Polyacetal resin composition

Abstract

The invention relates to a polyacetal resin composition. The purpose of the present invention is to provide a polyacetal resin composition which is capable of suppressing formaldehyde gas from a resin product during production, molding processing and molding processing, and which does not cause mold scale during molding processing, and which does not cause exudation of an additive from the resin product. The polyacetal resin composition according to the present invention is characterized by containing a polyacetal resin and a compound having at least one structure represented by formula (1). # imgabs0 # (1) (In formula (1), * 1 to * 4 represent bonding positions).

Description

Technical Field

[0001] The present invention relates to polyacetal resin compositions. Background Art

[0002] Polyacetal resin is a material with excellent rigidity, strength, toughness, sliding properties and creep properties. Polyacetal resin is used in a wide range of applications as a resin material for various mechanical parts such as automobile parts, electrical / electronic parts and industrial parts.

[0003] Polyacetal resin generates formaldehyde when it decomposes. In particular, there are concerns that formaldehyde gas generated during manufacturing and molding processing due to thermal decomposition may deteriorate the working environment, and that formaldehyde gas generated from resin products may deteriorate the indoor environment.

[0004] As a method for suppressing the generation of formaldehyde from polyacetal resin, a method of adding a formaldehyde-reactive substance is known. Polyacetal resin is easily decomposed by the action of acid, alkali, etc., and therefore, a formaldehyde scavenger having the effect of suppressing the release of formaldehyde without decomposing the polyacetal resin is required.

[0005] In addition, polyacetal resin is difficult to mix with other substances due to its very high crystallinity. In order to stabilize the performance of polyacetal resin for a long time, it is important to select additives that have good affinity with polyacetal resin and do not bleed out or aggregate under the use environment.

[0006] For example, when a large amount of conventionally known formaldehyde-reactive substances such as hydrazides, guanamines, ureas, and amides are added, mold deposits may occur during molding or bleed out under high temperature and high humidity conditions, and the generation of formaldehyde may not be sufficiently suppressed. Summary of the invention

[0007] Problems to be solved by the invention

[0008] The present invention has been completed in view of the above situation, and its purpose is to provide a polyacetal resin composition that can suppress formaldehyde gas during manufacturing, molding and from resin products, and does not generate mold deposits during molding, and does not cause additives to seep out of the resin products.

[0009] Means used to solve problems

[0010] Therefore, the present inventors have conducted intensive research and found that when a compound having a structure represented by the following formula (1) is added to a polyacetal resin, formaldehyde generated from the polyacetal resin can be well captured, and the amount of formaldehyde gas generated during manufacturing, molding and from resin products can be reduced. In addition, the compound having the above structure has good affinity with the polyacetal resin and is less likely to become mold deposit or bleed out, thereby completing the present invention.

[0011] That is, the present invention is as follows.

[0012] [1] A polyacetal resin composition comprising a polyacetal resin and a compound having at least one structure represented by the following formula (1).

[0013] ···(1)

[0014] (In formula (1), *1 to *4 represent bonding positions.)

[0015] [2] The polyacetal resin composition according to [1], wherein the polyacetal resin composition contains 0.01 mmol to 100 mmol of the compound based on 100 g of the polyacetal resin.

[0016] [3] The polyacetal resin composition according to [1] or [2], wherein in the compound, for a part or all of the structures contained in the compound, any two of the *1 to *4 in the structure are directly bonded to form a ring structure or are bonded via a connecting portion to form a ring structure.

[0017] [4] The polyacetal resin composition according to [1] or [2], wherein in the compound, for a part or all of the structure contained in the compound, the *3 and the *4 in the structure are directly bonded to form a ring structure or are bonded via a connecting portion to form a ring structure, and the connecting portion is an alkylene group which may be substituted or a heteroalkylene group which may be substituted.

[0018] [5] The polyacetal resin composition according to [1] or [2], wherein in the compound, for a part or all of the structures contained in the compound, the *3 and the *4 in the structure are directly bonded to form a ring structure or are bonded via a connecting portion to form a ring structure, the connecting portion is an alkylene group which may be substituted or a heteroalkylene group which may be substituted, and at least one of the *1 and the *2 in the structure is a hydrogen atom.

[0019] [6] The polyacetal resin composition according to [1] or [2], wherein the compound has one of the structures,

[0020] The *1 and the *2 are each independently a hydrogen atom, an alkyl group, a halogenated alkyl group, an aryl group or an ester group,

[0021] The *3 is a hydrogen atom, an alkyl group, a haloalkyl group, a thioalkyl group, an ether group or an alkoxy group,

[0022] The *4 is a hydrogen atom, an alkyl group, a thioalkyl group, an aryl group, a heteroaryl group, an amino group, an aminoalkyl group, an ether group or an alkoxy group.

[0023] [7] The polyacetal resin composition according to [6], wherein at least one of the *1 and the *2 in the structure is a hydrogen atom.

[0024] [8] The polyacetal resin composition according to [1] or [2], wherein the compound has two or more of the structures, and any one of *1 to *4 in the different structures is bonded directly or via a linker.

[0025] [9] The polyacetal resin composition according to [1] or [2], wherein the compound has two or more of the structures, and the *4 in different structures are bonded to each other via a linker, and the linker is a structure containing at least one selected from the group consisting of an ether group that may be substituted, a thioether group that may be substituted, an ester group that may be substituted, and an alkylene group that may be substituted.

[0026]

[10] The polyacetal resin composition according to [1] or [2], wherein the compound has two or more of the structures, the *4 in different structures are bonded to each other via a linker, and the linker is a structure containing at least one selected from the group consisting of an ether group that may be substituted, a thioether group that may be substituted, an ester group that may be substituted, and an alkylene group that may be substituted,

[0027] The *1 and *2 are each independently a hydrogen atom, an alkyl group, a halogenated alkyl group, an aryl group or an ester group.

