WO2007037446A1 - Polyacetal resin composition and molded article - Google Patents

Abstract

A stable polyacetal resin composition in which the amount of formaldehyde to be generated is on an extremely low level and which, even when placed in a closed space, does not adversely influence coexistent moldings of other resins. The polyacetal resin composition is characterized in that it comprises (A) 100 parts by weight of a polyacetal resin and (B) 0.01-5.0 parts by weight of a carboxylic acid hydrazide compound and that the carboxylic acid hydrazide compound (B), upon 10-minute heating at 200°C, generates hydrazine in an amount of 10 ppm or smaller in an examination by the head-space GC/MS method.

Description

Holacetal resin composition and molded product Technical field

 The present invention relates to a molded product formed from a stable resin composition of holacetal resin which suppresses the amount of formartite generated to an extremely low level and does not adversely affect other resin molded products. Background technique l

 Holiacetal resin is excellent in mechanical properties, fatigue resistance, friction resistance, wear resistance, and molding, so it is widely used in fields such as automobile parts, electrical equipment parts, daily life, cosmetic parts, and medical parts. As a result of advanced sophistication, it becomes more stable High quality holacetal resin with very little generation of mualthite.

US patent publ ication 3 1 5 2 1 0 1 Column 1 and column 3 include lucoholimer and specific sulfonate sulfonates (3- to 10-carbon sulfonate sulfonates, aromatic benzoate, aromatic sulfonates) It is disclosed whether it is an ancestor that contains a tribal nocarant. When these carboxylic acid hydrates are used, the stability is improved to some extent, and formaldehyde is generated. However, even if these carboxylic acid hydranoto compounds are used, the results are not sufficient. In addition, such a sulfonic acid hydranoto compound Disclosure of the invention

 The present invention provides a settal resin composition that suppresses the amount of formaldehyde that is generated to an extremely low level and does not adversely affect other resin molded products that coexist even in a sealed space, and a molded product formed from the resin composition. The present inventor conducted a search for a series of hydrocarbon compounds with respect to stabilizers for holacetal resin. As a result, formaldehyde obtained from a molded product of a specific benzoic acid hydrogenant acetal resin composition can be extremely suppressed and sealed. The present invention has been completed by finding that other resin molded products are adversely affected in space.

 That is, the present invention comprises: (A) 100 parts by weight of a holacetal resin and 100 to 50 parts by weight of a sulfonic acid hydrogenant compound, and the carnot compound (B) is 200. This is related to the Horia ancestral compound, characterized in that the amount of hetolanone produced by heating for 10 minutes is less than lOppm.

According to the present invention, the form produced from the molded article of the polyacetal resin composition can be suppressed to a very low level by adding a specific hydrate of carboxylic acid to the polyacetal resin. Furthermore, the molded product of the polyaceter has an adverse effect on other resin molded products that coexist even in a sealed space, and can improve stability and reliability. In addition, there is a specific thing that is not impaired by the presence of the additive of the present invention (weather resistance (light) stabilizer impact resistance improver slidability improver gloss control colorant etc.) According to the holiacetal resin composition and Detailed Description of the Invention

 The polyacetal resin composition of the present invention comprises a phosphonate hydranoto compound (B) of a horiacetal resin (A), and is obtained by molding the holacetal resin composition. Give an explanation.

 The horiacetal resin (A) used in the present invention is a polymer compound having okinomethyle as a constituent unit, and includes polyacetals containing other constituent units in addition to the horiaceter quinomethyleno group. In addition, the branched structure, the structure having a skeleton structure, the one having the furonoc structure, and all the conventionally known holiacetal resins are generally compared with the generalized holiacetal homopolymer, which is a water-filled formartite or a formaldehyde cyclic trimer. The polymerization of some trioxano is usually stabilized against cocoon degradation by terminal canov.

 In addition, the horiacetal co-polymer generally has a terminal labile portion by hydrolysis by copolymerizing form ore alartite with cyclic olicoma as a king monomer and a compound selected from cyclic ether or ruthene as a comonomer. For removal by soot decomposition, the main monomer is generally trioxy, which is a cyclic trimer of formartite. Trioxano is generally obtained by refining the aqueous solution of water in the presence of an acidic catalyst and then purifying by distillation. Trioxano is substantially preferred for impurities such as water, methanol and formic acid.

In addition, as comonomer cyclic ether and cyclic formal Further, as a comonomer component capable of forming a branched structure or a crosslinked structure, an linoleno eno eno linole eno linole eno linole eno linole eno linole eno linole no naphthyl clinino nor ether Cornolenc Nonnore Chilenogli Cornolenocri Nonolete nore Alcoleno or Polyalkylene Cricol Nocrino Nore These comonomers are used singly or in combination of two or more. In the present invention, the formation of formartite is preferably used from the viewpoint of a lower level of rehabilitation. Among these, compounds selected from (a-1), cyclic ethers and cyclic formals (above the former (a-1) the latter (a-2) = 9 9 9/0 1 to 8 0 (Weight ratio) It is preferable to be copolymerized or more preferably the latter = ratio of 9 95/0 5 to 9 0 0/100 (weight ratio).

