JP2006181277A - Deodorant and resin composition containing deodorant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To highly efficiently suppress aldehyde odor and surely collect aldehydes without impairing the characteristics of resin even if mixing it with polyacetal resin and the like. <P>SOLUTION: This deodorant is composed of phosphorus compound having active hydrogen atoms. This deodorant is useful for efficiently deodorizing the aldehyde odor. This deodorant can be used by being combined with auxiliary deodorizing agent (basic-nitrogen-containing compounds, weak acid or its metal salt, metal compounds, alcohols, polyphenols and adsorbent inorganic compounds) or combined with resin to be formed into a resin composition. The resin composition may include oxidation inhibitor, heat-resistant stabilizer, working stabilizer, weatherproof (light-resistant) stabilizer, gloss control agent, sliding property improving agent, colorant and filler. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a deodorant useful for deodorizing an aldehyde odor (particularly formaldehyde odor) and a resin composition containing the deodorant.

  Aldehydes, particularly formaldehyde, are used as raw materials for resins (for example, urea resins, melamine resins, phenol resins, polyacetal resins, etc.) in various fields such as residential building materials, adhesives, coating agents and molded products. However, there is a problem that formaldehyde is volatilized from such a resin, and the living environment and the health of residents are impaired by an irritating odor.

  Known aldehyde deodorants include, for example, activated carbon, melamines, ureas, amino acids, polyhydric alcohols, and the like. In addition, US Pat. No. 5,160,679 (Patent Document 1) discloses acetoacetamide, monomethylacetoacetamide, monoethylacetoacetamide and the like as formaldehyde scavengers. JP-A-4-293474 (Patent Document 2) discloses cyclic urea derivatives such as 2-imidazolidone, 4-methyl-2-imidazolidone, 2-oxy-hexahydro-pyrimidine, 2-oxy-1,3-diazepane. , Removing acetaldehyde. Furthermore, Japanese Patent Application Laid-Open No. 11-4879 (Patent Document 3) describes deodorization containing an azole compound (such as a diazole compound such as 3-methyl-5-pyrazolone), an azine compound, or a 1-aminopyrrolidine compound as an active ingredient. It is disclosed that the agent removes aldehydes such as acetaldehyde and formaldehyde.

  However, these conventional aldehyde deodorizers have insufficient performance to suppress aldehyde generation and heat resistance, and cannot reliably capture and deodorize aldehydes, or have high volatilization and exudation (blooming) Capturing ability or deodorizing ability cannot be maintained for a long time.

Among resins that produce aldehydes, thermoplastic resins such as polyacetal resin and polyvinyl acetal resin are molded by heating and melting (including pelletization), and from the viewpoint of productivity, the molded product is at a high temperature. (Including pellets) is often packed. In such a case, an aldehyde is easily generated by increasing the temperature of the molded product.
US Pat. No. 5,160,679 JP-A-4-293474 Japanese Patent Laid-Open No. 11-4879

  Therefore, the objective of this invention is providing the resin composition containing the deodorizer which can suppress an aldehyde odor efficiently, a deodorizer composition, and the said deodorizer.

  Another object of the present invention is to provide a deodorant, a deodorant composition, and a resin composition containing the deodorant that can reliably capture aldehyde without impairing the properties of the resin even when mixed with a resin. To provide things.

  Still another object of the present invention is to provide a deodorant, a deodorant composition, and a resin composition containing the deodorant capable of capturing or deodorizing aldehydes over a long period of time by suppressing bleeding out and volatilization. It is to provide.

  Another object of the present invention is to provide a deodorant and a deodorant composition that can greatly suppress the generation of aldehyde from a resin by using it mixed with a resin that produces an aldehyde.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a phosphorus compound having an active hydrogen atom or a salt thereof has an excellent aldehyde scavenging ability or deodorizing ability, and has completed the present invention.

  That is, the deodorizer of this invention is a deodorizer for deodorizing an aldehyde odor, and is comprised with the phosphorus compound which has an active hydrogen atom, or its salt. The phosphorus compound may be a compound represented by the following formula (1) or (2).

(Wherein R ¹ and R ² are the same or different and are a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a hetero atom-containing group which may have a substituent, or an organic group. R ¹ and R ² may be bonded to each other to form a ring with an adjacent phosphorus atom, and Y ¹ has an oxygen atom, a sulfur atom, a Se atom, a Te atom, or a substituent. An optional borane group.)
The hydrocarbon group represented by R ¹ and R ² may be an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group, and the heteroatom-containing group is a heterocyclic group or It may be a group —OR ³ (wherein R ³ represents a hydrogen atom, a hydrocarbon group or an acyl group). The ring formed by R ¹ and R ² together with the adjacent phosphorus atom may be a 4-20 membered heterocycle. The salt of the phosphorus compound may be a metal salt, an ammonium salt, or a salt with a basic nitrogen-containing compound (such as an aminotriazine compound, a guanidine compound, or a urea compound). The phosphorus compound may be at least one selected from phosphines, phosphine oxides, phosphinic acids and phosphonic acids.

  The deodorant composition of the present invention can be composed of the above deodorant and at least one deodorizing aid selected from basic nitrogen-containing compounds, weak acids or metal salts thereof, alcohols, and adsorptive inorganic compounds. . The proportion of the deodorizing aid may be about 0.01 to 10,000 parts by weight with respect to 100 parts by weight of the deodorant.

  The resin composition (for example, deodorant resin composition) of this invention can be comprised with the said deodorizer and resin at least. Examples of the resin include at least one selected from an olefin resin, a halogen-containing vinyl resin, a styrene resin, an acrylic resin, a polyester resin, and a polyurethane resin. In the resin composition, the proportion of the deodorant may be about 0.01 to 30 parts by weight with respect to 100 parts by weight of the resin.

  The present invention also includes a polyacetal resin composition containing a polyacetal resin and the phosphorus compound or a salt thereof. In the polyacetal resin composition, a pellet of the polyacetal resin and a master batch containing the phosphorus compound or a salt thereof may coexist.

  The resin composition (deodorant resin composition, polyacetal resin composition, etc.) further includes an antioxidant, a heat stabilizer, a processing stabilizer, a weather (light) stabilizer, an impact modifier, and a gloss control. It may contain at least one selected from an agent, a sliding property improving agent, a colorant and a filler.

The polyacetal resin molded product of the present invention is formed of the polyacetal resin composition. When the molded product is stored in a sealed space at a temperature of 80 ° C. for 24 hours, the amount of generated formaldehyde is 1.0 μg or less (for example, 0.1 to 1 μg) per 1 cm ² of the surface area of the molded product and / or (2 ) When stored in a sealed space at a temperature of 60 ° C. and saturated humidity for 3 hours, the amount of formaldehyde generated may be 1.2 μg or less (for example, 0 to 1.2 μg) per 1 cm ² of the surface area of the molded product. The molded article may be an automobile part, an electric / electronic part (electrical and / or electronic part), a building material / piping part (building material / and / or a piping part), a daily life part, a medical part, an office automation equipment part, an edible part or It may be a photographic part.

  Since the deodorizer of this invention is comprised with the specific phosphorus compound, it can suppress an aldehyde odor efficiently. Further, even when a deodorant or a deodorant composition is mixed with a resin or the like and used, aldehyde can be reliably captured without impairing the properties of the resin. Furthermore, bleed-out and volatile emission can be suppressed, and aldehyde can be captured or deodorized over a long period of time. In addition, when a deodorant or a deodorant composition is mixed with a resin that generates an aldehyde, the generation of aldehyde from the resin can be significantly suppressed.

[Deodorants]
(Phosphorus compound or salt thereof)
The deodorizer of the present invention contains a phosphorus compound having an active hydrogen atom or a salt thereof. A phosphorus compound or its salt can be used individually or in combination of 2 or more types. The phosphorus compound only needs to have at least one active hydrogen atom, and may be, for example, a compound having at least one hydrogen-phosphorus bond.

  Such phosphorus compounds include, for example, compounds represented by the following formula (1) or (2).

(Wherein R ¹ and R ² are the same or different and are a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a hetero atom-containing group which may have a substituent, or an organic group. R ¹ and R ² may be bonded to each other to form a ring with an adjacent phosphorus atom, and Y ¹ has an oxygen atom, a sulfur atom, a Se atom, a Te atom, or a substituent. An optional borane group.)
Preferred phosphorus compounds are represented, for example, by the following formulas (1a), (1b), (2a), (2b) and (2c).

(Wherein Y ² represents an oxygen atom or a sulfur atom (especially an oxygen atom), and rings Z ¹ and Z ² are the same or different and represent a 4- to 10-membered ring containing a phosphorus atom as a constituent atom of the ring, Z ³ represents a 5- to 10-membered ring containing a phosphorus atom and an atom Y ² as a ring-constituting atom, and the rings Z ⁴ and Z ⁵ are the same or different, and a 4- to 10-membered ring containing a phosphorus atom as a ring-constituting atom The rings Z ^{1 to} Z ⁵ may have a substituent, and R ¹ , R ² and Y ¹ are the same as above.
The expressions (1a) and (1b) correspond to the expression (1), and the expressions (2a) to (2c) correspond to the expression (2).

The halogen atoms represented by R ¹ and R ² include fluorine, chlorine, bromine and iodine atoms.