[0028] The *3 is a functional group of a hydrogen atom, an alkyl group which may be substituted, a haloalkyl group which may be substituted, a thioalkyl group which may be substituted, or an alkoxy group which may be substituted.

[0029]

[11] The polyacetal resin composition according to [1] or [2], excluding the case where the compound is a compound in which, in all the structures contained in the compound, the nitrogen atom in formula (1) and the carbon atom at the α-position of the carbonyl group form a 6-membered aromatic ring.

[0030]

[12] The polyacetal resin composition according to [1] or [2], excluding the case where the compound is uracil.

[0031]

[13] A method for suppressing formaldehyde release from a polyacetal resin, comprising mixing the polyacetal resin with a compound having at least one structure represented by the following formula (1).

[0032] ···(1)

[0033] (In formula (1), *1 to *4 represent bonding positions.)

[0034]

[14] Use of a compound having at least one structure represented by the following formula (1) for suppressing formaldehyde emission from a polyacetal resin.

[0035] ···(1)

[0036] (In formula (1), *1 to *4 represent bonding positions.)

[0037] Effects of the Invention

[0038] Since the polyacetal resin composition of the present invention has the above-mentioned structure, formaldehyde gas can be suppressed during production, and mold deposits are not generated during molding processing, and additives do not bleed out from the resin product. DETAILED DESCRIPTION

[0039] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") is described in detail. It should be noted that this embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment. That is, the present invention can be modified in various ways without departing from the scope of the present invention.

[0040] [Polyacetal resin composition]

[0041] The polyacetal resin composition of the present embodiment contains a polyacetal resin and a compound having at least one structure represented by the following formula (1).

[0042] ···(1)

[0043] (In formula (1), *1 to *4 represent bonding positions.)

[0044] The polyacetal resin composition of the present embodiment may be a composition consisting only of the above-mentioned compound and the above-mentioned polyacetal resin, or may further contain other components.

[0045] In addition, in this specification, a compound having at least one structure represented by formula (1) may be simply referred to as a “compound.” In addition, a structure represented by formula (1) may be simply referred to as a “structure.”

[0046] The above structure can be E-type or Z-type.

[0047]

[0048] When a plurality of the above structures are included, all of them may be either the E type or the Z type, or both the E type and the Z type may be included.

[0049] When two of the above structures are included, they may be bilaterally symmetrical or asymmetrical.

[0050]

[0051]

[0052] In the above structure, *1 to *4 in the structure may be bonded to each other to form a ring.

[0053]

[0054] Furthermore, when a plurality of the above structures are included, any of *1 to *4 in different structures may be bonded to each other to form a ring.

[0055] <Compound>

[0056] The number of the above structure contained in the above compound may be 1, 2, 3, 4, or 5. Among them, from the viewpoint of further suppressing the release of formaldehyde, the number is preferably 2 or less, and more preferably 1.

[0057] The above structures contained in the above compounds may be the same structure or different structures.

[0058] Examples of the *1 and *2 include a hydrogen atom, an alkyl group, a halogenated alkyl group, an aryl group, and an ester group.

[0059] Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms (preferably alkyl groups having 1 to 5 carbon atoms, and more preferably alkyl groups having 1 to 2 carbon atoms) such as methyl and ethyl groups. The alkyl group may be linear or branched. Examples of the halogenated alkyl group include chloroethyl groups.

[0060] Examples of the aryl group include phenyl, phenylmethyl, dichlorophenyl, 2-chloro-5-nitrophenyl, naphthyl, anthracenyl, phenanthrenyl, and pyrenyl.

[0061] Examples of the ester group include a 2-methyl-1-oxopropyl group and a 1,1-dimethylethylaminocarbonyl group.

[0062] Examples of the *3 include a hydrogen atom, an optionally substituted alkyl group, a halogenated alkyl group, a thioalkyl group, an ether group (for example, a monovalent group containing an ether group such as an alkyl ether group), and an alkoxy group.

[0063] Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms (preferably alkyl groups having 1 to 5 carbon atoms, and more preferably alkyl groups having 1 to 2 carbon atoms) such as methyl and ethyl groups. The alkyl group may be linear or branched. The alkyl group may be substituted to have an ether structure or an ester structure. For example, it may have an ester structure like 3-[(2-chloroethyl)amino]-2-pentenedioic acid 1,5-dimethyl ester, or it may have an ether structure like 3-amino-4-[2-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)ethoxy]-2-butenoic acid ethyl ester.

[0064] Examples of the halogen in the halogenated alkyl group include fluorine, chlorine, bromine, and iodine, preferably fluorine and bromine, and examples of the alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms (preferably alkyl groups having 1 to 5 carbon atoms, and more preferably alkyl groups having 1 to 2 carbon atoms), such as methyl and ethyl groups. Among them, trifluoromethyl and the like are preferred.

[0065] The thioalkyl group may have 1 to 10 carbon atoms, or 1 to 5 carbon atoms.

[0066] Examples of the alkoxy group include a structure in which an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 5 carbon atoms) is bonded to an oxygen atom.

[0067] Examples of the *4 include a hydrogen atom, an alkyl group, a thioalkyl group, an optionally substituted aryl group, a heteroaryl group, an amino group, an aminoalkyl group, an ether group (for example, a monovalent group containing an ether group such as an alkyl ether group), and an optionally substituted alkoxy group.

[0068] Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms (preferably alkyl groups having 1 to 5 carbon atoms), such as methyl and ethyl groups. The alkyl group may be linear or branched.

