WO2005044916A1 - アルデヒド抑制剤組成物およびポリアセタール樹脂組成物 - Google Patents
アルデヒド抑制剤組成物およびポリアセタール樹脂組成物 Download PDFInfo
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- WO2005044916A1 WO2005044916A1 PCT/JP2004/015699 JP2004015699W WO2005044916A1 WO 2005044916 A1 WO2005044916 A1 WO 2005044916A1 JP 2004015699 W JP2004015699 W JP 2004015699W WO 2005044916 A1 WO2005044916 A1 WO 2005044916A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/44—Materials comprising a mixture of organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
Definitions
- the present invention relates to an inhibitor composition for efficiently reducing or inhibiting the generation of aldehydes having an aldehyde generation source, a polyacetal resin composition containing the inhibitor composition, a method for producing the same, and the polyacetal.
- the present invention relates to a molded article formed of the resin composition. Background art
- aldehydes such as formaldehyde, acetaldehyde and acrolein have attracted attention as one of the factors that adversely affect the environment and health.
- these aldehydes have been used as raw materials for adhesive resins (phenol resins, melamine resins, urea resins, furan resins, xylene resins, polyacetal resins, etc.) and as preservatives.
- adhesive resins phenol resins, melamine resins, urea resins, furan resins, xylene resins, polyacetal resins, etc.
- acetic acid of polyester resin polyethylene terephthalate, polypropylene terephthalate, etc.
- acetoaldehyde diacrolein which is an oxidized product of a polymerization monomer as a raw material.
- aldehydes may elute from the product due to emission of the aldehyde from the product or contact with the liquid, contaminating the surrounding environment.
- the amount of aldehyde generated increases.
- a urea compound, an aminotriazine compound, a hydrazide compound, a basic nitrogen compound such as polyamide has been conventionally effective. It is known that there is.
- hydrazide conjugates particularly, carboxylic acid hydrazide
- JP-A-10-36681 discloses a deodorant composition containing a hydrazide compound (such as a monohydrazide compound, a dihydrazide conjugate, or a polyacrylic acid hydrazide) and a synthetic resin.
- JP-A-4-345648 discloses a hydrazide compound such as a monocarboxylic acid hydrazide, a dicarboxylic acid hydrazide, or a polyacrylic acid polyhydrazide. It is disclosed that when it is contained in a wool resin, the formaldehyde odor of the resin composition power can be reduced.
- carboxylic acid hydrazide has a high ability to suppress aldehydes to some extent, but as the danger of aldehydes attracts attention, it is required to suppress the generation of aldehydes at a higher level. .
- carboxylic acid hydrazide may cause discoloration under the action of heat or coexistence with other chemical substances, which impairs product quality and appearance.
- Patent Document 1 JP-A-10-36681 (Claim 1, paragraph numbers [0011], [0017] and
- Patent Document 2 Japanese Patent Application Laid-Open No. Hei 4 345648 (Claim 1, Paragraph Nos. [0001], [0009]-[0012])
- an object of the present invention is to provide an aldehyde inhibitor composition that can enhance the ability of carboxylic acid hydrazide to scavenge aldehydes and efficiently suppress the generation of aldehyde as a source of aldehyde generation.
- Another object of the present invention is to provide a polyacetal resin or a polyacetal resin composition capable of remarkably suppressing the generation of formaldehyde, which does not discolor the molded product or the strength of the molded product, a method for producing the same, and a molded product. Is to provide.
- Still another object of the present invention is to provide an aldehyde inhibitor yarn composition and a polyacetal resin composition that can efficiently suppress the generation of aldehyde from the polyacetal resin even when added in a small amount. .
- Another object of the present invention is to provide a polyacetal resin molded article in which discoloration and generation of formaldehyde are suppressed.
- Still another object of the present invention is to suppress the amount of formaldehyde generated from polyacetal resin and molded articles to an extremely low level, and to attain weather resistance (light), impact resistance, and (low) luster.
- Another object of the present invention is to provide a polyacetal resin composition and a molded article having improved properties such as slidability.
- the present inventor has proposed a carboxylic acid hydride which is an aldehyde inhibitor.
- the metal salt of hydroxy polyvalent carboxylate significantly improved the ability of carboxylic acid hydrazide to inhibit aldehydes without discoloring the resin due to carboxylic acid hydrazide.
- an inhibitor composition containing a carboxylic acid hydrazide and a hydroxy polycarboxylic acid metal salt is added to a polyacetal resin, it is possible to significantly suppress formaldehyde generated from a molded product of the polyacetal resin. Heading, the present invention has been completed.
- the aldehyde inhibitor composition of the present invention is an inhibitor composition for suppressing the generation of aldehyde-forming carboxylic acid, and comprises a carboxylic acid hydrazide and a hydroxy polycarboxylic acid metal salt.
- a carboxylic acid hydrazide examples include hydrocarbon hydrazide (aliphatic carboxylic acid hydrazide, alicyclic carboxylic acid hydrazide, aromatic carboxylic acid hydrazide, dimer acid or trimer acid hydrazide), and carboxylic acid having a heteroatom-containing group.
- hydrazide of polymer type and polymer type carboxylic acid hydrazide (acid hydrazide of a polymer having a carboxyl group) and the like.
- the metal salts of hydroxy polycarboxylic acids include hydroxy aliphatic polycarboxylic acids (such as hydroxy C aliphatic di- or tetracarboxylic acids such as taenoic acid, malic acid and tartaric acid) and alkali metals and alkaline earth metals (
- the ratio of the metal hydroxy polyvalent carboxylate may be about 0.01 to 100 parts by weight based on 1 part by weight of the carboxylic acid hydrazide.
- the inhibitor composition may include at least one selected from an adsorbent and a resin.
- an aldehyde inhibitor component containing at least the carboxylic acid hydrazide and the hydroxy polycarboxylic acid metal salt may be held or carried on a substrate.
- the present invention also includes a polyacetal resin composition containing the polyacetal resin and the aldehyde inhibitor composition, and a molded article formed from the resin composition.
- a pellet of the polyacetal resin and a master batch containing the aldehyde inhibitor composition or the aldehyde inhibitor composition may coexist.
- the resin composition further includes an antioxidant, a heat stabilizer, a processing stabilizer, a weather (light) stabilizer, and an impact resistance modifier. It may contain at least one selected from a good agent, a gloss control agent, a slidability improving agent, a coloring agent and a filler.
- the molded articles include automobile parts, electric and electronic parts (electric and
- the present invention provides a method for producing a resin composition in which a polyacetal resin and the aldehyde inhibitor composition are melt-mixed using an extruder, wherein (a) at least carboxylic acid hydrazide is added to a side of the extruder.
- the present invention also includes a method for producing a polyacetal resin composition in which feed force is also fed and mixed, and (b) a method for producing a polyacetal resin composition having an average residence time of 300 seconds or less in the extruder.
- the aldehyde inhibitor composition of the present invention combines carboxylic acid hydrazide and metal hydroxy polyvalent carboxylate, the aldehyde scavenging ability of the carboxylic acid hydrazide is enhanced to be adjacent to or mixed with the aldehyde generating source. For example, the generation of the aldehyde from the source can be efficiently suppressed, and the surrounding environment (work environment, use environment, etc.) can be greatly improved.
- the specific combination of the inhibitor composition causes the high temperature associated with the extrusion and Z or the molding process despite the use of carboxylic acid hydrazide.
- the aldehyde inhibitor composition of the present invention is composed of a carboxylic acid hydrazide and a hydroxy polyvalent metal carboxylate.
- the carboxylic acid forming the carboxylic acid hydrazide is a polyvalent carboxylic acid which may be a monovalent carboxylic acid (monocarboxylic acid), for example, a polycarboxylic acid such as dicarboxylic acid, tricarboxylic acid, or tetracarboxylic acid. It may be.
- the number of hydrazino carbonyl groups in the carboxylic acid hydrazide is not particularly limited as long as at least a part of the carboxylic acid of the corresponding carboxylic acid is hydrazide-ridden, and all the carboxyl-group hydrazide may be ridden.
- hydrazide of polycarboxylic acid monohydric or polyhydrazide of polycarboxylic acid (for example, mono- or dihydrazide of dicarboxylic acid, mono- to trihydrazide of tricarboxylic acid, etc.) may be used.
- the carboxylic acid hydrazide includes a hydrocarbon carboxylic acid hydrazide (for example, an aliphatic carboxylic acid hydrazide, an alicyclic carboxylic acid hydrazide, an aromatic carboxylic acid hydrazide, a dimer acid or a trimer acid hydrazide), and a hetero atom-containing group.
- a hydrocarbon carboxylic acid hydrazide for example, an aliphatic carboxylic acid hydrazide, an alicyclic carboxylic acid hydrazide, an aromatic carboxylic acid hydrazide, a dimer acid or a trimer acid hydrazide
- a hetero atom-containing group Any of hydrazide of a carboxylic acid having the same and polymer-type carboxylic acid hydrazide (acid hydrazide of a polymer having a carboxyl group, etc.) may be used.