Examples of the hydrocarbon group represented by R ¹ and R ² include an aliphatic hydrocarbon group (alkyl group, alkenyl group, alkapolyene-yl group (alkadienyl group, 1,3,5-hexatrienyl group, etc.). In addition to alkatrienyl groups, alkynyl groups, etc.), alicyclic hydrocarbon groups (cycloalkyl groups, cycloalkenyl groups, etc.), aromatic hydrocarbon groups (aryl groups, aralkyl groups, etc.), and polycyclic groups (Bridged cyclic hydrocarbon group, condensed polycyclic group, cyclic terpene group and the like).

Among the aliphatic hydrocarbon groups, examples of the alkyl group include linear or branched C _1-30 alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl. Examples of the alkenyl group include linear or branched C _2-30 alkenyl groups such as vinyl, allyl and isopropenyl. Examples of the alkadienyl group include linear or branched C _3-30 alkadienyl groups such as propadienyl and 1,4-octadienyl. Examples of the alkynyl group include linear or branched C _2-30 alkynyl groups such as ethynyl and propynyl.

Among the alicyclic hydrocarbon groups, examples of the cycloalkyl group include _C3-32 cycloalkyl groups such as cyclohexyl. Examples of the cycloalkenyl group include _C3-32 cycloalkenyl groups such as cyclohexenyl.

Among the aromatic hydrocarbon groups, the aryl group includes, for example, C _6-14 aryl groups such as phenyl and naphthyl. Aralkyl groups include, for example, C _6-14 aryl-C _1-4 alkyl groups such as benzyl and phenethyl.

Examples of the polycyclic group include C _6-20 bi or tricyclo groups such as bicyclohexyl, dicyclopentadienyl, and indenyl groups.

Examples of the hetero atom-containing group represented by R ¹ and R ² include an acyclic organic group or a cyclic organic group containing at least one hetero atom selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom (heterocycle Group).

Examples of the acyclic heteroatom-containing group include a hydroxyl group or a derivative group thereof [for example, a group —OR ³ (wherein R ³ represents a hydrogen atom, a hydrocarbon group, or an acyl group). In addition, when R ³ is a hydrocarbon group (such as the hydrocarbon group exemplified above) or an acyl group, the group —OR ³ may be simply referred to as a substituted hydroxyl group], a mercapto group or a derivative group thereof (for example, the substituted group A substituted mercapto group corresponding to a hydroxyl group), a carboxyl group or a derivative group thereof (for example, an ester group, an acyl group, an amide group, etc.), an amino group, or an N-substituted amino group (N substituted with the hydrocarbon group exemplified above) -Substituted amino group or N, N-disubstituted amino group, for example, N-mono such as methylamino group or C _1-6 acylamino group such as N, N-diC _1-4 alkylamino group, acetylamino group, etc. ), phosphino group (-PH ₂₎ or derivatives thereof (substituted phosphino group in which a hydrogen atom is substituted with such hydrocarbon groups exemplified above, for example, mono- or such as methyl phosphino group C _1-4, such as alkyl phosphino group), sulfinic acid group (-S (= O) -OH) or a derivative group (substituted sulfinyl group in which the hydroxyl groups of the sulfinic acid group is substituted by such as a hydrocarbon group exemplified above , For example, a C _1-4 alkylsulfinyl group such as methylsulfinyl), a sulfonic acid group (—S (═O) ₂ —OH) or a derivative group thereof (the hydroxyl group of the sulfonic acid group is the hydrocarbon group exemplified above) A substituted sulfonyl group substituted with, for example, a C _1-4 alkylsulfonyl group such as methylsulfonyl).

Examples of the substituted hydroxyl group include alkoxy groups (eg, linear or branched C _1-30 alkoxy groups such as methoxy, ethoxy and butoxy), alkenyloxy groups (C _2-30 alkenyloxy groups, etc.), cycloalkyloxy groups (For example, a _C3-32 cycloalkyloxy group such as cyclohexyloxy), a cycloalkenyloxy group (such as a cycloalkenyloxy group corresponding to the cycloalkyloxy group), an aryloxy group (for example, phenoxy, naphthyloxy, etc.) C _6-14 aryloxy group, etc.), aralkyloxy groups (eg, C _6-14 aryl-C _1-6 alkoxy groups such as benzyloxy, phenethyloxy groups, etc.), acyloxy groups [eg, formyloxy, acetyloxy ( aliphatic C _1-6 acyloxy group such as acetoxy); benzo And aromatic C _7-14 acyloxy group such as aryloxy], and the like.

Among the derivative groups of the carboxyl group, examples of the ester group include a linear or branched C _1-10 alkoxy-carbonyl group (such as an ethoxycarbonyl group) and a C _5-8 cycloalkyloxy-carbonyl group (such as a cyclohexyloxycarbonyl group). C _6-14 aryloxy-carbonyl group (such as phenoxycarbonyl group) and C _6-14 aryl-C _1-4 alkoxy-carbonyl group (such as benzyloxycarbonyl group). Examples of the acyl group include C _1-10 aliphatic acyl groups (acetyl, propionyl group, etc.), C _6-14 aryl-carbonyl groups (benzoyl group, etc.) and the like. Examples of the amide group include amide groups corresponding to the ester groups.

  The heterocyclic group preferably has at least one heteroatom selected from nitrogen, oxygen and sulfur atoms as a constituent atom of the ring. The heterocyclic group includes, for example, a 5- or 6-membered heterocyclic group containing the heteroatom and a condensed heterocyclic group obtained by condensing a heterocyclic ring with a hydrocarbon group. The heterocyclic group may be either an aromatic or non-aromatic heterocyclic group.

The organometallic group represented by R ¹ and R ² includes a silyl group [silanol, mono to tri C _1-4 alkylsilyl group (such as methylsilyl), di- or tri C _1-4 alkoxysilyl group (such as methoxysilyl) And the like, and organometallic groups corresponding to these silyl groups (such as selenium, tellurium or germanium atom-containing organometallic groups).

As the ring R ¹ and R ² form together with the phosphorus atom, 4 to 20 membered heterocyclic ring (phosphorus atom-containing hetero ring) having a phosphorus atom as a hetero atom constituting the ring, preferably 5 to 16 membered heterocycle Any of a non-aromatic ring and an aromatic ring may be used. The ring may be a bicyclo ring. The phosphorus atom-containing heterocycle may have a substituent.

The hydrocarbon group or heteroatom-containing group represented by R ¹ and R ² , or the substituent of the phosphorus atom-containing heterocycle includes the halogen atoms exemplified above, the hydrocarbon groups exemplified above, and the heteroatoms exemplified above. A containing group, a nitro group, a cyano group, a chalcogen-containing group (thio group, seleno group, tellurium group, etc.) and the like. The hydrocarbon group or heteroatom-containing group represented by R ¹ and R ² , or the phosphorus atom-containing group may have one of the substituents, and have a plurality of the same or different substituents. It may be.

As preferred R ¹ and R ² , a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group (alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, aralkyl group, etc.), A heterocyclic group which may have a substituent, a group —OR ³ (such as a hydroxyl group, an alkoxy group, a cycloalkyloxy group, a cycloalkenyloxy group, an aryloxy group or an aralkyloxy group), particularly hydrogen An aryl, an aralkyl group which may have a substituent, an aralkyl group, a hydroxyl group, an alkoxy group, or an aryloxy or aralkyloxy group which may have a substituent is preferable. R ¹ and R ² are a non-aromatic or aromatic phosphorus atom-containing ring (4 to 20-membered, preferably 4 to 10-membered phosphorus) which may have a substituent together with the adjacent phosphorus atom. It is also preferable to form an atom-containing ring or the like.

Y ¹ in the above formulas (2), (2a) to (2c) is an oxygen atom, a sulfur atom, a Se atom, a Te atom, or a borane group optionally having a substituent (for example, trimethylborane). Trialkylborane groups, and trihalogenated borane groups such as borane trichloride). Preferred Y ¹ is an oxygen atom or a sulfur atom (particularly an oxygen atom). Examples of compounds in which Y ¹ is an oxygen atom include phosphines, phosphine oxides, phosphinic acids and phosphonic acids.

In the above formulas (1b) and (2c), the ring Z ¹ (ring Z ² , Z ³ or Z ⁴ ) is 4 to 10 membered heterocycle, preferably 4 to 8 membered heterocycle, more preferably 5 to 6 A non-aromatic ring is preferable. In particular, it is preferable to form a bicyclo ring with rings Z ¹ and Z ² (or rings Z ⁴ and Z ⁵ ) and a phosphorus atom. The heterocycles Z ¹ and Z ² (or rings Z ⁴ and Z ⁵ ) may have the substituents exemplified in the above R ¹ section.

In the formula (2b), the ring containing the phosphorus atom represented by the ring Z ³ and the atom Y ² as a ring constituting atom is a heterocycle formed by R ¹ , R ² and the phosphorus atom in the formula (1). It is a 5- to 10-membered heterocyclic ring, preferably a 5- to 8-membered heterocyclic ring, particularly a 5- or 6-membered heterocyclic ring, and preferably a non-aromatic ring. The non-aromatic heterocycle Z ³ may have 1 to 2 carbon-carbon unsaturated bonds. Ring Z ³ may have the substituents exemplified in the above R ¹ section.

Ring Z ³ includes an aromatic ring as a substituent [an aromatic ring corresponding to the aryl group exemplified in the above R ¹ (C _6-10 aromatic ring such as benzene, naphthalene ring, particularly benzene ring). ] May be condensed by 1 to 3 (especially 1 or 2) (ortho condensation and ortho and peri condensation, especially ortho condensation).