[0069] The thioalkyl group may have 1 to 10 carbon atoms, or 1 to 5 carbon atoms.

[0070] Examples of the aryl group include phenyl, naphthyl, anthryl, phenanthrenyl, pyrenyl, etc. The aryl group may be substituted in the form of N-[3-[3-(dimethylamino)-1-oxo-2-propenyl]phenyl]-N-methylacetamide, N-[3-[3-(dimethylamino)-1-oxo-2-propenyl]phenyl]-N-ethylacetamide, or N-[3-[3-(dimethylamino)-1-oxo-2-propen-1-yl]phenyl]acetamide.

[0071] Examples of the heteroaryl group include groups having a heteroatom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.) between carbon atoms of the aryl group, and examples thereof include a pyridyl group and a thienyl group.

[0072] The aminoalkyl group may have 1 to 10 carbon atoms, or 1 to 5 carbon atoms.

[0073] Examples of the alkoxy group include a structure in which an alkyl group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 10 carbon atoms) is bonded to an oxygen atom. The alkoxy group may be substituted to have an ether structure like 2-methoxyethyl 3-amino-2-butenoate, may be substituted to have a hydroxyl group like 4-hydroxybutyl 3-amino-2-butenoate, or may have a substituted amino group like 2-[methyl(phenylmethyl)amino]ethyl 3-amino-2-butenoate or 2-[4-(diphenylmethyl)-1-piperazinyl]ethyl 3-amino-2-butenoate.

[0074] Examples of the above compounds include 3-(dimethylamino)-2-propenal, 4-amino-3-penten-2-one, 3-amino-2-butenoic acid methyl ester, 3-amino-2-butenoic acid ethyl ester, 3-amino-2-butenoamide, 3-(dimethylamino)ethyl acrylate, 3-amino-2-butenoic acid 1-methylethyl ester, 3-(ethylamino)-2-propenoic acid ethyl ester, 3-amino-2-butenoic acid 2-methoxyethyl ester, 3-amino-2-butenoic acid 4-hydroxybutyl ester, 3-(methylphenylamino)-2-propenal, 3-amino-2-butenoic acid 2-methylpropyl ester, 3-(dimethylamino)-2-butenoic acid 2-methylpropyl ester, Ethyl butylene oxide, 3-amino-2-butylene oxide tetradecyl ester, 3-dimethylamino-1-(3-pyridyl)-2-propene-1-one, 3-amino-2-butylene oxide hexadecyl ester, 3-amino-2-butylene oxide octadecyl ester, N-methyl-3-(methylamino)-2-butylene oxide, 3-dimethylamino-1-(2-pyridyl)-2-propene-1-one, 3-(dimethylamino)-1-(2-thienyl)-2-propene-1-one, 3-amino-4,4,4-trifluoro-2-butylene oxide ethyl ester, 4,4,4-trifluoro-3-(methylamino)-2-butylene oxide ethyl ester, 3 -(phenylamino)-2-butenoic acid ethyl ester, 3-[(2-chloroethyl)amino]-2-pentaconedioic acid 1,5-dimethyl ester, 3-amino 2-butenoic acid 2-[methyl(phenylmethyl)amino]ethyl ester, 3-[(2-methyl-1-oxopropyl)amino]-2-butenamide, 3-ethoxy-3-iminopropionic acid ethyl ester, 3-[[[(1,1-dimethylethyl)amino]carbonyl]amino]-2-butenoic acid methyl ester, N-[3-[3-(dimethylamino)-1-oxo-2-propenyl]phenyl]-N-methylacetamide, N-[3-[3-(dimethylamino)-1 Compounds in which the above structures do not form a ring structure, such as N-[3-[3-(dimethylamino)-1-oxo-2-propen-1-yl]phenyl]acetamide, 3-ethoxy-3-iminopropionic acid phenyl ester, 3-[(2-chloro-5-nitrophenyl)amino]-3-ethoxy-2-propenoic acid ethyl ester, 3-amino-2-butenoic acid 2-[4-(diphenylmethyl)-1-piperazinyl]ethyl ester, 3-amino-4-[2-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)ethoxy]-2-butenoic acid ethyl ester;4-(1-pyrrolidinyl)-3-butene-2-one, 4-(1-pyrrolidinyl)-3-pentene-2-one, 4-methyl-1-(4-morpholinyl)-1-pentene-3-one, 2-(formylmethylene)-1,3,3-trimethylindoline, ethyl 2-(3-ethyl-4-oxo-2-thiazolidinylidene)acetate, 1-(3-ethyl-2(3H)-benzothiazolylidene)-2-propanone, 1,2-dihydro-2-phenyl-3H-pyrazol-3-one, 2-(3-methyl-2(3H)-benzothiazolylidene)-1-phenylethanone, 3-amino-2-cyclohexen-1-one, 3-amino- Compounds having a ring structure formed by the above structures, such as 5-methyl-2-cyclohexene-1-one, 3-amino-5,5-dimethyl-2-cyclohexene-1-one, 3-(dimethylamino)-2-cyclohexene-1-one, 3-(dimethylamino)-5,5-dimethyl-2-cyclohexene-1-one, 5-amino-2H-pyran-3(6H)-one, 3-aminocyclopentene-1-one, 2,3-dihydro-4(1H)-pyridone, 4-amino-5-methyl-2(1H)-pyridone, and uracil; 1,2-ethylenebis(3-amino-2-butenoic acid) ester, 1,4-butylene 1,1'-bis(3-amino- 2-Butenoic acid) ester, 1-methyl-1,3-propylene bis(3-amino-2-butenoic acid) ester, thiobis(2,1-ethylene) 1,1'-bis(3-amino-2-butenoic acid) ester, oxybis(1-methyl-2,1-ethylene) bis(3-amino-2-butenoic acid) ester, N,N'-1,6-hexamethylenebis[3-amino-2-butenamide], 4-([3-[(3-oxo-1-buten-1-yl)amino]propyl]amino)-3-butene-2-one, 4,4'-(1,2-ethylenediimino)bis[3-penten-2-one], 4,4'-(1,6-hexamethylenediimino)bis[3-penten-2-one] Compounds having multiple structures of the above structures, such as 1,2-diamino)bis[3-penten-2-one], 4,4'-[(1-methyl-1,2-ethylidene)diimino]bis[3-penten-2-one], 2,12-diamino-2,11-tridecadiene-4,10-dione, 1,6-amino-1,6-diethoxy-1,5-hexadiene-3,4-dione, 5-amino-3-oxo-4-hexenoic acid 4-amino-2-oxo-3-penten-1-yl ester, 1-ethyl-1,2-ethylidene bis(3-amino-2-butenoic acid) ester, and 1,4-butylene 1,1'-bis(3-amino-2-butenoic acid) ester. ;