- examples of the aliphatic carboxylic acid hydrazide include monocarboxylic acid hydrazide [substituents such as lauric acid, stearic acid, 12-hydroxystearic acid, and linoleic acid (such as a hydroxyl group). ) Having a saturated / unsaturated C aliphatic monocarboxylic acid monohydrazide, etc.], a polyhydric carboxylic acid hydrazide [fat
- Mono- or polyhydrazides of aliphatic polycarboxylic acids such as saturated C aliphatic dicarboxylic acids
- Saturated C aliphatic dicarboxylic acids (itaconic acid, sorbic acid, 7, 11-octadecadiene-1
- hydroxycarboxylic acids lactic acid, D-form, L- or DL-form malic acid, D-form, L-form, DL-form or meso-form
- Hydrazides of mono- or polyhydroxy C mono- or polycarboxylic acids such as tartaric acid and citric acid
- the hydrazide of the polycarboxylic acid also includes polycarboxylic acid ester hydrazide, for example, dicarboxylic acid mono C alkyl ester hydrazide such as adipic acid monomethyl ester hydrazide, sebacic acid monomethyl ester hydrazide, dodecane diacid monomethyl ester hydrazide, and the like. It is. Further, the polycarboxylic acid hydrazide
- hydrazino groups one NHNH may be hydrazoned.
- the drazide includes, for example, monoketone hydrazone of dicarboxylic dihydrazide (for example, monoacetone hydrazone of adipate dihydrazide) and the like.
- dicarboxylic dihydrazide for example, monoacetone hydrazone of adipate dihydrazide
- aliphatic carboxylic acid hydrazides having about 210 carbon atoms C saturated carboxylic acid hydrazide, C unsaturated
- alicyclic carboxylic acid hydrazide monocarboxylic acid hydrazide (saturated or unsaturated C alicyclic monocarboxylic acid such as cyclohexane carboxylic acid, cyclohexene carboxylic acid, etc.)
- polyhydric carboxylic acid hydrazides saturated or unsaturated C alicyclic groups such as 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid, cyclohexanetricarboxylic acid, etc.
- polycarboxylic acid mono- or polyhydrazide etc.
- These alicyclic carboxylic acid hydrazides may have a substituent on the alicyclic ring.
- carboxylic acid hydrazide examples include monocarboxylic acid hydrazides [having a substituent on an aromatic ring, and may include benzoic acid and a mono- or ⁇ -naphthoic acid.
- Hydrazide of boric acid polyhydric carboxylic acid hydrazides [isophthalic acid mono- or dihydrazide, terephthalic acid mono- or dihydrazide, 1,2,4 benzenetricarboxylic acid mono- to trihydrazide, pyromellitic acid mono-tetrahydrazide, 1, (4) C-arene polycarboxylic acid mono- or polyhydrazide such as mono- or 2,6-naphthalenedicarboxylic acid mono- or dihydrazide, 1,4,5,8-naphthalenetetracarboxylic mono- or tetrahydrazide;
- Carboxylic acid bis (carboxyphenoxy) linear or branched C alkane (diphenoxy)
- aromatic polycarboxylic acid hydrazide includes aromatic polycarboxylic acid ester hydrazide, for example, isophthalic acid monomethyl ester hydrazide, 2,6 naphthalenedicarboxylic acid monomethyl ester hydrazide, 4,4, diphenyldicarboxylic acid monomethyl ester. Also included are aromatic dicarboxylic acid mono-C alkyl ester monohydrazides such as hydrazide.
- aromatic carboxylic acid hydrazides may have a substituent on the aromatic ring.
- aromatic carboxylic acid hydrazide having a substituent include, for example, substituted benzoic acid (o-, m- or p-methylbenzoic acid, 2, 4-, 3, 41, 3, 5- or 2, 5-Dimethylbenzoic acid, 4-hydroxy-3,5-dimethylbenzoic acid, 4-hydroxy-3,5-di-tert-butylbenzoic acid, 4-hydroxy-3-phenylbenzoic acid, 4-acetoxy-3-phenylbenzoic acid, 4- Hydrazide of substituted benzoic acid, 4 (4'-biphenyl) benzoic acid, o-, m- or p-hydroxybenzoic acid, o-, m- or p-acetoxybenzoic acid, substituted ⁇ - or j8- Naphthoic acid hydrazide (eg, 3-hydroxy-2-naphthoic acid
- dimer acid or trimer acid hydrazide examples include linear saturated (or hydrogenated) dimer acid or trimer acid hydrazide (linear or saturated (or hydrogenated) linole dimer acid mono- or dihydrazide, etc.) and linear unsaturated dimer Linear or unsaturated dimer acids or trimer hydrazides such as acid or trimer hydrazides (such as linear linolenic dimer acid mono or dihydrazides); cyclic saturated (or hydrogenated) dimer acids or trimer acid hydrazides (or cyclic saturated (or Hydrogenated) linole dimer acid mono- or dihydrazide, etc.), cyclic unsaturated dimer acid or trimer acid hydrazide (cyclic or unsaturated linole dimer acid, cyclic unsaturated oleic dimer acid, cyclic unsaturated linolenic dimer acid or other mono- or dihydrazide Cyclic saturated or unsaturated
- Monoacid hydrazide (such as cyclic c trimer acid mono to trihydrazide) may be used.
- examples of the linear carboxylic acid hydrazides having a nitrogen atom-containing group include amino acid hydrazides ⁇ - and ⁇ —Or ⁇ amino acids, for example, hydrazides such as tyrosine, histidine, tryptophan, etc.), iminodiacetic acid mono- or dihydrazide, tri-triacetic mono- or trihydrazide, ethylenediaminetetraacetic acid mono- to tetrahydrazide, 2,6-pyridindicarboxylic acid Mono- or dihydrazide, aliphatic carboxylic acid hydrazide having a 5- to 8-membered mono- to triazacycloalkane group (aliphatic carboxylic acid having an isocyanuric ring, for example, 1,3,5-tris (2-carboxyethyl) is
- carboxylic acid hydrazides described in JP-A-59-67256, JP-A-60-178851, and JP-A-61-183316 may be either an LD- or DL-form.
- carboxylic acid hydrazides may have, for example, a substituent on the heterocyclic ring.
- the carboxylic acid hydrazide having an oxygen atom-containing group is an aliphatic carboxylic acid hydrazide having a cyclic ether group. Is mentioned. This aliphatic carboxylic acid hydrazide may have a substituent on the cyclic ether group.
- Such carboxylic acid hydrazides include carboxylic acid hydrazides having a dioxane ring [eg, hydrazide of 5-methylol 5-ethyl-2- (1,1, dimethyl-2-carboxyethyl) -1,3 dioxane], tetraoxo, and the like.
- polymer type carboxylic acid hydrazide a poly (meth) acrylic acid hydrazide homopolymer or copolymer (for example, JP-A-53-142496, JP-A-54-21493, JP-A-54-49493) 43254, JP-A-56-2306, JP-A-58-69232 and JP-A-63-49300, polymers commercially available "Aminopolyacrylamide APA Series" Otsuka Chemical Co., Ltd. And the like).
- a poly (meth) acrylic acid hydrazide homopolymer or copolymer for example, JP-A-53-142496, JP-A-54-21493, JP-A-54-494903
- JP-A-56-2306, JP-A-58-69232 and JP-A-63-49300 polymers commercially available "Aminopolyacrylamide APA Series" Otsuka Chemical Co., Ltd. And the like).
- carboxylic acid hydrazides hydrocarbon carboxylic acid hydrazides, in particular, aliphatic carboxylic acid hydrazide (for example, aliphatic carboxylic acid hydrazide having about 2 to 16 carbon atoms) and aromatic carboxylic acid hydrazide are preferable. Better ,.
- carboxylic acid hydrazide may have a substituent! /.
- substituents include a linear or branched alkyl group (such as a methyl or ethyl group), a hydroxyalkyl group (such as a methylol or ethylol group), a phenyl group, a tamyl group, and a hydroxyl group.
- substitution position of the substituent is not particularly limited, as described above, it is usually on a hydrocarbon group (such as an aliphatic group, an alicyclic ring, or an aromatic ring) or a hetero atom-containing group bonded to a hydrazinocarbon group. You may have.
- the number of substituents is not particularly limited, and is preferably one to five. May be 1 to 4, more preferably about 1 to 3.
- the molecular weight of the carboxylic acid hydrazide is not particularly limited, and can be selected from a wide range of about 500 to 3,000,000.
- the carboxylic acid hydrazide is, for example, a low molecular weight compound having a molecular weight of about 60 to 300, a medium molecular weight compound having a molecular weight of about 300 to 1000, a high molecular weight compound having a molecular weight of about 1000 to 3000, and a number average molecular weight of about 300 to 3,000,000. Any of polymers having a molecular weight!