The aromatic ring condensed to the heterocycle Z ³ may have about 1 to 4, preferably 1 to 3 (for example, 1 or 2) substituents. Examples of the substituent include the substituents exemplified in the above R ¹ , in particular, a hydroxyl group, a hydrocarbon group (an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group), an alkoxy group, an acyl group, and a cyano group. An organic group such as

As the phosphorus-containing group formed by the ring Z ³ and Y ¹ condensed with such an aromatic ring, 10 H-9-oxa-10-phosphaphenanthrene oxide represented by the following formula in which Y ¹ is an oxygen atom: Groups and the like are preferred.

  The phosphorus compound may form a salt. Such phosphorus compound salts include the phosphorus compound and metals [alkali metals (potassium, sodium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (group 7 of the periodic table such as manganese). A metal; a periodic table Group 8 metal such as iron; a periodic table Group 9 metal such as cobalt; a periodic table Group 10 metal such as nickel; a periodic table Group 11 metal such as copper; Examples thereof include ammonium salts of the phosphorus compounds, and salts of the phosphorus compounds with basic nitrogen compounds [aminotriazine compounds (such as melamine and benzoguanamine), guanidine compounds (such as guanidine), urea compounds (such as urea), and the like]. Of these salts, alkali metal salts, alkaline earth metal salts, ammonium salts, and salts with aminotriazine compounds are particularly preferable.

Examples of the phosphines represented by the formula (1a) include phosphine; C _1-12 alkylphosphine optionally having the above-described substituent (such as hydroxyl group) such as methylphosphine and hydroxymethylphosphine; cyclohexylphosphine. It said substituents optionally C _3-8 cycloalkyl phosphine which may have (such as hydroxyl groups) such as; phenylphosphine, the substituent may have (such as hydroxyl groups) C ₆ such hydroxyphenyl phosphine _-10 arylphosphine; C _6-10 aryl-C _1-4 alkylphosphine such as benzylphosphine; C _1-10 alkoxyphosphine such as methoxyphosphine; C _3-10 cycloalkyloxyphosphine such as cyclohexyloxylphosphine; C _6-10 aryloxy phosphite of Hydroxylphosphines [hydroxyphosphine (phosphinic acid), 1-hydroxy-1-methyl-phosphine, etc., 1-hydroxy-phosphine having a hydrocarbon group at the 1-position, dihydroxyphosphine (phosphonous acid), etc.], etc. Is mentioned. Of these phosphines (1a), phosphines, arylphosphines, hydroxyphosphines (phosphinic acid, phosphonous acid, etc.) are particularly preferred.

Examples of the phosphines represented by the formula (1b) include 1,3-cyclobutylene phosphine, 1,3-cyclopentylene phosphine, 1,4-cyclooctylene phosphine, 1,5-cyclooctylene phosphine, and the like. _Examples thereof include cycloalkylene phosphine (preferably C _4-12 cycloalkylene phosphine, more preferably C _4-10 cycloalkylene phosphine, etc.).

Examples of the phosphine oxides represented by the formula (2a) include phosphine oxide; linear or branched C _1-12 alkyl phosphine oxide such as methyl phosphine oxide; C _3-10 cycloalkyl such as cyclohexyl phosphine oxide. Phosphine oxide; mono or di C _6-10 aryl phosphine oxide such as phenyl phosphine oxide, diphenyl phosphine oxide; C _6-10 aryl-C _1-4 alkyl phosphine oxide such as benzyl phosphine oxide; Branched C _1-10 alkoxyphosphine oxides; C _3-10 cycloalkyloxyphosphine oxides such as cyclohexyloxyphosphine oxide; C _6-10 aryloxyphosphine oxides such as phenoxyphosphine oxide; Examples thereof include xylphosphine oxides (phosphinic acids, phosphonic acids, etc.).

Examples of the phosphinic acids include phosphinic acid (hypophosphorous acid), substituted phosphinic acids (C _1-10 linear or branched alkylphosphinic acids such as methylphosphinic acid; C _3-10 cycloalkylphosphinic acids such as cyclohexylphosphinic acid; C _6-14 aryl phosphinic acid such as phenylphosphinic acid; C _6-10 aryl-C _1-4 alkyl phosphinic acid such as benzylphosphinic acid), ester derivatives of the above phosphinic acid or substituted phosphinic acids (for example, methyl phosphinate) Phosphinic acid C _1-10 alkyl such as phosphinic acid cyclohexyl, phosphinic acid C _3-10 cycloalkyl, phosphinic acid C _6-14 aryl such as phenyl phosphinic acid, etc. Salt) [for example, alkali metal salts (phosphite Such sodium), (such as calcium phosphinate), transition metal salt (phosphinic acid, manganese phosphine iron (III) alkaline earth metal salts, such as phosphinic acid nickel), such as phosphinic acid ammonium] and the like.

Examples of the phosphonic acids include phosphonic acid (phosphorous acid) and phosphonic acid esters (for example, phosphonic acid mono C _1-10 alkyl such as monomethyl phosphonic acid; phosphonic acid mono C _3-10 cycloalkyl such as phosphonic acid monocyclohexyl; Phosphonic acid mono-C _6-14 aryls such as phosphonic acid monophenyl; phosphonic acid diesters corresponding to these phosphonic acid monoesters), salts of the above phosphonic acids (phosphonic acid or phosphonic acid monoester) [for example, alkali metal salts (Such as sodium phosphonate), alkaline earth metal salts (such as magnesium phosphonate), transition metal salts (such as manganese phosphonate and copper (II) phosphonate), and ammonium phosphonate).

  Among the phosphine oxides (2a), in particular, aryl phosphine oxide (particularly diaryl phosphine oxide such as diphenylphosphine oxide), phosphinic acid or phosphonic acid, metal salts of phosphinic acid or phosphonic acid (sodium salt, potassium salt, etc.) Alkali metal salts; alkaline earth metal salts such as magnesium salts and calcium salts; ammonium salts, etc.) are preferred.

  The phosphine oxides represented by the formula (2b) may have a substituent [halogen atom, hydrocarbon group (alkyl group, aryl group etc.), hydroxyl group, alkoxy group etc.] on the benzene ring. 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is mentioned.

Examples of the phosphine oxides represented by the formula (2c) include 1,3-cyclobutylene phosphine oxide, 1,3-cyclopentylene phosphine oxide, 1,4-cyclooctylene phosphine oxide, 1,5-cyclooctylene. Examples thereof include cycloalkylene phosphine oxides such as lene phosphine oxide (preferably C _4-12 cycloalkylene phosphine oxide, more preferably C _4-10 cycloalkylene phosphine oxide).

[Deodorant composition]
The deodorant composition of this invention is comprised with the said deodorizer and a deodorizing adjuvant. By using a combination of a deodorant and a deodorizing aid, the generation of aldehyde can be suppressed synergistically, and the aldehyde odor can be efficiently deodorized.

  Deodorizing aids include basic nitrogen-containing compounds (i), weak acids or their metal salts (ii), alcohols (iii), adsorptive inorganic compounds (iv), polyphenols (v), polyvinyl alcohol, cyclodextrins Etc. can be used. Deodorizing aids can be used alone or in combination of two or more. The deodorizing aid may be reactive with aldehydes. In the deodorant composition, the deodorant is supported (adsorbed, intercalated) on a solid carrier and / or an inclusion body (among the deodorizing aids, adsorbing inorganic compounds, polyvinyl alcohol, cyclodextrin, etc.). , Inclusions, etc.) are also included.

(i) Basic nitrogen-containing compounds Basic nitrogen-containing compounds include low molecular weight compounds and high molecular weight compounds (nitrogen-containing resins) such as urea derivatives (ureas, aminotriazines, guanidines, etc.), polyamides, organic Carboxylic acid hydrazides, amino acids, amines, ammonium compounds (organic ammonium carboxylates, inorganic ammonium compounds, etc.) are included. These basic nitrogen-containing compounds can be used alone or in combination of two or more.

Examples of ureas include urea compounds described in JP-A No. 2002-212433, for example, non-cyclic urea compounds [N-substituted urea substituted with substituents such as urea and alkyl groups, acyclic urea condensates (biuret, Multimers of urea such as biurea; condensates of urea and aldehyde compounds such as methylene diurea and form nitrogen), cyclic urea compounds [cyclic monoureides such as C _1-10 alkylene urea (ethylene urea, crotonylidene urea, etc.) , Arylene urea (eg mesatin), diuretic acid ureido (parabanic acid, barbituric acid, isocyanuric acid, uramil etc.), β-aldehyde acid ureido (uracil, thymine, urazole etc.), α-oxyacid ureido (hydantoin) Hydantoins such as 5,5-dimethylhydantoin and allantoin Cyclic diureides, for example, uric acid, alkyl-substituted uric acid, acetylene urea (glycoluril), diureido of α-oxy acid (such as 1,1, -methylenebis (5,5-dimethylhydantoin)), diurea such as p-urazine, And dicarboxylic acid diureides (such as alloxanthin and purpuric acid).

  Examples of the aminotriazines include amino group-containing 1,3,5-triazines [melamine, substituted melamine (alkyl melamine such as 2-methylmelamine, guanylmelamine, etc.), melamine condensate (melam, melem, melon, etc.), Melamine or derivatives thereof such as melamine co-condensation resins (melamine-formaldehyde resin, phenol-melamine resin, benzoguanamine-melamine resin, aromatic polyamine-melamine resin, etc.); cyanuramides such as ammelin and ammelide; guanamine, acetoguanamine , Benzoguanamine, succinoguanamine, guanamine such as CTU-guanamine or derivatives thereof], amino group-containing 1,2,3-triazines (1,2,3-triazine, benzo-1,2,3-triazine, etc.) And 1, 2 And 4-triazines. The amino group may be substituted at an appropriate site (nitrogen atom and carbon atom, particularly carbon atom) constituting the triazine ring. The number of amino groups is not particularly limited, and is, for example, about 1 to 4, preferably about 1 to 3, and more preferably about 2 to 3. Among the aminotriazines, amino group-containing 1,3,5-triazines [melamine, melamine condensates (particularly melam, melem, melon, etc.), etc.] are particularly preferable.