[0075] Examples of the compound in which the above structure does not form a ring structure include the compound (b) described later.

[0076] Examples of the compound in which the above structure forms a ring structure include the compound (a) described below.

[0077] Examples of the compound having a plurality of the above structures include the compound (c) described below.

[0078] From the viewpoint of further suppressing formaldehyde emission, the above compound is preferably a compound in which the above structure forms a ring structure. Among them, from the viewpoint of particularly excellent suppression of formaldehyde emission, a compound in which *1 and *2 are both hydrogen atoms and the above structure forms a ring structure is preferred, and 3-amino-2-cyclohexene-1-one, 3-amino-5-methyl-2-cyclohexene-1-one, and 3-amino-5,5-dimethyl-2-cyclohexene-1-one are more preferred.

[0079] Among the compounds having the above structures not forming a ring structure, from the viewpoint of suppressing the amount of formaldehyde emission, compounds having the above structures in which either *1 or *2 is a hydrogen atom are preferred, and compounds in which both *1 and *2 are hydrogen atoms are more preferred.

[0080] From the viewpoint of being able to suppress bleeding even under high temperature and high humidity, the compound is preferably a compound having a plurality of the above structures.

[0081] As the above-mentioned compound, preferably:

[0082] (a) a compound in which, with respect to a part or all of the above structures contained in the compound, any two of the above *1 to the above *4 in one of the above structures are directly bonded to each other to form a ring structure or are bonded to each other via a linker to form a ring structure;

[0083] (b) a compound having one of the above structures, wherein *1 and *2 are each independently a hydrogen atom, an alkyl group, a haloalkyl group, an aryl group, or an ester group, *3 is a hydrogen atom, an alkyl group, a haloalkyl group, a thioalkyl group, an ether group (for example, a monovalent group containing an ether group such as an alkyl ether group), or an alkoxy group, and *4 is a hydrogen atom, an alkyl group, a thioalkyl group, an aryl group, a heteroaryl group, an amino group, an aminoalkyl group, an ether group (for example, a monovalent group containing an ether group such as an alkyl ether group), or an alkoxy group;

[0084] (c) A compound having two or more of the above structures, in which any one of *1 to *4 in the above different structures is bonded directly or via a linker.

[0085] In addition, in this specification, the compounds (a), (b), and (c) mentioned above may be referred to as compound (a), compound (b), and compound (c), respectively.

[0086] (Compound (a))

[0087] The compound (a) preferably has one of the above structures.

[0088] In the above compound (a), any two of the above *1 to the above *4 in one of the above structures are directly bonded to each other to form a ring structure or are bonded to each other via a linker to form a ring structure, preferably *1 or *2 and *4 form a ring structure or *3 and *4 form a ring structure. More preferably, *3 and *4 form a ring structure.

[0089] The number of the above-mentioned ring structure is preferably one.

[0090] The ring structure of the compound (a) is preferably formed via a linking group. Examples of the linking group include an alkylene group which may be substituted (e.g., an alkylene group having 1 to 10 carbon atoms) and an alkylene group which may be substituted (e.g., an alkylene group having 1 to 10 carbon atoms and containing a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom between bonds).

[0091] The above-mentioned alkylene group may be linear or branched.

[0092] Here, examples of the substituent include an alkyl group having 1 to 10 carbon atoms.

[0093] The above-mentioned ring structure may be a ring structure formed by bonding the above-mentioned *3 and the above-mentioned *4 via a linking group. In this case, the above-mentioned linking group is preferably a straight-chain or branched alkylene group having 2 to 5 carbon atoms, or a heteroalkylene group in which one carbon atom of the alkylene group having 2 to 5 carbon atoms is replaced by a heteroatom, and more preferably a straight-chain or branched alkylene group having 2 to 5 carbon atoms.

[0094] The ring structure may be a ring structure in which the *1 or *2 is bonded to the *4 via a linking group. In this case, the linking group is preferably a linear alkylene group having 2 to 5 carbon atoms.

[0095] In the compound (a), it is preferred that at least one of the *1 and *2 that do not form the ring structure is a hydrogen atom, and it is more preferred that all of the *1 and *2 that do not form the ring structure are hydrogen atoms.

[0096] (Compound (b))

[0097] The compound (b) has one of the above structures.

[0098] The compound (b) preferably does not have a ring structure formed by two of the above *1 to *4 being directly bonded to each other or a ring structure formed by two of the above *1 to *4 being bonded to each other via a linker.