- the number of the hydroxyl xyl groups is not particularly limited, and may be, for example, 114, preferably 113, and more preferably 1 or 2.
- hydroxy polycarboxylic acids examples include hydroxy polyaliphatic carboxylic acids, hydroxycycloaliphatic polycarboxylic acids (such as hydroxy C cycloalkanedi or tricarboxylic acids such as 1,4-dicarboxy-2-oxanol). ), Hydroxy aromatic polycarboxylic acids (e.g.
- Hydroxy c arenes and tetracarboxylic acids such as droxybenzene dicarboxylic acid
- Acid and the like can be used.
- hydroxy polyaliphatic carboxylic acid examples include hydroxyaliphatic polycarboxylic acids such as tartronic acid, malic acid, tartaric acid, citric acid and hydroxyhexadecane diacid (hydroxy C aliphatic dicarboxylic acid). Or tetracarboxylic acid). Note that
- the hydroxy polycarboxylic acid having an asymmetric center in the molecule may be any of the DLDL-form and the meso-form.
- hydroxy polycarboxylic acids may be used alone or in combination of two or more to form a metal salt with a metal.
- mono- to dihydroxy C aliphatics such as D-form, L-form, DL-form or meso-form tartaric acid, D-form, L-integral or DL-form malic acid, and citric acid Di- or tricarboxylic acids are preferred.
- the metal forming the metal salt examples include alkali metals (K, Na, etc.), alkaline earth metals (Mg, Ca, Ba, etc.), Group 3A metals of the periodic table, and Group 4A metals (Ti Etc.), 5A Metals (such as V), Group 6A metals (such as), Group 7A metals (such as Mn), Group 8 metals (such as Fe, Ru, Co, Ni, Pd), Group IB metals (such as Cu), Group 2B metals (such as Zn) ), Group 3B metals (such as A1), and Group 4B metals (such as Sn and Pb).
- the valence of the metal is not particularly limited, and may be, for example, 114, preferably 2 to 4, more preferably 2 or 3.
- alkali metals, alkaline earth metals, Group 2B metals, Group 3B metals, Group 4B metals, and Group 8 metals are exemplified. I like it.
- the metal may form a metal salt alone with the hydroxy polycarboxylic acid, or may form a double salt with the hydroxy polycarboxylic acid by combining a plurality of metals.
- the metal salt can be constituted by appropriately combining the hydroxy polycarboxylic acid and a metal.
- the metal salt may be a normal salt or a hydrogen salt which is a partial metal salt.
- the metal salt may be any of a hydrated salt and an anhydrous salt. Specific examples of such a metal salt include, for example, alkaline earth metal citrate [magnesium tenoate Mg (CH
- alkaline earth metal tartrate magnesium tartrate MgC H O
- metal salts for example, hydroxy C aliphatic di- or tricarboxylic acid (particularly
- Acid and a salt of an alkaline earth metal (especially Ca) are preferred.
- citrus acid lucidum (tricalcium taenoate) and magnesium citrate are preferred.
- the metal salt include hydrated salts, for example, hydrated salts of calcium citrate and magnesium citrate (trihydrate and tetrahydrate of tricalcium catenate; nonahydrate of magnesium citrate and fourteen hydrate) And the like are also preferable.
- the percentage of the hydroxy polycarboxylic acid metal salt is reduced.
- the total (weight ratio) is 0.001 to 100 parts by weight (for example, 0.003 to 50 parts by weight), preferably 0.005 to 30 parts by weight, more preferably 0.005 to 30 parts by weight based on 1 part by weight of the carboxylic acid hydrazide.
- 0.01 to 10 parts by weight for example, 0.01 to 5 parts by weight
- the aldehyde inhibitor composition of the present invention may further include at least one selected from an adsorbent and a resin.
- the aldehyde inhibitor component may be held or carried on a substrate.
- the inhibitor composition of the present invention also includes such a composite composition.
- Examples of the adsorbent include porous adsorbents such as zeolite, silica gel, alumina, activated carbon, and sepiolite, and cyclodextrin.
- the adsorbents can be used alone or in combination of two or more.
- the aldehyde inhibitor component containing at least the carboxylic acid hydrazide and the metal hydroxy polycarboxylic acid is added to the adsorbent by, for example, adsorption, interforce rate, inclusion, or the like. It may be carried or held.
- the resin examples include various synthetic resins such as thermoplastic or thermosetting resins, for example, olefin-based resins (eg, homopolymers such as polyethylene and polypropylene, and copolymers such as ethylene- Vinyl acetate copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, ethylene vinyl acetate-acrylate copolymer, etc.), halogen-containing resin (polyvinyl chloride, polyvinyl chloride / polyvinylidene, etc.), butyl-based resin Fats (polyvinyl acetate, polyvinyl alcohol, etc.), acrylic resins (homopolymers or copolymers of acrylic monomers such as (meth) acrylic acid, alkyl (meth) acrylate, etc.), styrene resins (polystyrene, etc.) In addition to homopolymers, copolymers such as AS resin, ABS resin, AES resin, S
- the aldehyde inhibitor component may be mixed with the resin to form fibers or Z or particles composed of the resin or the aldehyde inhibitor component. Minutes can be carried or held!
- Examples of the substrate include wood (natural wood, plywood, decorative board, etc.), paper, fiber, cloth (woven fabric, nonwoven fabric, etc.), ceramic and the like.
- the aldehyde inhibitor composition of the present invention can remove aldehydes in an aldehyde atmosphere efficiently by bringing it into close proximity (contact, coating, packaging, etc.) with an aldehyde generation source, The concentration can be reduced. Further, by using the aldehyde inhibitor composition contained in an aldehyde generation source, generation of aldehyde from the generation source can be suppressed.
- the type of aldehyde generating source is not particularly limited.
- building materials and furniture that generate aldehydes components that generate aldehyde odor
- components that generate aldehyde odor tobacco smoking sources, aldehyde-producing resins (phenolic resin, urea resin) Melamine resin, guanamine resin, furan resin, xylene resin, polyacetal resin, polyester resin, etc.).
- aldehyde inhibitor composition of the present invention particularly in combination with a polyacetal resin, can effectively suppress the generation of formaldehyde from the polyacetal resin.
- the polyacetal resin composition of the present invention comprises the aldehyde inhibitor composition and a polyacetal resin.
- Polyacetal resin is a high-acetal resin containing oxymethylene groups (one OCH—) as the main structural unit.
- a comonomer unit includes an oxyalkylene unit having about 2 to 6 carbon atoms (preferably about 2 to 4 carbon atoms) (for example, an oxyethylene group (one OCHCH one), an oxypropylene group, Methylene group
- the content of the comonomer unit may be small, for example, for the entire (monomer units constituting the polyacetal ⁇ ) polyacetal ⁇ , 0. 01- 20 mole 0/0, good Mashiku is 0. 03 15 Monore 0/0 (for example, 0.1 05 10 Monore 0/0), more preferably about 0.5 1 10 mol%.
- the polyacetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like.
- the polyacetanol copolymer may be a random copolymer, a block copolymer, a graft copolymer, or the like.
- the polyacetal resin may have not only a linear structure but also a crosslinked structure which may have a branched structure.
- the terminal of the polyacetal resin may be stabilized by esterification with a carboxylic acid such as acetic acid or propionic acid or an anhydride thereof, for example.
- the degree of polymerization, the degree of branching, and the degree of crosslinking of the polyacetal are not particularly limited as long as they can be melt-molded.
- the molecular weight of the polyacetal resin is not particularly limited, and may be, for example, a weight average molecular weight of 5,000 to 500,000, preferably about 10,000 to 400,000.
- the polyacetal resin includes, for example, aldehydes such as formaldehyde and paraformaldehyde, cyclic ethers such as trioxane, ethylene oxide, propylene oxide, 1,3-dioxolan, diethylene glycol formal, and 1,4 butanediol formal. It can be produced by polymerizing cyclic formal.
- aldehydes such as formaldehyde and paraformaldehyde
- cyclic ethers such as trioxane, ethylene oxide, propylene oxide, 1,3-dioxolan, diethylene glycol formal, and 1,4 butanediol formal. It can be produced by polymerizing cyclic formal.
- an aldehyde inhibitor composition composed of carboxylic acid hydrazide and hydroxypolycarboxylic acid metal salt
- formaldehyde from polyacetal resin can be obtained without discoloring the polyacetal resin.
- the aldehyde inhibitor composition of the present invention is used, a small amount of a stabilizing effect far exceeding that of the conventional stabilizer is exhibited, and extruding and molding processing stability (discoloration stability) is excellent.
- the resulting polyacetal resin composition can be obtained.
- the aldehyde generation can be efficiently suppressed only by adding a small amount of the inhibitor composition.