  Examples of guanidines include guanidines described in JP-A No. 2000-34417, for example, acyclic guanidine (glycosiamine, guanolin, guanidine, cyanoguanidine, etc.), cyclic guanidine (glycocyanidins such as glycocyanidine, creatinine; Oxalylguanidine, oxalylguanidine such as 2,4-diiminoparabanic acid or cyclic guanidine similar to the structure thereof; imino group-substituted urazole compound (iminourazole, guanazine, etc.); Examples include malonyl guanidine, tartronyl guanidine; and mesoxalyl guanidine.

  Examples of the polyamides include 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, Polyamide resins such as nylons such as nylon 6-66-610 or copolymerized polyamides; substituted polyamides having a methylol group or an alkoxymethyl group are included.

The organic carboxylic acid hydrazides, for example, aliphatic carboxylic acid hydrazide [12-hydroxystearic acid hydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, C _2-24 aliphatic, such as dodecanedioic acid dihydrazide (poly) carboxylic acid ( poly) hydrazide, etc.], an aromatic dicarboxylic acid hydrazide [benzoic acid hydrazide, hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, isophthalic acid dihydrazide, terephthalic acid, aromatic such as benzene tricarboxylic acid trihydrazide (poly) C _7-16 carboxylic Acid (poly) hydrazide, etc.]. Moreover, as organic carboxylic acid hydrazides, for example, hydrazides described in WO01 / 62309 can be used.

Amino acids include aliphatic amino acids [glycine, alanine, β-alanine, γ-aminobutyric acid, aminoheptanoic acid, aminononanoic acid, aminoundecanoic acid, hydroxyamino acids (such as serine), sulfur atom-containing amino acids (such as cysteine), acidic C _2-20 aliphatic amino acids such as amino acids (such as aspartic acid) and basic amino acids (such as lysine and arginine); C _2-20 aliphatic amino acids having a C _6-10 aryl group such as phenylalanine and tyrosine] and the like Family amino acids [C _7-18 aromatic amino acids such as anthranilic acid, o, m, p-aminobenzoic acid, etc.], heterocyclic amino acids (proline, hydroxyproline, histidine, tryptophan, etc.) and derivatives of these amino acids (esters) Derivatives, amide derivatives, etc.). The amino acid may have a plurality of amino groups and carboxyl groups.

Examples of the amines include aliphatic amines [mono to tri C _1-4 alkylamines such as diethylamine and triethylamine; mono to tris (hydroxy C _1- ) such as methanolamine, tris (hydroxymethyl) amine, ethanolamine, and diethanolamine. ₄ alkyl) amines], aromatic amines (aromatic secondary amines or tertiary amines such as o, m or p-toluidine, o, m or p-phenylenediamine), and the like.

  As the ammonium compound, for example, an ammonium compound described in WO01 / 62309 can be used.

Examples of organic carboxylates include ammonium salts of organic carboxylic acids such as saturated aliphatic carboxylic acids [saturated C _1-34 monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and valeric acid; succinic acid, adipic acid, and sebacin. Saturated C _2-30 dicarboxylic acids such as acids; these _oxyacids (lactic acid, hydroxybutyric acid, 12-hydroxystearic acid, etc.)] and unsaturated aliphatic carboxylic acids [(meth) acrylic acid, crotonic acid, etc. Examples thereof include ammonium salts of _C3-34 monocarboxylic acids; unsaturated C _4-30 dicarboxylic acids such as maleic acid and fumaric acid; oxyacids such as propiolic acid].

  Examples of inorganic ammonium compounds include ammonium salts of inorganic acids, such as ammonium halides (ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, etc.), ammonium sulfate (non-condensed sulfuric acid such as peroxomonosulfuric acid, sulfuric acid, sulfurous acid, etc.); And ammonium sulfates of various sulfuric acids such as condensed sulfuric acid such as peroxodisulfuric acid and pyrosulfuric acid), (poly) ammonium phosphate, and ammonium carbonate. Of the inorganic ammonium compounds, ammonium chloride and ammonium sulfate are preferred.

(ii) Weak acid or metal salt thereof Weak acid includes organic carboxylic acid and boric acid (non-condensed boric acid such as orthoboric acid, tetraboric acid, boric anhydride, etc.) exemplified in the section of the above organic carboxylic acid ammonium salt. Etc.).

  The weak acid metal salts include, for example, the weak acid metal salts described in WO01 / 62309. For example, the salts with the metals (alkali metal, alkaline earth metal, transition metal) exemplified in the section of the phosphorus compound. Etc. can be exemplified. Of the weak acid metal salts, alkali metal or alkaline earth metal salts are particularly preferable.

  These weak acids or their metal salts can be used alone or in combination of two or more.

(iii) Alcohols The alcohols are monoalcohols (saturated or unsaturated C _4-24 aliphatic alcohols such as myristyl alcohol, stearyl alcohol, oleyl alcohol; saturated or unsaturated C _5-8 alicyclics such as cyclohexyl alcohol). In general, it is preferable to use a polyhydric alcohol. Examples of the polyhydric alcohol include diols [for example, ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, decanediol, etc. C _2-12 alkylene glycol; polyoxy C _2-4 alkylene glycol (eg, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polytetramethylene glycol, etc.); alicyclic diol (eg, 1, 4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.)], glycerin, diglycerin, trimethylolpropane, trimethylol Tan, pentaerythritol, dipentaerythritol, poly pentaerythritol, polyhydric alcohols such as sorbitol can be exemplified. The alcohols can be used alone or in combination of two or more.

  Of the alcohols, polyoxyalkylene glycols such as diethylene glycol; polyhydric alcohols such as glycerin, (poly) pentaerythritol, and sorbitol are particularly preferable.

(iv) Adsorbing inorganic compound The adsorbing inorganic compound includes an inorganic compound known as a porous carrier. Examples of such adsorptive inorganic compounds include porous inorganic oxides (aluminum and / or silicon oxides such as zeolite, silica gel, alumina, and sepiolite), perlite, activated carbon (such as mineral activated carbon), and the like. It is. The zeolite may be a synthetic zeolite or a natural zeolite (such as faujasite). These adsorptive inorganic compounds can be used alone or in combination of two or more.

(v) Polyphenols Polyphenols include, for example, polyphenols, bisphenols, calixarene, catechins (catechin, epicatechin, gallocatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, quercetin, chemferol , Myricetin, etc.), theanines, tannins and lignins. The catechins can be obtained from Taiyo Kagaku Co., Ltd., for example, as “Sunflavone series (HG, P, etc.)”.

  Examples of the polyhydric phenols include dihydric phenols such as catechol, resorcin, hydroquinone, and 2,6-dihydroxynaphthalene; trihydric phenols such as pyrogallol and phloroglucin; phenol lignin and gallic acid.

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

The ratio of the deodorizing aid can be selected from a wide range, for example, about 0.01 to 10,000 parts by weight, for example, with respect to 100 parts by weight of the deodorant. The ratio is 0.01 to 500 parts by weight, preferably 0.01 to 100 parts by weight (for example, 0.02 to 50 parts by weight), more preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the deodorant. It may be about 30 parts by weight (for example, 0.1 to 15 parts by weight). In the composition in which the deodorant is supported on the solid carrier and / or the clathrate, the ratio is, for example, 0.01 to 5000 parts by weight (for example, 0. 01 to 3000 parts by weight), preferably 0.05 to 2000 parts by weight (eg 0.1 to 1500 parts by weight), more preferably 0.5 to 1500 parts by weight (eg 1.0 to 1000 parts by weight). ) Degree.
[Resin composition]
The resin composition (including the deodorant resin composition) of the present invention is composed of the deodorant (or deodorant composition) and a resin.

(resin)
As the resin, either a natural resin or a synthetic resin can be used, and either a thermosetting resin or a thermoplastic resin may be used.

  Examples of the natural resin include rosin, shellac, dammar, starch, and derivatives thereof. Among the synthetic resins, examples of the thermosetting resin include diallyl phthalate resin, vinyl ester resin, unsaturated polyester resin, maleic acid resin, epoxy resin, polyurethane resin, polyimide resin, phenol resin, amino resin (urea resin, melamine). Resin, guanamine resin, etc.), silicon resin and the like.

Preferred resins include thermoplastic resins such as olefin resins, halogen-containing vinyl resins, styrene resins, acrylic resins, polyester resins, polyamide resins, polyurethane resins, polyacetal resins, polyether resins [polyphenylene. Oxide resins, polyalkylene oxides (poly C _2-6 alkylene oxides such as polyethylene oxide, etc.), polyphenylene sulfide resins, polycarbonate resins, polyvinyl alcohol, polyvinyl acetate, polyvinyl acetals, polyamideimides, polyimides, polyethers Imide, polysulfone (thermoplastic polysulfone, poly (ether sulfone), poly (4,4'-bisphenol ether sulfone, etc.), polyether ether ketone, polyether keto , Cellulose derivatives (cellulose esters, celluloids, etc.), elastomers (polyurethane elastomers, etc.), rubbers (natural rubber, hydrochloric acid rubber, etc.), copolymers containing these polymer components as constituent units, and the like. The resins can be used alone or in combination of two or more.