[0099] The *1 and *2 of the compound (b) may be the same or different, but are preferably the same from the viewpoint of further suppressing the generation of formaldehyde gas.

[0100] In the compound (b), *1 and *2 are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. From the viewpoint of further suppressing the generation of formaldehyde gas, it is preferred that at least one of *1 and *2 is a hydrogen atom, and it is more preferred that both *1 and *2 are hydrogen atoms.

[0101] In the compound (b), *3 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is more preferably an alkyl group having 1 to 5 carbon atoms from the viewpoint of further suppressing the generation of formaldehyde gas.

[0102] In the above compound (b), the above *4 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a heteroaryl group having 5 to 8 carbon atoms and having a nitrogen atom, an amino group, or an alkoxy group having 1 to 5 carbon atoms.

[0103] From the viewpoint of obtaining excellent effects by adding a small amount, the compound (b) is preferably a compound in which *1 and *2 are both hydrogen atoms, *3 is an alkyl group having 1 to 5 carbon atoms (preferably an alkyl group having 1 to 2 carbon atoms), and *4 is an alkoxy group having 1 to 5 carbon atoms (preferably an alkoxy group having 1 to 2 carbon atoms).

[0104] (Compound (c))

[0105] The compound (c) preferably has two or more structures, more preferably two structures. For example, the two structures may be directly bonded or bonded via a divalent linker, or the three structures may be directly bonded or bonded via a trivalent linker.

[0106] The compound (c) preferably does not have a ring structure (for example, a ring structure formed by directly bonding any two of the above *1 to the above *4 to each other in one of the above structures or a ring structure formed by bonding any two of the above *1 to the above *4 to each other via a connecting portion, or a ring structure formed by directly bonding any two of the above *1 to the above *4 to each other in two different structures or via a connecting portion).

[0107] From the viewpoint of further suppressing the generation of formaldehyde gas, in the compound (c), preferably, the *1, *2, *3, and *4 of two different structures are directly bonded to each other or bonded via a connecting portion, and more preferably, the *4 of two different structures are directly bonded to each other or bonded via a connecting portion. The two structures are preferably identical in *1 to *3.

[0108] The linking portion is preferably an alkylene group which may be substituted (e.g., an alkylene group having 1 to 10 carbon atoms), ether (—O—), thioether (—S—), ester (—C(═O)O—), or a combination thereof. From the viewpoint of further suppressing the generation of formaldehyde gas, it is preferred that the above *4 of two structures above are both bonded to ether (—O—), and only an alkylene group which may be substituted (e.g., an alkylene group having 1 to 10 carbon atoms), thioether (—S—), or a combination thereof is sandwiched between the two ethers. It is more preferred that the above *4 of two structures above are both bonded to ether (—O—), and only an alkylene group which may be substituted (e.g., an alkylene group having 1 to 10 carbon atoms) is sandwiched between the two ethers.

[0109] Here, examples of the substituent include an alkyl group having 1 to 10 carbon atoms.

[0110] In the above structure of the above compound (c), the above *1 and the above *2 are preferably a hydrogen atom, an alkyl group, a halogenated alkyl group, an aryl group, an ester group or a combination thereof, and more preferably a hydrogen atom, an alkyl group, an aryl group or an ester group. In all of the above structures, the above *1 and the above *2 are preferably a hydrogen atom.

[0111] Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms (preferably alkyl groups having 1 to 5 carbon atoms), such as methyl and ethyl groups. The alkyl group may be linear or branched.

[0112] Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthrenyl group, and a pyrenyl group.

[0113] Examples of the ester group include a 2-methyl-1-oxopropyl group and a 1,1-dimethylethylaminocarbonyl group.

[0114] The *3 in the structure of the compound (c) is preferably a hydrogen atom, an alkyl group which may be substituted, a haloalkyl group which may be substituted, a thioalkyl group which may be substituted, an alkoxy group which may be substituted, or a combination thereof, and more preferably a hydrogen atom, an alkyl group which may be substituted, a haloalkyl group which may be substituted, a thioalkyl group which may be substituted, or an alkoxy group which may be substituted.

[0115] Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms (preferably alkyl groups having 1 to 5 carbon atoms), such as methyl and ethyl groups. The alkyl group may be linear or branched.

[0116] Examples of the halogen in the halogenated alkyl group include fluorine, chlorine, bromine and iodine, and examples of the alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms (preferably alkyl groups having 1 to 5 carbon atoms) such as methyl and ethyl groups.

[0117] The thioalkyl group may have 1 to 10 carbon atoms, or 1 to 5 carbon atoms.

[0118] Examples of the alkoxy group include a structure in which an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 5 carbon atoms) is bonded to an oxygen atom.

[0119] The two *3 in the structure of the compound (c) are preferably alkyl groups having 1 to 10 carbon atoms (preferably alkyl groups having 1 to 5 carbon atoms), such as methyl and ethyl groups. The alkyl groups may be linear or branched.

[0120] Examples of the substituent of the alkyl group, halogenated alkyl group and thioalkyl group include an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group and a halogen atom.

[0121] From the viewpoint of being able to further suppress the generation of formaldehyde gas, the above-mentioned compound is preferably a compound other than uracil, more preferably a compound other than uracil which may be substituted with an alkyl group having 1 to 5 carbon atoms, further preferably a compound other than a compound in which all of the above-mentioned structures contained in the above-mentioned compound comprise a six-membered aromatic ring between the nitrogen atom in formula (1) and the carbon atom at the α-position of the carbonyl group, and particularly preferably a compound other than a compound in which all of the above-mentioned structures contained in the above-mentioned compound comprise a six-membered aromatic ring between the nitrogen atom in formula (1) and the carbon atom at the α-position of the carbonyl group.