- the ratio of the aldehyde inhibitor composition is not particularly limited, and is, for example, 0.001 to 20 parts by weight, preferably 0.002 to 10 parts by weight, per 100 parts by weight of the polyacetal resin. Parts by weight (for example, 0.003 to 3 parts by weight), more preferably about 0.005 to 2 parts by weight. If the proportion is too small, it is difficult to efficiently reduce the amount of formaldehyde generated, and if it is too large, the formability and mechanical strength are reduced. The degree may be reduced.
- the ratio of the carboxylic acid hydrazide is, for example, 0.0001 to 10 parts by weight, preferably ⁇ 0.001 to 5 parts by weight, and more preferably 0.01 to 100 parts by weight of the polyacetal resin. — It may be about 1 part by weight.
- the ratio of the metal salt of the hydroxy polycarboxylic acid is, for example, 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 0.005 to 100 parts by weight of the polyacetal resin. It may be about 2 parts by weight (for example, 0.01-1 part by weight).
- the formation of formaldehyde can be remarkably suppressed and the processing stability can be improved only by blending the aldehyde inhibitor composition.
- Hindered phenol compounds, hindered amine compounds processing stabilizers, heat stabilizers, weather (light) stabilizers, impact modifiers, slidability modifiers, colorants and fillers. May be included.
- the stabilizer the antioxidant, the processing stabilizer, the heat stabilizer and the weather (light) stabilizer
- Antioxidants include hindered phenolic compounds and hindered amine compounds.
- a conventional phenol-based antioxidant or stabilizer for example, a monocyclic hindered phenol compound (such as 2,6-di-tert-butyl-p-taresole), a hydrocarbon group or Polycyclic hindered phenol compounds linked by a group containing a zeo atom [2,2'-methylenebis (4-methyl-6t-butylphenol), 4,4'-methylenebis (2,6-di-butylbutylphenol), 1 Alkylenebis or tetrakis (t-butylphenol) such as 1,1,3-tris (2-methyl-4-hydroxy-5-tbutylphenyl) butane
- a monocyclic hindered phenol compound such as 2,6-di-tert-butyl-p-taresole
- hydrocarbon group or Polycyclic hindered phenol compounds linked by a group containing a zeo atom [2,2'-methylenebis (4-methyl-6t-butylphenol), 4,4'-methylenebis (2,
- T-alkylphenols having a oxy group for example, t-butylphenol and t-pentylphenol); hindered phenols having a phosphonate group such as di-n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate
- hydrazine N, N, -bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propioyl] hydrazine, 1,3,5-tris It has amide units such as (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate.
- Hindered phenolic dangled products, etc. Among them, a phenol compound having a t-butyl (particularly, a plurality of t-butyl) groups (particularly, a compound having a plurality of t-butyl phenol sites) is preferable.
- These hindered phenol compounds can be used alone or in combination of two or more.
- hindered amine-based compound examples include piperidine derivatives having a sterically hindered group, for example, ester group-containing piperidine derivatives [4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,2.
- Aliphatic acyloxypiperidines such as 6,6-tetramethylpiperidine, 4 atariloyloxy 2,2,6,6-tetramethylpiperidine (C aliphatic aliphaticoxy-tetramethylpiperidine, etc.); 4 Benzoyloxy 2, 2 , 6
- Aromatics such as bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate and tris (2,2,6,6-tetramethyl-4-piperidyl) benzene 1,3,5-tricarboxylate Bis- or tetrakispiperidyl esters of aromatic di- or tetracarboxylic acids (such as bis- or trispiperidyl esters of aromatic di- or tri-carboxylic acids), ether-containing piperidine derivatives [4-methoxy-2,2,6,6-tetramethylpiperidine, etc.] End of C
- Cycloalkyloxypiberidi such as oxy 2,2,6,6-tetramethylpiperidine
- Phenyloxypiperidines such as 4 phenoxy 2,2,6,6-tetramethylpiperidine; Caryl carbons such as 4-benzyloxy 2,2,6,6-tetramethylpiperidine
- alkylenedioxybibispiperidine C alkylenedioxybispiperidine
- amide group-containing piperidine derivatives [4 (phenylcarbamoyloxy) Carbamoyloxy-piperidines such as -2,2,6,6-tetramethylpiperidine; carbamoyloxy-substituted alkylenedienes such as bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene 1,6-dicarbamate Oxybispiperidine, etc.].
- a high-molecular-weight piperidine derivative polycondensate (dimethyl succinate-11- (2-hydroxyethyl) -14-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly ⁇ 6-— ( 1,1,3,3-tetramethylbutyl) imino— 1,3,5-triazine-2,4 diyl] [2- (2,2,6,6-tetramethylpiperidyl) amino] hexamethylene [4— (2, 2, 6, 6-tetramethylpiperidyl) imino] ⁇ ).
- These hindered amine compounds can be used alone or in combination of two or more.
- antioxidants can be used alone or in combination of two or more.
- the ratio of the antioxidant is 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the polyacetal resin. Degree.
- processing stabilizer examples include at least one kind selected from the group consisting of (a) a long-chain fatty acid or a derivative thereof, (b) a polyoxyalkylene dalycol, and (c) a silicone compound.
- the long chain fatty acid may be a saturated fatty acid or an unsaturated fatty acid. Further, those in which a part of hydrogen atoms are substituted with a substituent such as a hydroxyl group can also be used.
- Such long-chain fatty acids include monovalent or divalent fatty acids having 10 or more carbon atoms, for example, monovalent saturated fatty acids having 10 or more carbon atoms [lauric acid, palmitic acid, stearic acid, behenic acid, monic acid, etc. C-saturated fatty acids, etc.], monounsaturated fatty acids having 10 or more carbon atoms
- Acid linoleic acid, linolenic acid, and other C-unsaturated fatty acids] divalent having 10 or more carbon atoms
- Fatty acids dibasic fatty acids
- divalent C saturated fats such as sebacic acid and dodecane diacid
- the fatty acids 10-30 fatty acids; divalent C-unsaturated fatty acids such as decenedioic acid, etc.].
- the fatty acids divalent C-unsaturated fatty acids such as decenedioic acid, etc.].
- fatty acids having one or more hydroxyl groups in the molecule include hydroxy-saturated C fatty acids such as 12-hydroxystearic acid. These fatty acids
- Derivatives of long-chain fatty acids include fatty acid esters and fatty acid amides.
- the structure of the fatty acid ester is not particularly limited, and a straight or branched fatty acid ester may be used.
- the ester of a long-chain fatty acid with an alcohol eg, monoester, diester, triester, tetraester, etc.
- an ester having one or more ester bonds of the above eg, monoester, diester, triester, tetraester, etc.
- the alcohol constituting the long-chain fatty acid ester is not particularly limited and may be a monohydric alcohol, but usually a polyhydric alcohol is often used.
- polyhydric alcohol examples include polyhydric alcohols having about 2 to 8 carbon atoms or polymers thereof, for example, diols such as alkylene glycol (eg, ethylene glycol, diethylene glycol, propylene glycol); glycerin, triglyceride, and the like. Triols such as methylolpropane or derivatives thereof; tetraols such as pentaerythritol, sorbitan or derivatives thereof; and homo- or copolymers of these polyhydric alcohols (for example, polyglycols such as polyethylene glycol and polypropylene glycol).
- diols such as alkylene glycol (eg, ethylene glycol, diethylene glycol, propylene glycol); glycerin, triglyceride, and the like.
- Triols such as methylolpropane or derivatives thereof; tetraols such as pentaerythritol, sorbitan or derivatives
- Oxyalkylene glycol homo- or copolymer, polyglycerin, dipentaerythritol, polypentaerythritol, etc.) can be exemplified.
- the average degree of polymerization of the polyoxyalkylene glycol is 2 or more (for example, 2 to 500), and preferably 16 or more (for example, about 20 to 200).
- the alcohols can be used alone or in combination of two or more.
- Examples of such a long-chain fatty acid ester include ethylene glycol ester (ethylene glycol mono- or dipalmitate, stearic acid, behenic acid or montanate corresponding to the palmitate), glycerin ester (Glycerine mono to tripalmitic acid ester, stearic acid, behenic acid or montanic acid ester corresponding to this palmitic acid ester, etc.), pentaerythritol ester (pentaerythritol mono to tetrapalmitic acid ester, stearic acid corresponding to this palmitic acid ester) Acid, behenic acid or montanic acid ester), polyglycerin tristearate ester, trimethylolpropane monopalmitate, pentaerythritol monoundecylate Le, sorbitan monostearate, polyalkylene glycol (polyethylene glycol, polypropylene glycol, etc.) mono or dilaurate, palmitate corresponding
- fatty acid amides include acid amides (monoamides, bisamides, etc.) of the long-chain fatty acids (monovalent or divalent long-chain fatty acids) and amines (monoamine, diamine, polyamines, etc.). ) Can be used.
- acid amides monoamides, bisamides, etc.
- bisamides are particularly preferred.
- Examples of the monoamide include primary amides of saturated fatty acids such as lauric amide, palmitic amide, and stearamide, primary amides of unsaturated fatty acids such as oleic amide, and stearyl stearamide. And secondary amides of saturated and Z- or unsaturated fatty acids such as stearyl oleic acid amides and monoamines.