  Incidentally, the deodorant and deodorant composition of the present invention is excellent in aldehyde scavenging effect, so even when combined with a resin that generates aldehyde by the action of heat, light, oxygen, acid, alkali, water, etc. Generation of aldehyde can be efficiently suppressed. Moreover, even if an aldehyde is generated, it can be efficiently deodorized. Examples of resins that generate aldehyde include polyacetal resins (polyacetal homopolymer or copolymer, etc.), polyvinyl acetals (eg, polyvinyl formal, polyvinyl butyral, etc.), phenol resins (eg, novolac-type or resol-type phenol resins, etc.), furan resins. And the amino resin (aminoaldehyde-based resin).

  The resin is preferably a resin having moldability (for example, film formability, thermoformability such as injection moldability), and may have not only a straight chain but also a branched chain structure and a crosslinked structure. The degree, the degree of branching, the state of copolymerization (for example, random, block, graft, etc.) and the copolymer composition ratio are not particularly limited.

  Among the thermoplastic resins, examples of the olefin resin include homo- or copolymers of α-olefins such as ethylene, propylene, 4-methylpentene (polyethylene, polypropylene, ethylene-propylene copolymers, etc.); And copolymerizable monomers (vinyl halide compounds such as vinyl chloride, vinyl acetate, acrylic monomers, etc.) or derivatives thereof (ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer) Polymers); halogen-containing olefin resins (chlorinated polyethylene, etc.).

  Examples of the halogen-containing vinyl resin include, for example, a homo- or copolymer of a halogen-containing vinyl monomer such as vinyl chloride or vinylidene chloride (polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, etc.); halogen -Containing vinyl monomers and copolymerizable monomers [vinyl monomers such as vinyl acetate, styrene monomers, acrylic monomers, and maleic anhydride; diene monomers such as butadiene and isoprene] (For example, vinyl chloride-vinyl acetate copolymer, vinyl chloride-styrene copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride- (meth) acrylic acid ester copolymer, etc.) It is.

  Examples of the styrenic resin include aromatic vinyl monomers (such as styrene and α-methylstyrene) or copolymers (such as polystyrene); aromatic vinyl monomers and copolymerizable monomers [ Copolymers with (meth) acrylonitrile, acrylic monomers such as (meth) acrylic acid esters, maleic anhydride, etc.] [for example, acrylonitrile-styrene copolymer (AS resin), (meth) acrylic acid ester- Acrylic monomer such as styrene copolymer-styrene copolymer, etc.]; Rubber-modified styrene copolymer [styrene and elastomer (butadiene rubber, acrylic rubber, etc.) or maleic acid copolymer such as acrylonitrile -Butadiene-styrene copolymer (ABS resin, etc.)] and the like.

Acrylic resins include, for example, poly (meth) acrylonitrile, poly (meth) acrylic acid esters (for example, poly (meth) acrylic acid C _1-10 alkyl esters such as polymethyl methacrylate and polyethyl acrylate), and the like. It is.

Examples of the polyester resin include homopolymers such as poly C _2-6 alkylene terephthalate (eg, polyethylene terephthalate, polybutylene terephthalate, etc.) poly C _2-6 alkylene naphthalate (eg, polyethylene naphthalate, polybutylene naphthalate, etc.). Polyester; C _2-6 alkylene terephthalate or copolyester having C _2-6 alkylene naphthalate as the main repeating unit; polyarylate, polyester elastomer and the like.

  Examples of the amide-based resin include polyamides such as polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 46, polyamide 610, and polyamide 612, polyamide elastomers, and the like. Examples of the polyurethane resin include polyurethane and polyurethane elastomer.

Examples of the polyacetal resin include a polymer compound having an oxymethylene group (—OCH ₂ —) as a main structural unit, such as polyacetal homopolymer or polyoxymethylene (for example, trade name “Delrin” manufactured by DuPont, USA, Asahi Kasei Kogyo Co., Ltd.) And a polyacetal copolymer containing an oxymethylene unit and a comonomer unit (for example, a product name “Duracon” manufactured by Polyplastics Co., Ltd.). In the copolymer, the comonomer unit includes an oxyalkylene unit (for example, an oxyethylene group (—OCH ₂ CH ₂ —), an oxypropylene group, an oxytetramethylene group having about 2 to 6 carbon atoms (preferably about 2 to 4 carbon atoms). Group). The content of the comonomer unit is a small amount, for example, 0.01 to 20 mol%, preferably 0.03 to 15 mol% (for example, 0.05 to 10 mol%), more preferably based on the whole polyacetal resin. It can select from the range of about 0.1-10 mol%.

  The polyacetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like. The polyacetal copolymer is a random copolymer, a block copolymer (for example, a copolymer described in JP-B-2-24307, manufactured by Asahi Kasei Kogyo Co., Ltd., trade names “TENAC LA”, “TENAC LM”, etc.), a graft copolymer, and the like. There may be. Moreover, the polyacetal resin may have a branched structure as well as a linear structure, and may have a crosslinked structure. Furthermore, the terminal of the polyacetal resin may be stabilized by, for example, esterification with a carboxylic acid such as acetic acid or propionic acid or an anhydride thereof, urethanization with an isocyanate compound, or etherification. The polymerization degree, branching degree, and crosslinking degree of the polyacetal are not particularly limited as long as it can be melt-molded. The molecular weight of the polyacetal resin is not particularly limited, and is, for example, a weight average molecular weight of 5,000 to 500,000, preferably about 10,000 to 400,000. The polyacetal resin also includes a mixture of a polyacetal copolymer and a polyacetal terpolymer that may have a branched structure.

  The polyacetal resin may be, for example, homopolymerization or copolymerization of aldehydes such as formaldehyde, paraformaldehyde, and acetaldehyde, and components such as trioxane and tetraoxane, or the above components and other cyclic ethers (ethylene oxide, propylene oxide, butylene). Oxide, styrene oxide, cyclohexane oxide, cyclohexene oxide, 1,3-dioxolane, 1,3-dioxane, etc.) and / or cyclic formal (diethylene glycol formal, 1,4-butanediol formal, etc.) it can. Further, as a copolymerization component, 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) Ether, triethylene glycol diglycidyl ether, butanediol diglycidyl ether, etc.), alkyl or aryl glycidyl alcohol, cyclic esters (eg, β-propiolactone) and / or vinyl compounds (eg, styrene, vinyl ether, etc.) You can also

  Of the resins, thermoplastic resins such as polyacetal resin, olefin resin, halogen-containing vinyl resin, styrene resin, acrylic resin, polyester resin, and polyurethane resin are preferable.

  The resin may be used in the form of a solid, or in the form of a solution (organic solvent solution, aqueous solution, etc.) or a dispersion (aqueous emulsion, etc.).

  The deodorant and deodorant composition of the present invention can effectively capture aldehydes (formaldehyde, etc.) and deodorize them even in a small amount, and have high affinity with the resin. Therefore, the characteristics of the resin composition are not impaired, bleeding out from the resin can be prevented, and the aldehyde capturing ability or deodorizing ability can be maintained for a long time.

  The proportion of the deodorant may be an effective amount that expresses an ability to capture aldehyde (formaldehyde, etc.), for example, 0.01 to 30 parts by weight (for example, 0.01 to 25 parts per 100 parts by weight of the resin). Parts by weight), preferably 0.02 to 15 parts by weight, more preferably about 0.05 to 10 parts by weight, and about 0.1 to 5 parts by weight (for example, 0.1 to 3 parts by weight) Can effectively suppress the aldehyde odor.

  When the resin composition contains a deodorizing aid, the proportion of the deodorizing aid may be an effective amount that exhibits a scavenging ability for aldehyde (formaldehyde, etc.), and is, for example, 0 with respect to 100 parts by weight of the resin. 0.0001 to 10 parts by weight (for example, 0.001 to 10 parts by weight), preferably 0.005 to 5 parts by weight, more preferably about 0.01 to 5 parts by weight, and 0.1 to 3 parts by weight ( For example, it may be about 0.1 to 1 part by weight.