[0122] <Polyacetal resin>

[0123] Examples of the polyacetal resin include polyacetal homopolymers and polyacetal copolymers. The polyacetal resin may be used alone or in combination of two or more.

[0124] The polyacetal homopolymer is not particularly limited, and examples thereof include: a polyacetal homopolymer substantially composed of only oxymethylene units obtained by polymerizing a formaldehyde monomer or a cyclic oligomer of formaldehyde such as a trimer (trimethoxymethylene) or a tetramer (tetramethoxymethylene). In addition, as the polyacetal homopolymer, for example, a polyacetal homopolymer having a block component obtained by polymerizing a formaldehyde monomer or a cyclic oligomer of formaldehyde in the presence of a compound having a functional group such as a hydroxyl group at both ends or one end, for example, a polyalkylene glycol, can also be used.

[0125] The polyacetal copolymer is not particularly limited, and for example, a polyacetal copolymer obtained by copolymerizing a cyclic oligomer of formaldehyde such as a formaldehyde monomer or a trimer thereof (trimethoxymethylene) or a tetramer (tetramethoxymethylene) with a diol such as ethylene oxide, propylene oxide, epichlorohydrin, 1,3-dioxolane, 1,4-butanediol formal, a cyclic ether such as a cyclic formal of a glycol, and / or a cyclic formal can be cited as a representative example. In addition, as a polyacetal copolymer, for example, a polyacetal copolymer having a block component obtained by copolymerizing a formaldehyde monomer or a cyclic oligomer of formaldehyde with a cyclic ether and / or a cyclic formal in the presence of a compound having a functional group such as a hydroxyl group at both ends or one end, for example, hydrogenated polybutadiene diol can also be used. Furthermore, as the polyacetal copolymer, for example, a polyacetal copolymer having a branch obtained by copolymerizing a monofunctional glycidyl ether or a polyacetal copolymer having a crosslinked structure obtained by copolymerizing a polyfunctional glycidyl ether can also be used.

[0126] When the polyacetal resin contains a polyacetal copolymer, it is preferable to use trioxymethylene, which is a trimer of formaldehyde, for copolymerization of the polyacetal copolymer.

[0127] As a polymerization catalyst for the polymerization of the polyacetal copolymer, it is preferred to use a cationic active catalyst such as a Lewis acid, a protonic acid, and its ester or anhydride. Examples of the Lewis acid include halides of boron, tin, titanium, phosphorus, arsenic, and antimony, and specifically, boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride, antimony pentafluoride, and complexes or salts thereof. In addition, specific examples of the protonic acid, its ester or anhydride include perchloric acid, trifluoromethanesulfonic acid, tert-butyl perchlorate, acetyl perchlorate, trimethylolsulfonic acid, t-butyl perchlorate ... Hexafluorophosphate, etc.

[0128] The polymerization method of the polyacetal copolymer is not particularly limited, and is usually carried out by bulk polymerization, either intermittently or continuously. As the polymerization apparatus used, a self-cleaning extrusion mixer such as a co-kneader, a twin-screw continuous extrusion mixer, or a twin-screw paddle continuous mixer is used, and the molten monomer is supplied to the polymerization machine to obtain a solid block of the polyacetal copolymer as the polymerization proceeds.

[0129] From the viewpoint of further suppressing the generation of formaldehyde gas, the MFR of the polyacetal resin is preferably 1 (g / 10 min) to 50 (g / 10 min).

[0130] In addition, MFR can be measured by the method described in Examples mentioned later.

[0131] The mass ratio of the polyacetal resin relative to 100 mass % of the polyacetal resin composition of the present embodiment is preferably 80 mass % or more, more preferably 90 mass % or more, and further preferably 95 mass % or more. In addition, it can be 95 mass % or less, 99 mass % or less, and can also be less than 100 mass %.

[0132] The mass ratio of the above compound relative to 100 mass % of the polyacetal resin composition of the present embodiment is preferably greater than 0 mass % and 20 mass % or less, more preferably 0.01 mass % to 10 mass %, and further preferably 0.05 mass % to 3 mass %.

[0133] The total mass ratio of the polyacetal resin and the compound is preferably 95 mass % or more, more preferably 97 mass % or more, and further preferably 100 mass % relative to 100 mass % of the polyacetal resin composition of the present embodiment.

[0134] The mass ratio of the polyacetal resin relative to 100 mass % of the resin component contained in the polyacetal resin composition of the present embodiment is preferably 70 mass % or more, more preferably 90 mass % or more, and further preferably 100 mass %.

[0135] In the polyacetal resin composition of the present embodiment, the molar ratio of the compound is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and even more preferably 0.3 to 20 mmol, relative to 100 g of the polyacetal resin.

[0136] The amount of formaldehyde generated by the polyacetal resin composition of the present embodiment is preferably less than 15 mg / kg, more preferably 10 mg / kg or less.

[0137] In addition, the amount of formaldehyde generation can be measured by the method described in Examples described later.

[0138] The polyacetal resin composition of the present embodiment can be produced by, for example, a known melt-kneading method.

[0139] For example, the polyacetal resin and the compound may be mixed using a stirrer such as a Henschel mixer, and then supplied to a single-screw or twin-screw melt-kneading device (extruder) for melt-kneading. Alternatively, the polyacetal resin may be supplied from the upstream of the single-screw or twin-screw extruder to be molten, and then the compound may be supplied from the downstream of the single-screw or twin-screw extruder for melt-kneading.

[0140] The polyacetal resin composition of the present embodiment can be used as a raw material for molded products and can be used even if molded into any shape, for example, it can be used for injection molded products, fibers and nonwoven fabrics, sheets and films, and special-shaped extruded products.