- Bisamides include bisamides of C alkylenediamine and the above fatty acids, and the like.
- amides include ethylenediamine dipalmitic acid amide, ethylenediamine distearic acid amide (ethylenebisstearylamide), hexamethylenediamine distearic acid amide, and behenic acid and montan acid corresponding to these acid amides.
- examples include acid, oleic acid or erlic acid amide.
- the bisamide a bisamide having a structure in which a different acyl group is bonded to an amine moiety of an alkylenediamine such as ethylenediamine (stearic acid amide) oleic acid amide can also be used.
- the fatty acid constituting the acid amide is preferably a saturated fatty acid.
- Polyoxyalkylene glycols include alkylene glycols [eg, C alkylene glycols such as ethylene glycol, propylene glycol, and tetramethylene glycol].
- alkylene glycols eg, C alkylene glycols such as ethylene glycol, propylene glycol, and tetramethylene glycol.
- polyoxyalkylene glycol examples include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
- polyoxyethylene polyoxypropylene copolymers such as random or block copolymers
- copolymers such as polyoxyethylene polyoxypropylene glyceryl ether and polyoxyethylene polyoxypropylene monobutyl ether.
- polymers having oxyethylene units such as polyethylene glycol, polyoxyethylene polyoxypropylene copolymer and derivatives thereof, are preferred. That's right.
- the number average molecular weight of the polyoxyalkylene glycol is 3 ⁇ 10 2 —1 ⁇ 10 6 (for example, 5
- X 10 2 - 5 X 10 5 preferably 1 X 10 3 - a 5 X 10 4) about - 1 X 10 5 (e.g., 1 X 10 3.
- Polyoxyalkylene glycols can be used alone or in combination of two or more.
- Silicone compounds include (poly) organosiloxanes and the like.
- Examples of the (poly) organosiloxane include monoorganosiloxanes such as dialkylsiloxanes (eg, dimethylsiloxane), alkylarylsiloxanes (eg, methylmethylsiloxane), and diarylsiloxanes (eg, diphenylsiloxane). And homopolymers thereof (for example, polydimethylsiloxane, polyphenylmethylsiloxane, etc.) and copolymers. Note that the polyorganosiloxane may be an oligomer.
- (poly) organosiloxane has an epoxy group, a hydroxyl group, an alkoxy group, a carboxyl group, an amino group or a substituted amino group (such as dialkylamino group), an ether group, Modified (poly) organosiloxane (for example, modified silicone) having a group or a substituent such as a (meth) atalyloyl group is also included.
- modified silicone compounds can be used alone or in combination of two or more.
- the ratio of the processing stabilizer is, for example, 0.1% by weight based on 100 parts by weight of the polyacetal resin.
- the heat stabilizer includes (a) a basic nitrogen compound, (b) a metal salt of an organic carboxylic acid or an organic carbonate, (c) an alkali or alkaline earth metal compound, (d) talc, talcite, (E) zeolite and ( ⁇ -phosphine ligated compounds).
- the basic nitrogen compound is selected from a triazine compound, a guanidine compound, a urea compound, an amino acid compound, an amino alcohol compound, an imide compound, and an amide compound. At least one can be used.
- the aminotriazine conjugate includes melamine or a derivative thereof [melamine, a melamine condensate (melam, melem, melon) or the like], guanamine or a derivative thereof, and an aminotriazine resin [co-condensed resin of melamine ( Melamine formaldehyde resin, phenol-melamine resin, melamine phenol-formaldehyde resin, benzoguanamine melamine resin, aromatic polyamine melamine resin, etc., guanamine co-condensation resin (benzoguanamine monoformaldehyde resin, benzoguanamine monophenol) Such as ruformaldehyde resin).
- guanamine derivatives include aliphatic guanamine compounds.
- Monocarbamines such as sancarboguanamine, norbornenecarboguanamine, cyclohexenecarboguanamine, norbornanecarboguanamine, etc., aromatic guanamine conjugates [monoguanamines (benzoguanamine, benzoguanamine having a substituent, for example, toldaanamine, Xyloganamin, phenylbenzoguanamine, hydroxybenzoguanamine, 4- (4-hydroxyphenyl) benzoguanamine, cyanobenzoguanamine, 3,5-dimethyl-4-hydroxybenzoguanamine, 3,5-di-tert-butyl-4-hydroxybenzoguanamine A- or ⁇ -naphthoguanamine, polyguanamines (phthaloganamin, isophthaloganamin, terephthaloganamin, naphthalenediguanamine, biphenylenediguanamine Etc.), aralkyl or aralkylenedianamine
- Guanamines containing a tetraoxospiro ring (CTU—guanamine, CMT U—guanamine, etc.), guanamines containing an isocyanuric ring (1,3,5-tris [2- (4,6, diamino-s-triazine) - 2 - I le) Echiru] Isoshianureto, 1, 3, 5-tris [3- (4 ,, 6, - Diamino-s-triazine-2, -yl) propyl] isocyanurate; guanamines containing an imidazole ring (such as guanamine compounds described in JP-A-47-41120); and JP-A-2000-154181. Guanamine compounds).
- the guadinine conjugates include, for example, acyclic guanidines (glycosamine, guanoline, guanidine, cyanoguanidine and the like), cyclic guanidines (glycocyanidins such as glycosiamidine and creatinine; oxalyl guanidine) Oxaryl guanidines such as 2,4-diiminoparabanic acid or cyclic guanines similar to the structure thereof); imino group-substituted perazole conjugates (such as iminourazole and guanazine); isocyanuric imides ( Isoammelide, isoammeline, etc.); maloninoleguanidine, tanoretro dinoleguanidine, mesoxalinoleganidine and the like.
- acyclic guanidines glycosiamidine and creatinine; oxalyl guanidine
- urea compound examples include a non-cyclic urea compound [N-substituted urea substituted with a substituent such as urea and an alkyl group, a non-cyclic urea condensate (urea multimer such as piuret and piurea; methylene Condensates of urea such as diurea and form nitrogen with aldehyde conjugates), cyclic urea compounds [cyclic monoureides, such as alkylene urea (ethylene urea, crotonylidene urea, etc.), arylene urea (imesatin, etc.), dicarboxylic acid Acid ureides (parabanic acid, barbituric acid, isocyanuric acid, peramyl, etc.), j8-aldehyde acid ureides (peracyl, thymine, perazole, etc.), ⁇ -oxyacid ureides (hydantoins, eg, h
- crotilidene direa dioleide of ⁇ -hydroxy acid (1,1, -methylenebis (5,5-dimethylhydantoin), etc.), diurea such as ⁇ -perazine, diureide of dicarboxylic acid (aloxanthin, purpuric acid, etc.) Etc.].
- Amino acids include ⁇ -amino acids [monoaminomonocarboxylic acids (glycine, alanine, oral isine, isoleucine, fenylalanine, tyrosine, serine, proline, hydroxyproline, tryptophan, methionine, cysteine, ⁇ -aminobutyric acid, Xahydropicolinic acid, etc.), monoaminodicarboxylic acids (aspartic acid, glutamic acid, asparagine, glutamine, hexahydrodipicolinic acid, hexahydroquinolinic acid, etc.), diaminomonocarboxylic acids (lysine, arginine, histidine, etc.) Amino acids ( ⁇ -alanine, ⁇ -aminobutyric acid, hexahydrocincomeronic acid, etc.), ⁇ amino acids ( ⁇ -aminobutyric acid, etc.), ⁇ amino acids ( ⁇ -amino
- the amino acids may be in D-, L-, or DL-form.
- the carboxyl group may be converted to a metal chloride (such as an alkali metal salt or an alkaline earth metal salt), amidated, or hydrazide.
- a metal chloride such as an alkali metal salt or an alkaline earth metal salt
- amidated, or hydrazide includes amino acid derivatives that are esterified or esterified (methyl ester, ethyl ester, etc.).
- Amino alcohol compounds include monoethanolamine, diethanolamine, 2-amino-1 butanol, 2-amino-2-methyl-1 propanol, 2-amino-2-methyl-1,3-propanepandiol, 2-amino- Examples thereof include amino C aliphatic mono- or polyols such as 2-ethyl-1,3-propanediol and tris (hydroxymethyl) aminomethane.
- aromatic polycarboxylic imides such as phthalimide, trimellitimide, and pyromellitic imide can be used.
- the amido conjugates include aliphatic carboxylic acid amides (malonamide, adipic amide, sebacic amide, dodecane diamide, etc.), cyclic carboxylic acid amides (e.g.
- Aromatic carboxylic acid amides (benzoic acid amide, ⁇ -, m- or ⁇ -aminobenzamide, isophthalic acid diamide, terephthalic acid amide, etc.), polyamide-based resin [for example, nylon 3 (poly j8-alanine), nylon 46, Nylon 6, Nylon 66, Nylon 11, Nylon 12, Nylon MXD6, Nylon 6-10, Nylon 6-11, Nylon 6-12, Nylon 6-66-610, Nylon 9T etc.], Polyester amide, Polyamide imide , Polyurethane, cross-linked Poly (meth) acrylic amide homopolymer or copolymer [such as the polymer described in US Pat. No.