The resin composition further comprises a foaming agent, a nitrogen-containing compound [amides (polycarboxylic acid amides such as malonamide, isophthalic acid diamide, p-aminobenzamide, etc.), hydrazines (hydrazine, hydrazone, etc.)], stable Agents [antioxidants (hindered phenols, hindered amines, etc.), UV absorbers, heat stabilizers (aminotriazine compounds (melamine, benzoguanamine, CTU-guanamine, etc.), guanidine compounds (allitein, hydantoin, 5,5-dimethyl) Basic compounds such as hydantoins, urea compounds (such as biurea), hydrazide compounds (such as sebacic acid dihydrazide), amino alcohol compounds, imide compounds; organic acids or inorganic acid salts of alkali or alkaline earth metals (12-hydroxy) Steer Calcium phosphate); zeolites; phosphine compound), a processing stabilizer {long chain fatty acids (C _10-26 saturated aliphatic mono- or dicarboxylic acids, such as C _10-20 unsaturated aliphatic mono- or dicarboxylic acid) or a derivative thereof (Acid amide (such as ethylene bisstearyl amide) with amines such as monoamine or diamine, ester with aliphatic mono or polyol, etc.), polyoxyalkylene glycol (polyoxy C _2-6 alkylene glycol (for example, number average molecular weight 3 × 10 ² to 1 × 10 ⁶ polyoxy C _2-4 alkylene glycol, etc.), silicone compounds (di C _1-6 alkyl siloxane, C _1-4 alkyl C _6-10 aryl siloxane, di C _6-10 aryl siloxane, etc.) Monoorganosiloxane; homopolymer or copolymer of monoorganosiloxane)), weather resistance (Light) stabilizers (benzophenone compounds, aromatic benzoate compounds, cyanoacrylate compounds, oxalic acid anilide compounds, hydroxyphenyl-1,3,5-triazine compounds, etc.)], impact resistance improvers [ Acrylic core-shell polymer, polyurethane resin, polyester resin, etc.], gloss control agent [in addition to the resin exemplified in the section of impact resistance improver, acrylic resin (C _1-10 alkyl such as polymethyl methacrylate (meta ) Acrylate homopolymer or copolymer, AS resin, AES resin, etc.), Styrenic resin (styrene homopolymer or copolymer, etc.)], Slidability improver [Olefin resin, silicone resin, fluorine resin Etc.], plasticizer, reinforcing agent, filler [fibrous filler (inorganic fibers such as glass fiber, carbon fiber, whisker; Organic fibers such as mid fibers), plate-like fillers (glass flakes, mica, various metal foils, etc.), granular fillers (glasses such as milled fibers and glass beads); metal oxides such as zinc oxide and alumina; Sulfates such as calcium sulfate; carbonates such as calcium carbonate; silicates such as talc; sulfides such as molybdenum disulfide; carbides such as graphite fluoride and silicon carbide)], antistatic agents, surfactants , Flame retardants, lubricants, colorants [dyes (such as organic dyes such as solvent-based dyes), inorganic or organic pigments, etc.], antifungal agents, antibacterial agents and the like. These additives can be used alone or in combination of two or more.

Among the antioxidants, hindered phenols include, for example, C ₂₋ such as 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]. ₁₀ alkylene glycol-bis (mono or di t-butyl-hydroxyphenyl acylate); di- or trioxy C _2-4 alkylene glycol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ], Di- or trioxy _C2-4 alkylene glycol-bis (mono or di-t-butyl-hydroxy) such as triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] Phenyl acylate); glycerin-bis or tris [3- (3,5-di-t-butyl-4-hydroxyphene); C _3-8 alkanetriol-bis or tris (mono- or di-t-butyl-hydroxyphenyl acylate) such as nyl) propionate; pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4- C _4-8 alkanetetraol-bis to tetrakis (mono- or di-t-butyl-hydroxyphenyl acylate) such as hydroxyphenyl) propionate]. Examples of the hindered amines include tri- or tetra-C _1-3 alkylpiperidine or a derivative thereof, bis (tri-, tetra- or penta-C _1-3 alkylpiperidine) C _2-20 alkanedicarboxylic acid ester [for example, bis (2 , 2,6,6-tetramethyl-4-piperidyl) ogisalate, etc.], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl) -4-piperidyl) sebacate, 1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) ethane, phenylnaphthylamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, N, N'-diphenyl-1,4-phenylenediamine, N-phenyl-N'-cyclohexyl-1,4-phenylenediamine, etc. And the like.

  Among the additives, usually from antioxidants, heat stabilizers, processing stabilizers, weathering (light) stabilizers, impact modifiers, gloss control agents, slidability modifiers, colorants and fillers. At least one kind selected can be used. Moreover, each additive can also be used individually or in combination of 2 or more types.

  When a resin composition contains the said additive, the ratio of each additive can be selected from the following ranges. The proportion of the antioxidant may be about 0.001 to 5 parts by weight, preferably about 0.005 to 3 parts by weight (for example, 0.01 to 2 parts by weight) with respect to 100 parts by weight of the resin. The ratio of the heat stabilizer may be, for example, about 0.001 to 10 parts by weight, preferably about 0.001 to 5 parts by weight (particularly 0.01 to 2 parts by weight) with respect to 100 parts by weight of the resin. Good. The ratio of the processing stabilizer is, for example, 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably about 0.03 to 3 parts by weight with respect to 100 parts by weight of the resin. Also good. The proportion of the weathering (light) stabilizer is, for example, 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably about 0.1 to 2 parts by weight with respect to 100 parts by weight of the resin. There may be. The ratio of the impact modifier may be, for example, 0.1 to 30 parts by weight, preferably 0.5 to 25 parts by weight, and more preferably about 1 to 20 parts by weight with respect to 100 parts by weight of the resin. Good. The ratio of the gloss control agent is, for example, 0.01 to 30 parts by weight, preferably 0.02 to 10 parts by weight, and more preferably about 0.05 to 5 parts by weight with respect to 100 parts by weight of the resin. Also good. The ratio of the slidability improver may be, for example, about 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably about 3 to 20 parts by weight with respect to 100 parts by weight of the resin. The ratio of the colorant is, for example, about 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably about 0.2 to 2 parts by weight with respect to 100 parts by weight of the resin. Also good. The proportion of the filler may be, for example, 1 to 100 parts by weight, preferably 3 to 80 parts by weight, and more preferably about 5 to 50 parts by weight with respect to 100 parts by weight of the resin.

  The resin composition may be a powdery mixture or a molten mixture, and may be a resin (polyacetal resin or the like), the deodorant, and, if necessary, a deodorizing aid and / or other additive [stabilizer (oxidation Inhibitors, processing stabilizers, heat stabilizers, weathering (light) stabilizers), impact modifiers, gloss control agents, slidability improvers, colorants and / or fillers, etc.] in a conventional manner It can be prepared by mixing.

  The polyacetal resin composition composed of a deodorant (or a deodorant composition) and a polyacetal resin is particularly suitable for formaldehyde due to oxidation or thermal decomposition of the polyacetal resin in a molding process (particularly melt molding process). Generation can be remarkably suppressed, and the working environment can be improved. In addition, adhesion of decomposition products and additives to the mold (mold deposit) and exudation of decomposition products and additives from the molded product can be remarkably suppressed, and various problems associated with the molding process can be improved.

  Since the resin composition can efficiently deodorize the aldehyde odor, it is useful for use as a deodorant resin molded article. That is, this invention also includes the molded object formed with the resin composition (or deodorant resin composition) comprised with the said deodorizer (or deodorant composition) and the said resin.

  The deodorant (or deodorant composition) or deodorant resin composition (or molded product formed from the deodorant resin composition) of the present invention is (1) close to (in contact with) the aldehyde generation source. , Odor or odor can be efficiently removed (captured aldehyde).

  In addition, the kind in particular of an aldehyde production | generation source is not restrict | limited, For example, the chemical factory which uses aldehydes, the component which produces | generates an aldehyde odor (tobacco smoking source, resin which produces | generates an aldehyde, etc.), etc. are contained.

  The form of the deodorant, the deodorant composition, and the deodorant resin composition may be, for example, a solution, a dispersion, a powder, or the like, depending on the application or use form. The solution or the dispersion liquid resin composition may be a paint, printing ink, coating agent, adhesive, glue or the like.

  In the method (1) of bringing the aldehyde generation source close to the above, (i) the deodorant (deodorant composition or deodorant resin composition) may be brought close to the aldehyde generation source alone, An odorant may be applied to a substrate (including a molded product) to form a deodorant molded product, and the molded product may be brought close to an aldehyde generation source.

  In the use form (i), for example, the solution (or dispersion liquid) containing the deodorant may be coated or coated on at least a part of the surface of the aldehyde generation source, and the aldehyde generation source is added to the solution. It may be impregnated or immersed. Moreover, you may laminate | stack the deodorizing layer containing the said deodorizer on an aldehyde production | generation source by the lamination method etc. You may make the molded article formed with the deodorant resin composition adjoin to an aldehyde production | generation source. The form of the molded product formed with the deodorant resin composition is not particularly limited, and may be, for example, a granular material (pellet or the like), a fiber, a film (or sheet), a bag or a container (packaging material), or the like. May be. Among the molded products, the granular material can be prepared by, for example, kneading and extruding the constituents of the resin composition with an extruder, pelletizing or crushing the molten mixture, and the fibers can be doped or melted in the resin composition. It can be obtained by discharging the mixture from a nozzle and stretching it if necessary.

  In the use mode (ii), a solution containing the deodorant is coated or applied on the surface of the base material, the base material is impregnated with the solution, or the deodorant layer is laminated on the base material. Thus, deodorant property can be imparted to the base material, and the obtained deodorant base material can be shaped as necessary and brought close to the aldehyde generation source. Examples of the base material include paper and paper products (wallpaper, etc.), fibers and fiber products (nonwoven fabric, nonwoven fabric filters, etc.), synthetic resin molded products (films, sheets, etc.), wood and products thereof (decorative boards, plywood) And building materials such as particle boards), metals (metal plates, metal foils, etc.), ceramics, and the like. The substrate may be porous.

  In the above method (1), the aldehyde generation source itself is coated with the deodorant, or the deodorant is applied to a packaging or packaging material (wrapping paper, packaging bag, container, etc.) to package the aldehyde generation source. Or, packing can efficiently deodorize the aldehyde odor. For example, even when a thermoplastic resin (polyacetal resin pellets, etc.) at a high temperature is packed with the packing material, the aldehyde is efficiently captured and the space formed by the packing is prevented from filling the aldehyde. it can. Moreover, even if a molded product (deodorant powder) of a deodorant resin composition such as pellets is brought close to a resin (resin molded product, resin pellet, etc.) that generates aldehyde, it is very close to the source of generation. Since the deodorant can coexist, the aldehyde odor can be efficiently deodorized and aldehyde diffusion can be effectively prevented. In particular, when a resin pellet of the same series as the deodorant powder is used as the resin pellet for generating aldehyde, the deodorant powder can be used as it is without being separated or removed.

