (e.g., metal thin film magnetic tape cassettes, magnetic disk cartridges, magneto-optical disk cartridges, etc.) at least partially composed of a polyacetal resin molded article, more specifically, metal tape cassettes for music, digital audio It is also applicable to tape cassettes, 8 mm video tape cassettes, floppy disk cartridges, mini disk cartridges, and the like. Specific examples of optical and magnetic media components include tape cassette components (body of tape cassette, reel, hub, guide, roller, stopper, lid, etc.), disk cartridge parts (body of the cartridge (case), shutter, clamping plate, etc.). ), And the like.
    In addition, the polyacetal resin molded article of the present invention includes building materials and piping parts such as lighting fixtures, windows, piping, cocks, faucets, and bathroom peripheral parts, stationery, lip cream and loose containers, cleaners, water purifiers, spray nozzles, spray containers, It is suitably used for a wide range of life-related parts, cosmetic parts, and medical parts, such as aerosol containers, general containers, and holders of injection needles.
    权利要求:
    Claims (18)
    [1" claim-type="Currently amended] A polyacetal resin composition composed of a polyacetal resin and a glyoxydiurade compound.
    [2" claim-type="Currently amended] The polyacetal resin composition according to claim 1, wherein the glyoxydiuraide compound is glyoxydiuraide or a metal salt thereof.
    [3" claim-type="Currently amended] The compound according to claim 1, wherein the glyoxydiurade compound comprises glyoxydiureide, an alkali metal, an alkaline earth metal, a periodic table 1B metal, a periodic table 2B metal, a periodic table 3B metal, a periodic table 4B metal and A polyacetal resin composition which is a salt with at least one metal selected from Group 8 metals.
    [4" claim-type="Currently amended] The polyacetal resin composition according to claim 1, wherein the glyoxydiuraide compound is allantoindihydroxyaluminum.
    [5" claim-type="Currently amended] The polyacetal resin composition according to claim 1, wherein the amount of the glyoxydiurade compound used is 0.01 to 10 parts by weight based on 100 parts by weight of the polyacetal resin.
    [6" claim-type="Currently amended] The polyacetal resin composition according to claim 1, further comprising 0.01 to 10 parts by weight of the basic nitrogen-containing compound based on 100 parts by weight of the polyacetal resin.
    [7" claim-type="Currently amended] The polyacetal resin composition according to claim 6, wherein the basic nitrogen-containing compound is melamine, melamine resin, polyacrylamide or polyamide resin.
    [8" claim-type="Currently amended] The polyacetal resin composition according to claim 6, comprising 0.03 to 5 parts by weight of the glyoxydiuraide compound and 0.03 to 5 parts by weight of the basic nitrogen-containing compound, based on 100 parts by weight of the polyacetal resin.
    [9" claim-type="Currently amended] The polyacetal resin composition according to claim 1, further comprising an antioxidant.
    [10" claim-type="Currently amended] The polyacetal resin composition according to claim 9, wherein the ratio (weight ratio) of the glyoxydiurade compound and the antioxidant is the former / the latter = 0.5 to 10.
    [11" claim-type="Currently amended] The compound according to claim 1, which comprises at least one glyoxydiurade compound selected from glyoxydiurade, glyoxydiurade derivatives and metal salts thereof, and at least one of an antioxidant and a basic nitrogen-containing compound. The resin composition described above, wherein the basic nitrogen-containing compound is at least one selected from melamine, melamine resin, polyacrylamide, and polyamide resin, and the ratio of the glyoxydiurade compound is 100 parts by weight of the polyacetal resin. A polyacetal resin composition having 0.05 to 2.5 parts by weight, the ratio of the antioxidant to 0.05 to 2.5 parts by weight, and the ratio of the basic nitrogen-containing compound to 0.05 to 2.5 parts by weight.
    [12" claim-type="Currently amended] The polyacetal resin composition according to claim 11, wherein the metal salt of glyoxydiurade and the metal salt of glyoxydiurade derivatives are divalent to tetravalent metal salts.
    [13" claim-type="Currently amended] The method according to claim 11, wherein the glyoxydiuraide or derivative thereof is glyoxydiuraide, C 1-4 alkyl substituted glyoxydiuraide, aryl substituted glyoxydiuraide, glyoxydiuraide and amino groups or already Polyacetal resin composition which is at least 1 sort (s) chosen from reaction product with a no-group containing compound.
    [14" claim-type="Currently amended] The manufacturing method of the polyacetal resin composition which mixes a polyacetal resin and a glyoxydiurade compound.
    [15" claim-type="Currently amended] The manufacturing method of the polyacetal resin composition of Claim 14 which further mixes at least 1 sort (s) chosen from a basic nitrogen containing compound and antioxidant.
    [16" claim-type="Currently amended] a polyacetal resin composition comprising (a) a polyacetal resin and a glyoxydiurade compound, or (b) a polyacetal resin composition comprising a polyacetal resin, a glyoxydiurade compound and a basic nitrogen-containing compound The molded article, a polyacetal resin molded article having a formaldehyde amount of 1.5 μg or less per 1 cm 2 surface area of the molded article when stored in a closed space at a temperature of 80 ° C. for 24 hours.
    [17" claim-type="Currently amended] The polyacetal resin molded article according to claim 16, wherein the amount of formaldehyde generated when stored for 3 hours in an airtight space having a temperature of 60 DEG C and a saturated humidity is 2.5 µg or less per square centimeter of the molded article.
    [18" claim-type="Currently amended] 17. The polyacetal resin molded article according to claim 16, wherein the molded article is at least one member selected from automobile parts, electric and electronic parts, building materials, piping parts, living and cosmetic parts, and medical parts.
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    同族专利:
    公开号 | 公开日
    MY124132A|2006-06-30|
    CN1175041C|2004-11-10|
    CA2273098A1|1998-07-09|
    US6642289B2|2003-11-04|
    CA2273098C|2008-03-18|
    DE69727834T2|2005-01-13|
    US20050075429A1|2005-04-07|
    EP0955337A4|2000-03-15|
    US7041718B2|2006-05-09|
    EP0955337A1|1999-11-10|
    TW474967B|2002-02-01|
    BR9713872A|2000-03-14|
    KR100502597B1|2005-07-22|
    CN1242031A|2000-01-19|
    WO1998029510A1|1998-07-09|
    DE69727834D1|2004-04-01|
    PL334295A1|2000-02-14|
    US20030158301A1|2003-08-21|
    EP0955337B1|2004-02-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-12-27|Priority to JP34992096
    1996-12-27|Priority to JP96-349920
    1997-12-22|Application filed by 가스가 다쿠조우, 폴리플라스틱스 가부시키가이샤
    1997-12-22|Priority to PCT/JP1997/004758
    2000-10-25|Publication of KR20000062354A
    2004-11-25|First worldwide family litigation filed
    2005-07-22|Publication of KR100502597B1
    2005-07-22|Application granted
    优先权:
    申请号 | 申请日 | 专利标题
    JP34992096|1996-12-27|
    JP96-349920|1996-12-27|
    PCT/JP1997/004758|WO1998029510A1|1996-12-27|1997-12-22|Polyacetal resin composition and moldings|
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