- poly (vinyl lactam) homopolymer or copolymer [poly (N-vinylpyrrolidone) homopolymer or copolymer] Polymers and the like] (for example, homo- or copolymers described in JP-A-55-52338 and U.S. Pat. No. 3,204,014), poly (N-vinylcarboxylic amide), N-vinylcarboxylic acid Copolymers of amides with other bullet monomers (for example, JP-A-2001-247745, JP-A-2001-131386, JP-A-8-311302, JP-A-59-86614, U.S. Pat. 5455042, U.S. Pat. No. 5,407,996, and homo- or copolymers described in U.S. Pat. No. 5,338,815).
- poly (vinyl lactam) homopolymer or copolymer [poly (N-vinylpyrrolidone) homopolymer or cop
- organic carboxylic acid a carboxyl group-containing compound having a pKa of 3.6 or more can be used.
- organic carboxylic acids include the organic carboxylic acids described in JP-A-2000-239484.
- Examples of the metal salts of organic carboxylic acids include salts of organic carboxylic acids with metals (such as alkali metals such as Li, Na and K; alkaline earth metals such as Mg and Ca; and transition metals such as Zn).
- metals such as alkali metals such as Li, Na and K; alkaline earth metals such as Mg and Ca; and transition metals such as Zn).
- the organic carboxylic acid forming the metal salt may be a low-molecular or high-molecular-weight (! / ⁇ ) long-chain saturated or unsaturated aliphatic carboxylic acid exemplified in the section of the long-chain fatty acid.
- lower saturated or unsaturated aliphatic carboxylic acids having less than 10 carbon atoms, polymers of unsaturated aliphatic carboxylic acids, and the like can also be used.
- monocarboxylic acid may have a hydroxyl group.
- the lower saturated aliphatic carboxylic acids include saturated C monocarboxylic acids (acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isoval
- Succinic acid dataric acid, adipic acid, pimelic acid, cornic acid, azelaic acid, etc.).
- Examples of the polymer of the unsaturated aliphatic carboxylic acid include a polymerizable unsaturated carboxylic acid [a, an ethylenically unsaturated carboxylic acid, for example, a polymerizable unsaturated monocarboxylic acid such as (meth) acrylic acid, and the like.
- Polymerizable unsaturated polycarboxylic acids such as itaconic acid, maleic acid and fumaric acid
- acid anhydrides or monoesters of the above-mentioned polycarboxylic acids such as mono-C alkyl esters such as monoethyl maleate
- olefins ethylene A C, such as propylene
- organic carboxylic acids or metal salts of organic carboxylic acids can be used alone or in combination of two or more.
- Alkali or alkaline earth metal compounds include metal oxides such as CaO and MgO, metal hydroxides such as LiOH, Ca (OH) and Mg (OH), and metal inorganic acid salts (LiCO, NaCO ,
- Metal carbonates such as KCO, CaCO, and MgCO; inorganic acid salts such as borate and phosphate
- metal oxidized products and metal hydroxylated products are particularly preferred.
- an alkaline earth metal compound is preferable.
- alkali or alkaline earth metal compounds can be used alone or in combination of two or more.
- talcites in the mouth and the mouth examples include talcites in the mouth and the mouth described in JP-A-60-1241 and JP-A-9-59475. Saito daggers and the like can be used.
- M 2+ is Mg 2+, Mn 2+, Fe 2+ , a divalent metal ion such as Co 2+, M 3+ is Al 3+, Fe 3 +, 3 such as Cr 3+ Indicate valent metal ions, where A n — is an 11-valent (such as CO 2 —, OH—, HPO 2 —, SO 2 )
- hide mouth talcites can be used alone or in combination of two or more.
- Hydrate talcite is available from Kyowa Chemical Industry Co., Ltd. under the name of "DHT-4A”, “DHT-4A-2", “Almizer Meiser”. [0096] (e) Zelite
- zeolite examples include, but are not particularly limited to, zeolite other than the H-type, for example, a zeolite described in JP-A-7-62142 [the minimum unit cell of which is an alkali and a crystalline aluminosilicate of Z or alkaline earth metal.
- zeolite described in JP-A-7-62142 [the minimum unit cell of which is an alkali and a crystalline aluminosilicate of Z or alkaline earth metal.
- zeolites can be used alone or in combination of two or more.
- the phosphine compounds include alkyl phosphines (for example, tri-linear or branched C alkyl phosphines such as triethyl phosphine), cycloalkyl phosphines (for example,
- Tri C cycloalkyl phosphine such as tricyclohexyl phosphine), aryloxy
- Sphines eg, triphenylphosphine, p-tolyldiphenylphosphine, di-p-tolylphenylphosphine, tri-m-aminophenylphosphine, tri (2,4-dimethylphenyl) phosphine, tri (2, Amino group such as 4,6-trimethylphenyl) phosphine, tri (o-, m- or p-tolyl) phosphine, etc.
- Tri-C aryl which may have a substituent such as C alkyl group
- aralkylphosphine for example, tri (C-aryl-alkyl) phosphine such as tri (o-, m- or p-a-silylphosphine), arylalkylphosphine, etc.
- Fins eg, mono- or di-C aryl phosphine such as diphenyl phosphine, aryl diphenyl phosphine or mono C aryl phosphine
- Mono- or di-C-aryldi- or mono (C-arylC-alkyl) phosphines such as sphines (for example, p-silyldiphenylphosphine, di (p-silyl) phenylphosphine)
- Phosphine compounds such as [fuino) C alkane]. Phosphination of these compounds
- the compounds can be used alone or in combination of two or more.
- heat resistant stabilizers can be used alone or in combination of two or more.
- basic nitrogen-containing compounds and metal salts of organic carboxylic acids, alkali or alkaline earth metals When the compound, the talc, the talcite, the zeolite, and the phosphine compound are used in combination with at least one selected compound, the heat resistance can be imparted in a smaller amount.
- the ratio of the heat stabilizer is, for example, 0.001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the polyacetal resin.
- a range of about 0.3 parts by weight, more preferably about 0.005 to 3 parts by weight (particularly 0.01 to 2 parts by weight) can be selected.
- weather (light) stabilizer examples include (a) a benzotriazole compound, (b) a benzophenone compound, (c) an aromatic benzoate compound, (d) a cyanoacrylate compound, and (e) Acid-based compounds, (1) hydroxyaryl 1,3,5-triazine-based compounds and (g) hindered amine-based compounds.
- Benzotriazole-based compounds include 2- (2'-hydroxy-5'methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di (t-butyl) phenyl) benzotriazole, Hydrate such as 2- (2'-hydroxy-3 ', 5'-di (t-amyl) phenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-diisoamylphenyl) benzotriazole Benzotriazole having aryl group substituted by xyl group and C alkyl group
- hydroxyl groups such as 2- [2'-hydroxy-3 ', 5'bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] benzotriazole and aryl groups substituted with aralkyl (or aryl) groups Having a benzotriazole substituted with a hydroxyl group and an alkoxy (C alkoxy) group such as 2- (2'-hydroxy-4 'otatoxyl) benzotriazole
- Benzotriazoles having a phenyl group are preferred.
- benzophenones having a plurality of hydroxyl groups Di to tetrahydroxybenzophenones such as 2,4-dihydroxybenzophenone; benzophenones having a hydroxyl group such as 2-hydroxy-4-hydroxybenzylbenzophenone and a hydroxyl-substituted aryl or aralkyl group); Benzophenones having a hydroxyl group and an alkoxy (C alkoxy) group (2-hydroxy-4-methoxybenzene)
- Nzophenone 2-hydroxy-4-otatooxybenzophenone, 2-hydroxy-4-dodecyl xybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophene
- 2-hydroxy-4-methoxy-5-sulfobenzophenone and the like.
- benzophenones having a hydroxyl-substituted C aryl (or C aryl C alkyl) group together with a hydroxyl group, particularly
- Nons are preferred.
- aromatic benzoate-based compound examples include alkylaryl salicylates (particularly, alkylphenol salicylate, etc.) such as p-t-butylphenol salicylate and p-octylphenol-salicylate.
- cyanoacrylate compounds examples include 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate and cyanyl-containing diaryl acrylates such as ethyl-2 cyano-3,3-diphenyl acrylate. (Particularly diphenyl atalylate containing a cyano group) and the like.
- oxalic acid-based compounds examples include N— (2-ethylfuryl) N ′ — (2-ethoxy-5tbutylphenyl) oxalic acid diamide, N— (2-ethylfuryl) N ′ (2-ethoxy
- examples thereof include oxalic acid diamides having an aryl group (such as a phenyl group) substituted on a nitrogen atom such as (phenyl) oxalic acid diamide.