  The method (2) for containing the deodorant in the aldehyde production source is effective when the aldehyde production source is a resin that mainly produces aldehyde, and suppresses aldehyde production from the resin or the resin molded product. it can. In this method (2), a deodorant (deodorant composition or deodorant resin composition) and a resin that forms an aldehyde are mixed to form a resin composition, which may be further molded into a molded product or the like. . If necessary, the obtained resin composition or molded article may be brought into proximity (coating, coating, coexistence, etc.) to the aldehyde generation source.

  In the method (2), a deodorant (deodorant composition or deodorant resin composition) is mixed with a resin that generates an aldehyde, whereby a resin composition in which the generation of the aldehyde itself is significantly suppressed is obtained. Obtainable. Furthermore, when this resin composition is used, various molded products in which the generation of aldehydes is suppressed can be produced according to applications.

In addition, a molded article (molded article) formed of the polyacetal resin composition is excellent in extrusion and / or molding process stability, and generates very little formaldehyde. That is, a molded article made of a conventional polyacetal resin containing a stabilizer such as an antioxidant generates a relatively large amount of formaldehyde, and pollutes the living environment and the working environment in addition to corrosion and discoloration. For example, the amount of formaldehyde generated from a commercially available polyacetal resin molding is generally about ^{2 to 5} μg per 1 cm ^{2 of} surface area in a dry type (in a constant temperature dry atmosphere) and / or in a wet type (in a constant temperature and humid atmosphere), a surface area of 1 cm ^2. It is about 3 to 6 μg per unit.

On the other hand, since the polyacetal resin molded product (molded article) of the present invention contains a phosphorus compound or a salt thereof, the amount of formaldehyde generated can be effectively reduced. Specifically, in a dry process, the amount of formaldehyde generated is 1.5 μg or less (about 0 to 1.5 μg), preferably 1.0 μg or less (about 0 to 1.0 μg), more preferably 1 cm ² of the surface area of the molded product. It is about 0-0.6 micrograms, Usually, 0.001-1.0 microgram, Furthermore, about 0-0.1 microgram can also be achieved. Further, in the wet process, the amount of formaldehyde generated is 2.5 μg or less (about 0 to 2.5 μg) per 1 cm ² of the surface area of the molded product, preferably 0 to ² μg (for example, 0 to 1.2 μg), more preferably 0 to 0. It may be about 4 μg. In the present invention, the amount of formaldehyde generated in a wet process can be about 0 to 0.2 μg, and the amount generated is usually 1.2 μg or less (about 0 to 1.2 μg), particularly 0.001. It may be about 1.2 μg.

  The molded body of the present invention only needs to have the formaldehyde generation amount in either one of the dry type and the wet type, and in particular, often has the formaldehyde generation amount in both the dry type and the wet type. . The molded body of the present invention can also be used as a material that can cope with a more severe environment.

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

After the polyacetal resin molded product is cut as necessary and the surface area is measured, an appropriate amount of the molded product (for example, a surface area of 10 to 50 cm ² ) is put in a sealed container (capacity 20 mL) and heated at a temperature of 80 ° C. Leave for hours. Thereafter, 5 mL of water is injected into this sealed container, and the amount of formalin in this aqueous solution is determined according to JIS K0102, 29 (formaldehyde term) to determine the amount of formaldehyde generated (μg / cm ² ) per surface area of the molded product.

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

After the polyacetal resin molded product is cut as necessary and the surface area is measured, an appropriate amount of the molded product (for example, a surface area of 10 to 100 cm ² ) is covered with a sealed container (capacity 1 L) containing 50 mL of distilled water. It is hung and sealed and left in a thermostatic bath at a temperature of 60 ° C. for 3 hours. Then, it is allowed to stand at room temperature for 1 hour, and the amount of formalin in the aqueous solution in the sealed container is quantified according to JIS K0102, 29 (formaldehyde term) to determine the amount of formaldehyde generated (μg / cm ² ) per surface area of the molded product.

  In the present invention, the numerical definition of the amount of formaldehyde generated is a polyacetal resin composition containing conventional additives (ordinary stabilizers, mold release agents, etc.) as long as the polyacetal resin and the specific phosphorus compound or salt thereof are included. Most of the surface of the molded product (for example, 50 to 100%) is composed of a polyacetal resin not only for the molded product but also for a molded product of a composition containing an inorganic filler or other polymer. The present invention can also be applied to molded products (for example, multicolor molded products and coated molded products).

  The deodorant (deodorant composition) and deodorant composition of the present invention are used in close proximity to an aldehyde production source, such as packaging materials or packaging materials (paper, bags, containers, etc.), building materials (wallpaper). , Plywood, etc.), filters (nonwoven fabric filters, etc.), and powdered molded products such as resin pellets.

  Further, the resin composition of the present invention (particularly polyacetal resin composition) can be produced by a conventional molding method (for example, injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, etc. The method is useful for molding various molded articles.

  Further, the polyacetal resin molded product (molded product) of the present invention can be used for any application in which formaldehyde is harmful (for example, a knob, a lever, etc. as a bicycle component). Interior parts such as trunk openers, various switches and levers; Electrical system parts such as meters and connectors; In-vehicle electrical and electronic parts such as audio equipment and car navigation equipment; Parts that come into contact with metals such as carrier plates for window regulators; Door lock actuator parts, mirror parts, wiper motor system parts, mechanical parts such as fuel system parts, etc.) and electrical / electronic parts (active parts and passive parts, for example, parts or parts of equipment with many metal contacts ( For example, audio equipment, video camera Keyboards attached to any video equipment or OA (office automation) equipment such as copiers, facsimiles, computers, etc., and toys, telephones, computers, etc. that operate with driving force such as motors, specifically chassis (base) , Gears, levers, cams, pulleys, bearings, etc.], building materials and piping parts (lighting fixtures, fittings, piping, faucets, faucets, toilet peripheral parts, etc.), daily necessities (life), cosmetic parts, and medical (medical / treatment) ) Parts (fasteners, stationery, lip balm / lipstick containers, washers, water purifiers, spray nozzles, spray containers, aerosol containers, general containers, needle holders, etc.), food parts [eg tableware ( Containers, trays, spoons, etc.), food and cooking utensils (air rollers, mesh rollers, kitchen knives, etc.) ), Faucets (drinking water cocks, etc.), packages, cooking equipment parts (ice cream maker parts, etc.), freezer parts, washing machine parts (vegetable washing machine, dishwasher, bottle washing machine, etc.), dryer parts ( Tableware dryer, etc.), water purifier parts, pot parts, thermos parts, jar parts, mixer parts, etc.], photographic parts (camera parts, photographic film parts, etc.), etc. Also, optical and magnetic media Parts (for example, metal thin film type magnetic tape cassette, magnetic disk cartridge, magneto-optical disk cartridge, etc.), for example, metal tape cassette for music, digital audio tape cassette, 8 mm video tape cassette, floppy (registered trademark) disk cartridge, mini disk It can also be applied to cartridges.

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

  In Examples and Comparative Examples, the moldability (amount of mold deposit), the amount of formaldehyde generated from dry and wet molded products, and the leachability were evaluated as follows.

[Moldability (amount of mold deposit)]
A molded product of a specific shape (diameter 20 mm x thickness 1 mm) is continuously molded (100 shots) from a pellet formed of the polyacetal resin composition using a 30-ton injection molding machine, and the degree of mold deposits is evaluated in five stages. did. In addition, it means that there are few mold deposits, ie, there are few mold deposits, so that a numerical value is small.

[Formaldehyde generation amount from dry molded products]
Ten test pieces (2 mm × 2 mm × 50 mm) (total surface area of about 40 cm ² ) of resin samples are put in a sealed container (capacity 20 mL), heated at a temperature of 80 ° C. for 24 hours in a thermostatic chamber, and then cooled to room temperature. Distilled water (5 mL) was injected with a syringe. The amount of formaldehyde in this aqueous solution was quantified according to JISK0102, 29 (formaldehyde term), and the amount of formaldehyde gas generated per surface area (μg / cm ² ) was calculated.

[Formaldehyde generation amount and exudation properties from wet molded products]
^Two flat test pieces (100 mm × 40 mm × 2 mm; total surface area 85.6 cm ² ) are suspended and sealed on the lid of a polyethylene bottle (capacity 1 L) containing 50 mL of distilled water, and the temperature is 60 ° C. in a thermostatic bath. And left at room temperature for 1 hour. The amount of formalin in the aqueous solution in the polyethylene bottle was quantified according to JISK0102, 29 (formaldehyde term), and the amount of formaldehyde generated per surface area (μg / cm ² ) was calculated.

  Furthermore, the surface of the flat test piece (molded article) after the test was observed, and the degree of bleeding was evaluated according to the following criteria.

○: No seepage is observed Δ: Slight seepage is seen ×: Significant seepage is seen

Examples 1-11 and Comparative Examples 1-2
To 100 parts by weight of a polyacetal resin copolymer (melt index = 9 g / 10 min), as an antioxidant, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] 0.3 30 parts diameter twin screw extruder pre-blended with 0.1 parts by weight of calcium 12-hydroxystearate as a heat stabilizer and 0.2 parts by weight of ethylenebisstearylamide as a processing stabilizer and having one ventro The mixture was melted and mixed to prepare a pellet-like polyacetal composition.