[0141] [Method for inhibiting formaldehyde release from polyacetal resin]

[0142] The above-mentioned compound can capture formaldehyde generated from the polyacetal resin.

[0143] The method for suppressing formaldehyde emission from a polyacetal resin according to the present embodiment includes mixing the above-mentioned compound with the polyacetal resin.

[0144] For example, when the polyacetal resin and the compound are mixed to form a polyacetal resin composition and then molded, the compound captures formaldehyde gas generated by decomposition of the polyacetal resin during molding, thereby suppressing the amount of formaldehyde gas generated.

[0145] In the method for suppressing formaldehyde release from a polyacetal resin of the present embodiment, the molar ratio of the compound is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and even more preferably 0.3 to 20 mmol, relative to 100 g of the polyacetal resin.

[0146] [How to use the compound]

[0147] The method of using the compound of the present embodiment is a method of using the compound for suppressing formaldehyde release from a polyacetal resin. The method of using the compound of the present embodiment may be the method of using the compound described above.

[0148] The compound in the method of using the compound of the present embodiment refers to the above-mentioned compound contained in the polyacetal resin composition of the present embodiment described above.

[0149] In the method of using the compound of this embodiment, the compound is used in an amount of preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and even more preferably 0.3 to 20 mmol, based on 100 g of the polyacetal resin.

[0150] Example

[0151] Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

[0152] The raw material components used in Examples and Comparative Examples are as follows.

[0153] (Polyacetal resin)

[0154] Copolymer

[0155] A polyacetal resin copolymer (MFR=9.0 g / 10 minutes) obtained by copolymerizing trioxymethylene and 1,3-dioxolane (4.2 mol % relative to the resin) was used.

[0156] The MFR value was measured in accordance with ISO 1133-1 using MELT INDEXER manufactured by Toyo Seiki Co., Ltd. at a cylinder temperature of 190° C. and a load of 2.16 kg.

[0157] Homopolymer

[0158] A polyacetal resin homopolymer obtained by polymerizing formaldehyde (MFR=20.0 g / 10 minutes) was used. The MFR value was measured in accordance with ISO 1133-1 using a MELT INDEXER manufactured by Toyo Seiki Co., Ltd. at a cylinder temperature of 190° C. and a load of 2.16 kg.

[0159] (Compound)

[0160] B1: 3-(dimethylamino)-2-propenal (Tokyo Chemical)

[0161] B2: 3-Dimethylamino-1-(3-pyridyl)-2-propen-1-one (Santa Cruz Biotechnology, Inc.)

[0162] B3: 3-(Methylphenylamino)-2-propenal (Santa Cruz Biotechnology, Inc.)

[0163] B4: 3-(Ethylamino)-2-propenoic acid ethyl ester (Alfa Chemistry)

[0164] B5: 4-amino-3-penten-2-one (Tokyo Chemical)

[0165] B6: 3-amino 2-butenoic acid methyl ester (Tokyo Chemical)

[0166] B7: 3-amino 2-buteneamide (Angene Chemical)

[0167] B8: 3-amino 2-butenoic acid 1-methylethyl ester (Tokyo Chemical)

[0168] B9: 3-amino-4,4,4-trifluoro-2-butenoic acid ethyl ester (Tokyo Chemical)

[0169] B10: 1,4-butylene 1,1'-di(3-amino-2-butenoic acid) ester (Tokyo Chemical)

[0170] B11: Di(2,1-ethylene)1,1'-di(3-amino-2-butenoic acid)thioate (Finetech Industry)

[0171] B12: 1-Methyl-1,3-propylene di(3-amino-2-butenoic acid) ester (Alfa Chemistry)

[0172] B13: 3-amino-2-cyclohexene-1-one (Tokyo Chemical)

[0173] B14: 3-amino-5-methyl-2-cyclohexene-1-one (Tokyo Chemical)

[0174] B15: 3-amino-5,5-dimethyl-2-cyclohexene-1-one (Tokyo Chemical)

[0175] B16: 5-amino-2H-pyran-3(6H)-one (Combi-Blocks)

[0176] B17: 3-amino-2-cyclopenten-1-one (Ambeed)

[0177] B18: 2,3-Dihydro-4(1H)-pyridone (Combi-Blocks)

[0178] B19: 6-methyluracil (Tokyo Chemical)

[0179] B20: Adipic acid dihydrazide (Tokyo Chemical Industry Co., Ltd.)

[0180] B21: Hydantoin (Tokyo Chemical)

[0181] B22: Benzoguanamine (Tokyo Chemical)

[0182] The measurement method and evaluation method are as follows.

[0183] (1) Formaldehyde production

[0184] Using an injection molding machine (IS-100GN manufactured by Toshiba Machine), test pieces (flat plates of 100 mm × 40 mm × 3 mm) were molded from the polyacetal resin compositions obtained in the examples and comparative examples under the conditions of a mold temperature of 80°C, a barrel temperature of 220°C, an injection pressure of 35 MPa, an injection time of 15 seconds, and a cooling time of 20 seconds.

[0185] The amount of formaldehyde generated from the test piece was measured according to the method described in the German Association of the Automotive Industry standard VDA275. Specifically, the test piece was suspended in a 1L polyethylene bottle containing 50mL of distilled water and sealed without contact with distilled water. It was heated at 60°C for 3 hours and allowed to stand at room temperature for 60 minutes. The formaldehyde in the distilled water was reacted with acetylacetone in the presence of ammonium ions, and the reaction product was used as the object. The absorption peak at a wavelength of 412nm was measured using a UV spectrometer, and the formaldehyde generation was calculated. It should be noted that the formaldehyde generation is expressed as the amount of formaldehyde (μg / g) relative to 1g of polyacetal resin. The smaller the value, the more the formaldehyde generation is suppressed, which is preferred.