- Hydroxyaryl 1,3,5-triazine compounds include 2,4-dicarboxylic 6 — (Mono or dihydroxy C aryl) — 1, 3, 5-triazine [C alkyl with aryl group
- 2,4-diphenyl 6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-di (p-tolyl or 2,4,4-dimethylphenyl) -6 — (2-Hydroxy-4-benzyloxyphenyl) — 1,3-, 5-Hydroxyaralkyloxyaryltriazine such as triazine; 2,4-diphenyl-6- (2-hydroxy-4— ( 2-butoxyethoxy) phenyl) -1
- hydroxyphenyl 1,3,5-triazine compounds in which aryl is a phenol may be used.
- the hindered amine compound As the hindered amine compound, the hinderdamine compound exemplified in the section of the anti-oxidation agent can be used.
- These weather (light) stabilizers may be used alone or may be the same or different. Two or more stabilizers may be used in combination.
- a combination of (g) a hindered amine compound and another weather (light) stabilizer is preferable to use a combination of (g) a hindered amine compound and another weather (light) stabilizer.
- the proportion of the weather (light) stabilizer is, for example, 0 to 5 parts by weight (for example, 0.01 to 5 parts by weight), preferably 0.1 to 4 parts by weight based on 100 parts by weight of the polyacetal resin. Parts, more preferably about 0.1 to 12 parts by weight.
- Various dyes or pigments can be used as the colorant.
- the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, and naphthoquinone dyes, which are preferably solvent dyes.
- azo dyes anthraquinone dyes
- phthalocyanine dyes phthalocyanine dyes
- naphthoquinone dyes which are preferably solvent dyes.
- pigments both inorganic pigments and organic pigments can be used.
- inorganic pigments include titanium pigments, zinc pigments, carbon black (such as furnace black, channel black, acetylene black, and Ketjen black), iron pigments, molybdenum pigments, cadmium pigments, and lead pigments.
- examples include pigments, cobalt pigments, and aluminum pigments.
- organic pigment examples include azo pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, dioxazine pigments, and sullen pigments. it can.
- the coloring agents as described above may be used alone or in combination of a plurality of coloring agents. If a colorant with a high light-shielding effect (carbon black, titanium white (titanium oxide), phthalocyanine pigment, perylene pigment (particularly carbon black, perylene black pigment), etc.) is used, the weather (light) resistance Can be improved.
- a colorant with a high light-shielding effect carbon black, titanium white (titanium oxide), phthalocyanine pigment, perylene pigment (particularly carbon black, perylene black pigment), etc.
- the content of the colorant is, for example, 0 to 5 parts by weight (for example, 0.01 to 5 parts by weight), preferably 0.1 to 4 parts by weight, and more preferably 100 to 100 parts by weight of the polyacetal resin. Preferably 0.1 It is about 2 parts by weight.
- the polyacetal resin composition of the present invention may contain, if necessary, a conventional additive, for example, an antioxidant (such as a phosphorus-based, iodo-based, hydroquinone-based, or quinoline-based antioxidant).
- a conventional additive for example, an antioxidant (such as a phosphorus-based, iodo-based, hydroquinone-based, or quinoline-based antioxidant).
- Carboxylic acid such as carboxylic acid described in JP-A-2000-239484
- impact modifier [acrylic core-shell polymer, thermoplastic polyurethane resin, styrene elastomer and thermoplastic polyester elastomer] At least one selected from the group]
- gloss control agent [acrylic resin (C alkyl (meth) ataryl
- Styrene-based resin such as styrene homo- or copolymer and at least one selected from styrene-based resin
- slidability improver [olefin polymer, silicone-based resin, and At least one selected from fluoroplastics] release agents, nucleating agents, antistatic agents, flame retardants, foaming agents, surfactants, antibacterial agents, antifungal agents, fragrances, fragrances, various polymers
- Polycarbonate resin, polyolefin-based elastomer or resin, polyvinyl alcohol-based resin, aliphatic polyester-based resin (poly-L-lactic acid, poly-D-lactic acid, poly-DZL-lactic acid, polydalicholic acid, glycolic acid and lactic acid ( Or a copolymer with D-, L- or DZL lactic acid), or a filler may be used alone or in combination of two or more.
- a conventional fibrous, plate-like, powdery or other filler may be used alone or in combination of two or more.
- the fibrous filler include inorganic fibers (such as glass fibers, carbon fibers, boron fibers, and titanate-based lithium fibers (whiskers)) and organic fibers (such as amide fibers).
- the plate-like filler include glass flake, my strength, graphite, and various metal foils.
- Powdered fillers include metal oxides (zinc oxide, alumina, etc.), sulfates (calcium sulfate, magnesium sulfate, etc.), carbonates (calcium carbonate, etc.), glasses (milled fiber, glass beads, glass balloons, etc.) ), Silicates (talc, kaolin, silica, diatomaceous earth, clay, wollastonite, etc.), sulfides (molybdenum disulfide, molybdenum disulfide, tungsten tungsten, etc.), carbides (fluorinated graphite, silicon carbide) And boron nitride.
- metal oxides zinc oxide, alumina, etc.
- sulfates calcium sulfate, magnesium sulfate, etc.
- carbonates calcium carbonate, etc.
- glasses milled fiber, glass beads, glass balloons, etc.
- Silicates talc, kaolin, silica, diatomace
- the polyacetal resin composition of the present invention comprises a polyacetal resin, which may be a granular mixture or a molten mixture, the inhibitor composition, and if necessary, other additives [stabilizer (acid Antioxidants, processing stabilizers, heat stabilizers, weather (light) stabilizers), impact modifiers, gloss control agents, slidability modifiers, colorants and Z or fillers.
- stabilizer acid Antioxidants, processing stabilizers, heat stabilizers, weather (light) stabilizers
- impact modifiers e.g., impact modifiers, gloss control agents, slidability modifiers, colorants and Z or fillers.
- the inhibitor composition is prepared by mixing carboxylic acid hydrazide and hydroxy polycarboxylic acid metal salt in advance, and then mixing each component with other components (polyacetal resin and, if necessary, other additives). , And the other components.
- the polyacetal resin composition is prepared by, for example, preparing (1) pellets by extruding by kneading with an extruder (such as a single-screw or twin-screw extruder) a main feed rocker feed of all components, and extruding.
- an extruder such as a single-screw or twin-screw extruder
- a component such as a metal salt of hydroxy polycarboxylic acid, polyacetal resin, or the above-mentioned other additives which does not contain carboxylic acid hydrazide in the inhibitor composition;
- a method comprising feeding a component containing acid hydrazide (other components such as polyacetal resin and the above-mentioned other additives) through a side feed rocker, kneading and extruding with an extruder to prepare pellets, and then molding (3. )
- a component containing a part of the inhibitor composition (polyacetal resin, other additives, etc. as other components) from the main feed port, and a component containing the rest of the inhibitor composition.
- the method (4) is carried out by feeding the components (polyacetal resin, other additives, etc. as other components) also to a side feed rocker, kneading and extruding with an extruder to prepare a pellet, and then molding.
- the inhibitor composition is added to a polyacetal resin pellet. After coexisting or adhering by spraying, coating (surface coating or the like) or the like, a method of molding and obtaining a molded article having a predetermined composition can be adopted.
- the above methods (1), (2) and (3) are preferred, and in particular, melt mixing in a single-screw or twin-screw extruder having one or more devolatilization vent ports. Is preferred.
- side feed of carboxylic acid hydrazide is possible from either the feed port before or after the devolatilization vent port.
- water and processing aids such as Z or alcohols (methanol, ethanol, isopropyl alcohol, n-propyl alcohol, etc.) are injected from the feed port before the pre-blend or devolatilization vent port, and deaerated.
- the ratio of water and Z or alcohols is not particularly limited, and a force in the range of 0 to 20 parts by weight based on polyacetal resin loos by weight can be generally selected, preferably 0.01 to 10 parts by weight, More preferably, it may be about 0.1 to 5 parts by weight.
- the melt-kneading time (average residence time) in the extruder is short, for example, 300 seconds or less (for example, about 5 to 300 seconds), preferably 250 seconds or less (for example, about 10 to 250 seconds), and more preferably.
- the extrusion preparation method is preferably used for a time of 200 seconds or less (for example, about 10 to 200 seconds), particularly about 10 to 150 seconds.
- the powder of the polyacetal resin serving as the base for example, a powder obtained by pulverizing part or all of the polyacetal resin
- other components When mixed with an aldehyde inhibitor composition and other additives (stabilizer, impact modifier, gloss control agent, slidability modifier, coloring agent and Z or filler, etc.) and melt-kneaded, This is advantageous for improving the dispersion of additives.
- the polyacetal resin composition of the present invention can remarkably suppress the formation of formaldehyde due to oxidation or thermal decomposition of the polyacetal resin, particularly in a molding (particularly, melt molding) step, and The environment can be improved. Further, it is possible to prevent the resin or the resin composition from being discolored due to the carboxylic acid hydrazide during the extrusion process or the molding process.