  After externally adding the phosphorus compound (a) and, if necessary, the heat stabilizer (b) to 100 parts by weight of this polyacetal resin, a predetermined test piece is molded by an injection molding machine, and the moldability (mold Deposit), the amount of formaldehyde generated from the test piece and the exuding property were evaluated.

  As comparative examples, an example in which no specific phosphorus compound was included (Comparative Example 1) and an example in which only the heat stabilizer (b-1) was externally added without including the specific phosphorus compound (Comparative Example 2) were evaluated. The results are shown in Table 1.

Example 12
Polyacetal resin copolymer (melt index = 9 g / 10 min) 100 parts by weight, phosphorus compound (a-1) 0.1 part by weight, antioxidant triethylene glycol bis [3- (3-t-butyl- 5-methyl-4-hydroxyphenyl) propionate] 0.3 parts by weight, 0.1 parts by weight of calcium 12-hydroxystearate as a heat stabilizer, 0.3 parts by weight of benzoguanamine (b-6), ethylene bis as a processing stabilizer 0.2 parts by weight of stearyl amide was pre-blended, put into the main feed of a 30 mm diameter twin screw extruder having one ventro, and melt mixed to prepare a pellet-like polyacetal composition.

  A predetermined test piece was molded from this polyacetal resin by an injection molding machine, and the moldability (mold deposit), the amount of formaldehyde generated from the test piece and the exudation property were evaluated. The results are shown in Table 1.

Example 13
100 parts by weight of polyacetal resin copolymer (melt index = 9 g / 10 min), 0.1 part by weight of phosphorus compound (a-1), pentaerythritol tetrakis [3- (3,5-di-t-butyl) as an antioxidant -4-hydroxyphenyl) propionate], 0.3 parts by weight, 0.1 parts by weight of calcium 12-hydroxystearate as a heat stabilizer, 0.3 parts by weight of CTU-guanamine (b-7), and ethylene bis as a processing stabilizer 0.2 parts by weight of stearyl amide was pre-blended, put into the main feed of a 30 mm diameter twin screw extruder having one ventro, and melt mixed to prepare a pellet-like polyacetal composition.

  A predetermined test piece was molded from this polyacetal resin by an injection molding machine, and the moldability (mold deposit), the amount of formaldehyde generated from the test piece and the exudation property were evaluated. The results are shown in Table 1.

Example 14 and Comparative Example 3
1 g of phosphorus compound (a-1) as a deodorant was added to methanol to prepare a methanol solution having a phosphorus compound concentration of about 10% by weight. A polyester nonwoven fabric (10 cm × 10 cm) was impregnated with the methanol solution and dried.

  The obtained deodorant-impregnated nonwoven fabric was held on the middle plate of a glass desiccator (6 L) having an upper opening and a side opening, and the desiccator was filled with 20 ppm of formaldehyde gas and sealed. In this state, the desiccant was allowed to stand at 30 ° C. for 3 hours, and then the residual formaldehyde concentration in the desiccant was measured with a gas detector tube. The residual formaldehyde concentration was 0.05 ppm or less, and it was revealed that the phosphorus compound has a formaldehyde deodorizing and removing effect even when held in a nonwoven fabric.

  For comparison, the same operation as described above was performed using a non-impregnated polyester nonwoven fabric in the methanol solution, and the formaldehyde residual concentration was measured. As a result, the formaldehyde residual concentration was 18 ppm.

Example 15
1 g of phosphorus compound (a-6) as a deodorant was added to water to prepare an aqueous solution having a phosphorus compound concentration of about 10% by weight. A polyester nonwoven fabric (10 cm × 10 cm) was impregnated in the aqueous solution and dried.

  The obtained deodorant-impregnated non-woven fabric is held on the center plate of a glass desiccator (6L) having an upper opening and a side opening, and the desiccant overnight is filled with 20 ppm formaldehyde gas in the desiccator and sealed. After allowing to stand at 30 ° C. for 3 hours, the residual formaldehyde concentration in the desiccator was measured with a gas detector tube. The residual formaldehyde concentration was 0,05 ppm or less, and it became clear that the phosphorus compound had a formaldehyde deodorizing and removing effect even when held in a nonwoven fabric.

The phosphorus compounds and heat stabilizers used in the examples and comparative examples are as follows.
1. Phosphorus compound a
[Specific phosphorus compounds]
(A-1): 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (a-2): salt of (a-1) and melamine ((a-1) / melamine ( Molar ratio) = 1/1)
(A-3): salt of (a-1) and melamine ((a-1) / melamine (molar ratio) = 2/1)
(A-4): salt of (a-1) and melamine ((a-1) / melamine (molar ratio) = 3/1)
(A-5): 1,4-cyclooctylene phosphine oxide and 1,5-cyclooctylene phosphine oxide mixture (a-6): calcium hypophosphite Heat stabilizer (basic nitrogen compound) b
(B-1): Melamine (b-2): Sebacic acid dihydrazide (b-3): Allantoin (b-4): 5,5-dimethylhydantoin (b-5): Biurea (b-6): Benzoguanamine ( b-7): CTU-guanamine [Ajinomoto Fine Techno Co., Ltd.]

Claims (18)

  A deodorant for deodorizing an aldehyde odor, comprising a phosphorus compound having an active hydrogen atom or a salt thereof. The phosphorus compound is represented by the following formula (1) or (2)

(Wherein R ¹ and R ² are the same or different and are a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, a hetero atom-containing group which may have a substituent, or an organic group. R ¹ and R ² may be bonded to each other to form a ring with an adjacent phosphorus atom, and Y ¹ has an oxygen atom, a sulfur atom, a Se atom, a Te atom, or a substituent. An optional borane group.)
The deodorizer according to claim 1, which is a compound represented by the formula: The hydrocarbon group represented by R ¹ and R ² is an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group, and the heteroatom-containing group is a heterocyclic group or a group —OR ^{3. 3.} wherein R ³ represents a hydrogen atom, a hydrocarbon group or an acyl group, and the ring formed by R ¹ and R ² together with the adjacent phosphorus atom is a 4- to 20-membered hetero ring. Deodorant.   The deodorant according to claim 1 or 2, wherein the salt of the phosphorus compound is a metal salt, an ammonium salt, or a salt with a basic nitrogen-containing compound. The deodorizer according to claim 1, wherein the phosphorus compound is at least one of the compounds represented by the following formulas (1a), (1b), (2a), (2b) and (2c).

(Wherein R ¹ and R ² are the same or different and each has a hydrogen atom, an optionally substituted cycloalkyl, aryl or aralkyl group, hydroxyl group, alkoxy group, or substituent. An aryloxy group or an aralkyloxy group, wherein Y ¹ and Y ² are the same or different and each represents an oxygen atom or a sulfur atom, and rings Z ¹ and Z ² are the same or different, and a phosphorus atom is a constituent atom of the ring 4 to 10-membered ring is included, ring Z ³ is a 5- to 10-membered ring containing a phosphorus atom and atom Y ² as a constituent atom of the ring, and rings Z ⁴ and Z ⁵ are the same or different, 4 to 10-membered ring included as a constituent atom of the ring Z ^{1 to} Z ⁵ may have a substituent.   The deodorizer according to claim 1, wherein the phosphorus compound is at least one selected from phosphines, phosphine oxides, phosphinic acids and phosphonic acids.   A deodorant composition comprising the deodorant according to claim 1 and at least one deodorizing aid selected from a basic nitrogen-containing compound, a weak acid or a metal salt thereof, an alcohol, and an adsorptive inorganic compound.   The deodorant composition according to claim 7, comprising 0.01 to 10,000 parts by weight of a deodorizing aid with respect to 100 parts by weight of the deodorant.   A resin composition comprising at least the deodorant according to claim 1 and a resin.   The resin composition according to claim 9, wherein the resin is at least one selected from an olefin resin, a halogen-containing vinyl resin, a styrene resin, an acrylic resin, a polyester resin, and a polyurethane resin.   The resin composition of Claim 9 which contains 0.01-30 weight part of deodorizers with respect to 100 weight part of resin.   Furthermore, at least one selected from an antioxidant, a heat stabilizer, a processing stabilizer, a weather resistance (light) stabilizer, an impact resistance improver, a gloss control agent, a slidability improver, a colorant and a filler. The resin composition of Claim 9 or 10 containing.   A polyacetal resin composition comprising a polyacetal resin and at least the phosphorus compound or salt thereof according to claim 1.   Furthermore, at least one selected from an antioxidant, a heat stabilizer, a processing stabilizer, a weather resistance (light) stabilizer, an impact resistance improver, a gloss control agent, a slidability improver, a colorant and a filler. The resin composition according to claim 13.   The resin composition according to claim 13, wherein the pellet of the polyacetal resin and the master batch containing the phosphorus compound or salt thereof according to claim 1 coexist.   A polyacetal resin molded product formed of the resin composition according to claim 13. (1) When stored in a sealed space at a temperature of 80 ° C. for 24 hours, the amount of formaldehyde generated is 1.0 μg or less per 1 cm ² of surface area of the molded product and / or (2) stored in a sealed space at a temperature of 60 ° C. and saturated humidity for 3 hours. The molded product according to claim 16, wherein the amount of formaldehyde generated is 1.2 µg or less per 1 cm ² of surface area of the molded product.   The molded article according to claim 16, which is an automobile part, an electric / electronic part, a building material / piping part, a daily life part, a medical part, an office automation equipment part, an edible part or a photographic part.