[0186] (2) Exudative

[0187] Using an injection molding machine (IS-100GN manufactured by Toshiba Machine), test pieces (flat plates of 100 mm × 40 mm × 3 mm) were molded from the polyacetal resin compositions obtained in the examples and comparative examples under the conditions of a mold temperature of 80°C, a barrel temperature of 220°C, an injection pressure of 35 MPa, an injection time of 15 seconds, and a cooling time of 20 seconds.

[0188] The surface of each molded product after treatment at 60°C and 95% RH for 24 hours or at 85°C and 95% RH for 168 hours was visually observed using a constant temperature and humidity chamber (PL-2KT manufactured by Espec), and the amount of bleed out was evaluated according to the following criteria.

[0189] ○ (Excellent): No bleeding was observed

[0190] △ (good): The surface is slightly blurred overall

[0191] × (poor): Thick bleeding was observed overall, and the product looked like powder.

[0192] [Example 1 to Example 33, Comparative Example 1 to Comparative Example 5]

[0193] The compositions shown in Tables 1 and 2 were mixed and supplied to a twin-screw extruder (PCM30 manufactured by Ikegai) for melt kneading at a screw speed of 60 rpm and a barrel set temperature of 200°C, and then pelletized. The obtained pellets were dried for 3 hours in a hot air dryer at a temperature of 80°C, and then molded and evaluated by the above method.

[0194] The evaluation results are summarized in Tables 1 and 2.

[0195] [Table 1]

[0196]

[0197] [Table 2]

[0198] .

Claims

1. A polyacetal resin composition, wherein The polyacetal resin composition comprises a polyacetal resin and a compound having at least one structure represented by the following formula (1): ···（1） In formula (1), *1 to *4 represent bonding positions.

2. The polyacetal resin composition according to claim 1, wherein The polyacetal resin composition includes 0.01 mmol to 100 mmol of the compound relative to 100 g of the polyacetal resin.

3. The polyacetal resin composition according to claim 1 or 2, wherein In the compound, with respect to a part or all of the structures contained in the compound, any two of the *1 to *4 in the structures are directly bonded to form a ring structure or are bonded via a linker to form a ring structure.

4. The polyacetal resin composition according to claim 1 or 2, wherein In the compound, for a part or all of the structure contained in the compound, the *3 and the *4 in the structure are directly bonded to form a ring structure or are bonded via a connecting portion to form a ring structure, and the connecting portion is an alkylene group that may be substituted or a heteroalkylene group that may be substituted.

5. The polyacetal resin composition according to claim 1 or 2, wherein In the compound, for a part or all of the structure contained in the compound, the *3 and the *4 in the structure are directly bonded to form a ring structure or are bonded via a connecting part to form a ring structure, the connecting part is an alkylene group that may be substituted or a heteroalkylene group that may be substituted, and at least one of the *1 and the *2 in the structure is a hydrogen atom.

6. The polyacetal resin composition according to claim 1 or 2, wherein The compound has 1 structure, The *1 and the *2 are each independently a hydrogen atom, an alkyl group, a halogenated alkyl group, an aryl group or an ester group, The *3 is a hydrogen atom, an alkyl group, a haloalkyl group, a thioalkyl group, an ether group or an alkoxy group, The *4 is a hydrogen atom, an alkyl group, a thioalkyl group, an aryl group, a heteroaryl group, an amino group, an aminoalkyl group, an ether group or an alkoxy group.

7. The polyacetal resin composition according to claim 6, wherein At least one of the *1 and the *2 of the structure is a hydrogen atom.

8. The polyacetal resin composition according to claim 1 or 2, wherein The compound has two or more of the structures, and any one of *1 to *4 in the different structures is bonded directly or via a linker.

9. The polyacetal resin composition according to claim 1 or 2, wherein The compound has two or more of the structures, and the *4 in different structures are bonded to each other via a connecting portion, and the connecting portion is a structure containing at least one selected from the group consisting of an ether group that may be substituted, a thioether group that may be substituted, an ester group that may be substituted, and an alkylene group that may be substituted.

10. The polyacetal resin composition according to claim 1 or 2, wherein The compound has two or more of the structures, the *4 in different structures are bonded to each other via a connecting portion, and the connecting portion is a structure containing at least one selected from the group consisting of an ether group that may be substituted, a thioether group that may be substituted, an ester group that may be substituted, and an alkylene group that may be substituted, The *1 and *2 are each independently a hydrogen atom, an alkyl group, a halogenated alkyl group, an aryl group or an ester group. The *3 is a functional group of a hydrogen atom, an alkyl group which may be substituted, a haloalkyl group which may be substituted, a thioalkyl group which may be substituted, or an alkoxy group which may be substituted.

11. The polyacetal resin composition according to claim 1 or 2, wherein The case where the compound is a compound in which, in all the structures contained in the compound, the nitrogen atom in the formula (1) and the carbon atom at the α-position of the carbonyl group form a 6-membered aromatic ring is excluded.

12. The polyacetal resin composition according to claim 1 or 2, wherein The case where the compound is uracil is excluded.

13. A method for inhibiting formaldehyde release from a polyacetal resin, wherein: The method comprises mixing a polyacetal resin with a compound having at least one structure represented by the following formula (1), ···（1） In formula (1), *1 to *4 represent bonding positions.

14. Use of a compound having at least one structure represented by the following formula (1) for suppressing formaldehyde emission from a polyacetal resin, ···（1） In formula (1), *1 to *4 represent bonding positions.

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