- the present invention also includes a molded article formed from the resin composition.
- the molded article of the present invention contains a combination of a polyacetal resin and an aldehyde inhibitor composition, and is excellent in extrusion and Z or molding stability, and generates a very small amount of formaldehyde.
- molded articles made of conventional polyacetal resins containing stabilizers such as antioxidants generate relatively large amounts of formaldehyde, and in addition to corrosion and discoloration, contaminate the living and working environments. I do.
- the polyacetal resin molded article of the present invention is characterized in that the carboxylic acid hydrazide and the carboxylic acid hydrazide are combined with an aldehyde inhibitor composition comprising a hydroxy polycarboxylic acid metal salt.
- the amount of formaldehyde generated from molded articles can be effectively controlled with a smaller amount of addition than that of a single product to a powerful region where it could not be reached until now.
- the amount of formaldehyde generated is 1.5 g or less, preferably 0 to 1.
- O / zg more preferably about 0 to 0.6 g per 1 cm 2 of the surface area of the molded product, and is usually about 0 to 0.6 g.
- the amount of formaldehyde generated is less than 2. (about 0 to 2 g), preferably 0 to 1.2 g, more preferably 0 to 0.4 g, and more preferably 0 to 2 g per 1 cm 2 of the surface area of the molded article. About 0.2 g can be achieved, and usually about 0.001 to 1.2 g.
- the molded article of the present invention may have the amount of formaldehyde generated in either dry or wet type, and particularly in both dry type and wet type. It often has formaldehyde emission. Therefore, the molded article of the present invention can be used as a material that can cope with a more severe environment.
- the amount of formaldehyde generated in a dry system can be measured as follows.
- the amount of formaldehyde generated by the wet method can be measured as follows.
- the numerical definition of the amount of formaldehyde generated in the present invention is such that a polyacetal resin containing a conventional additive (such as a normal stabilizer or a release agent) is used as long as the polyacetal resin and the aldehyde inhibitor composition are included.
- a polyacetal resin containing a conventional additive such as a normal stabilizer or a release agent
- most of the surface of the molded article (for example, 50-100% ) Can also be applied to molded articles composed of polyacetal resin (for example, multicolor molded articles and coated molded articles).
- the aldehyde inhibitor of the present invention is used in the vicinity of an aldehyde generation source, for example, packaging materials or packaging materials (paper, bags, containers, etc.), building materials (wallpaper, plywood, etc.), filters (nonwoven fabrics).
- an aldehyde generation source for example, packaging materials or packaging materials (paper, bags, containers, etc.), building materials (wallpaper, plywood, etc.), filters (nonwoven fabrics).
- This is useful in applications such as filters, etc., and powdery and granular molded products such as resin pellets.
- the polyacetal resin composition can be formed into various molded products by conventional molding methods (for example, injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, etc.). It is useful for molding.
- the molded article (molded article) of the present invention can also be used for applications where formaldehyde is detrimental! / Slippage (for example, knobs and levers for bicycle parts). Electric and electronic parts (active and passive parts, etc.), building materials, plumbing parts, daily necessities (life), parts for cosmetics, and medical (medical and medical) parts.
- automobile parts include inner handles such as inner handles, fuel trunk openers, seat belt buckles, assist wraps, various switches, knobs, levers, clips, and other interior parts, and meters and connectors.
- System parts in-vehicle electric and electronic parts such as audio equipment and car navigation equipment, parts that come into contact with metals, such as window regulator carrier plates, door lock actuator parts, mirror parts, wiper motor system parts, and fuel systems And other mechanical components.
- Electric or electronic parts include parts or members of equipment composed of a polyacetal resin molded article and having a large number of metal contacts [for example, audio equipment such as a cassette tape recorder, VTR (video tape) Recorder), 8mm video, video camera Video equipment, or OA (office automation) equipment such as copiers, facsimile machines, word processors, computers, etc., as well as toys that are driven by driving power such as motors and splicers, telephones, keyboards attached to computers, etc.] Can be exemplified. Specific examples include chassis (base), gears, levers, cams, pulleys, and bearings.
- optical and magnetic media parts for example, metal thin film type magnetic tape cassettes, magnetic disk cartridges, magneto-optical disk cartridges, etc.
- optical and magnetic media components include tape cassette components (tape cassette body, reels, hubs, guides, rollers, stoppers, lids, etc.), disk cartridge components (disk cartridge body (case), shutters, etc.). , A clamping plate, etc.).
- the polyacetal resin molded product of the present invention can be used for building materials, piping parts, fasteners (slide fasteners, snap fasteners, hook-and-loop fasteners) such as lighting fixtures, fittings, piping, cocks, faucets, toilet peripheral parts and the like. , Rail fasteners, etc.), stationery, lip balm 'lipstick containers, washers, water purifiers, spray nozzles, spray containers, aerosol containers, general containers, needle holders, etc. It is suitably used for medical related parts.
- processing stability (discoloration tendency of molded products), and the amount of formaldehyde generated in dry and wet molded products were as follows. Was evaluated.
- a flat molded product (100 mm X 40 mm X 2 mm) of a specific shape is molded from the pellets formed of the polyacetal resin composition, and the discoloration (hue) of the molded product is evaluated by visual observation. did.
- a plate-like test piece (10011111 ⁇ 40111111 2111111; total surface area: 85.6 cm 2 ) was prepared from a polyethylene bottle (1 L capacity) containing 50 mL of distilled water.
- Carboxylic hydrazide, hydroxy polycarboxylic acid metal salt, antioxidant, processing stabilizer, heat stabilizer, coloring agent, weather (light) stabilizer are added to 100 parts by weight of polyacetal resin copolymer in the proportions shown in Table 1.
- LZD 35
- extrusion temperature 200 ° C
- screw rotation speed 100 rpm
- the degree of vent vacuum was 70 cmHg (93. lkPa), the discharge amount was 15 kgZhr, and the average residence time was 100 seconds) to prepare a pellet-shaped composition.
- Example 4 After pre-blending 95 parts by weight of polyacetal resin copolymer with a metal salt of hydroxy polycarboxylic acid, an antioxidant, and a processing stabilizer in the proportions shown in Table 1, a 30 mm diameter twin shaft with one reduced pressure vent port While being charged into the main feed port of the extruder, 5 parts by weight of the polyacetal resin copolymer and 0.1 part by weight of carboxylic acid hydrazide were charged from the side feed port and melt-mixed to prepare a pellet-shaped composition. Using the obtained pellets, a predetermined test piece was molded by an injection molding machine, and the processing stability (discoloration of the molded product: hue) and the amount of formaldehyde generated from the test piece were evaluated. Table 1 shows the results.
- a predetermined test piece was molded by an injection molding machine, and the color of the test piece and the amount of formaldehyde were evaluated. As a result, the hue of the molded product was white, and the amount of formaldehyde generated was 0.08 ⁇ cm in dry type and 0.14 ⁇ gzcm in wet type.
- the stabilizers are as follows.
- the above melt index is a value (gZlO content) determined under the conditions of 190 ° C and 2169 g according to ASTM-D1238.
Abstract
Description
Claims
Priority Applications (4)
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EP04792841A EP1683838A4 (en) | 2003-11-10 | 2004-10-22 | ALDEHYDINHIBITOR COMPOSITION AND POLYACETAL RESIN COMPOSITION |
CN2004800401800A CN1902279B (zh) | 2003-11-10 | 2004-10-22 | 醛抑制剂组合物和聚缩醛树脂组合物 |
US10/578,304 US20090143506A1 (en) | 2003-11-10 | 2004-10-22 | Aldehyde inhibitor composition and polyacetal resin composition |
KR1020067011396A KR101098086B1 (ko) | 2003-11-10 | 2006-06-09 | 알데히드 억제제 조성물 및 폴리아세탈 수지 조성물 |
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JP2003380187A JP4516301B2 (ja) | 2003-11-10 | 2003-11-10 | ポリアセタール樹脂組成物 |
JP2003-380187 | 2003-11-10 |
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US (1) | US20090143506A1 (ja) |
EP (1) | EP1683838A4 (ja) |
JP (1) | JP4516301B2 (ja) |
KR (1) | KR101098086B1 (ja) |
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Also Published As
Publication number | Publication date |
---|---|
US20090143506A1 (en) | 2009-06-04 |
TW200519161A (en) | 2005-06-16 |
KR101098086B1 (ko) | 2011-12-26 |
TWI354687B (en) | 2011-12-21 |
JP2005137785A (ja) | 2005-06-02 |
EP1683838A1 (en) | 2006-07-26 |
CN1902279A (zh) | 2007-01-24 |
JP4516301B2 (ja) | 2010-08-04 |
KR20070012322A (ko) | 2007-01-25 |
EP1683838A4 (en) | 2008-08-13 |
CN1902279B (zh) | 2010-11-24 |
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