 In addition, as a compound selected from cyclic ethers and cyclic formals, it is particularly preferable to use one of the following:

The above-mentioned holacetal copolymers are generally obtained by carrying out cationopolymerization using an appropriate amount of cationopolymerization catalyst. Molecular weight regulator used cationopolymerization catalyst Polymerization method Polymerization equipment Deactivation treatment of the polymer The obtained crude holiacetal coholomerization treatment / undone is known from many literatures, and basically they can be obtained. Next, the citrate phosphono acid compound (B) used in the present invention is a strong lponoate citrate compound that has been released from histolone by a GC / MS method using a hetosose GC between two. Henotos ^^ Iss GC Analytical analyzer Example: Henotos ^^ Susanofra Selective Detector 5973 manufactured by Anolenot Co., Ltd. To detect. The detection temperature is kept at 50 ° C, the temperature is raised at a rate of 10 ° C / min, GC / MS is measured, and the corresponding heater is assigned. In addition, it is determined that no detection is actually caused by the detection sensitivity (S / N).

 Carboxylic acid histanoto compound (B) used in the present invention is an amount of hydranono generated by decomposition of caranoto compound by heating at 200 ° C for 10 minutes, which is a general processing condition of a holoa composition, or less than lOppm. The When the amount is higher than the amount of hydrano produced by decomposition of the hydranoto compound of the benzoic acid, it has a negative influence on the hydranone and / or its anti-component in the holiasta product to which the hydranoto carboxylic acid compound is added. I have something to do. Carboxylic acid used in the present invention

As (B), it is particularly preferred that it does not substantially generate hydranono. Also, it is possible to obtain a sulfonic acid hydranoto compound used in the present invention.

(1) How to add estenole of carboxylic acid (including alkyl ester and hydranone hydrate) / Left (2) Method of reversing halonic acid of carboxylic acid 3) How to add / remove carpanoate (4) How to make acid with citrate for carboxylic acid and (5) Urate of hyponoic acid and hypohalokenoate It is possible to use it.

 As a specific chemical structure in which it is difficult to substantially release the sulfonic acid hydranoto compound by heating at 200 ° C. for 10 minutes, a sulfonic acid hydranoto compound having the following chemical formula (1) is preferable.

[Wherein X represents an aromatic ring, R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms, an elementary atom or an alkyl group or an ananol group having 1 to 30 carbon atoms, an integer of 4 and b represents 0 to Indicates an integer of 4. ]

 In the formula (1), the aromatic ring represented by X includes a hezeneno ring, an anthraceno ring, an aromatic ring such as a phenanotreno ring, and the like [Hifeninore, Hysarrelealkano (Nofeninoremethane 2, Rufrohan ]) Something is mentioned. The aromatic ring X is preferably a no-ring naphthalene ring.

In the formula (1), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms and is a substituent bonded to the carbon atom constituting the above. Carbonization represented by R ¹ is an alkynole group (a methyl group, an ethyl group, an inofuroyl group, a butyl group, an s —a butyl group, a linear or branched alkyl group such as a t-butyl group) An integer of 0 to 3, especially an integer of 0 to 2 is preferred. Further, when it is an aromatic ring X, a is preferably an integer of 0 to 4, particularly an integer of 0 to 2. In the above case, R ¹ may be the same or different.

In the formula (1), the group 1 OR ² is a carbon substituent constituting the ring of the aromatic ring X. The group OR ² is a derivative of a hydrogenoquinoloxy group that is R ² or hydrogen (alcohol having 1 to 30 carbon atoms, such as a methoxy group, ie R ² is an alkyl group, such as a methyl group) acetyl group And the silicon group.]

In the formula (1), the number b of the group OR ² bonded to the aromatic ring X is an integer of 0 to 4, preferably an integer of 0 to 3, preferably an integer of 0 to 2. For example, when an aromatic ring is X or a henoseno ring, an integer of 3, particularly an integer of 0 to 2, is preferred. When aromatic ring X or naphth is used, b is preferably an integer of 0 to 4, particularly preferably an integer of 0 to 2. In this case, the base OR ² may be the same or different.

Examples of the carboxylic acid and its derivative used in the carboxylic acid hydranoto compound (B) used in the present invention include benzoic acid m-toluic acid p-toluic acid 2-ethyl benzoic acid 3-acid 4 1-ethyl benzoic acid 4 1 ^ f Noprohill benzoic acid 4 1 n-Phic acid 2 3 4 5—Tetramethylbenzoic acid Hentamethyl benzoic acid Nomethyl benzoic acid 2, 4-Nomethyl benzoic acid 2 5— Nomethy 6-nomethylbenzoic acid 3 4-N-methylbenzoic acid 3, 5--no 2, 3 4 Trimethylbenzoic acid 2 3 5-Trimethylbenzoic acid 6-Trimethylbenzoic acid 2 4 5-Trimethylbenzoic acid Perfume acid 2 Benzoic acid 2,4,5-trichitoquinobenzoic acid 2,4 6-benzoic acid 3-methylsalicylic acid 4-methylsalicylic acid 5-hydroxylic acid 3-hydroxyquinoic acid 2-methylbenzoic acid 2—Hytroquino 3, rubenzoic acid 3—Hytroquino 4—Innoprohill benzoic acid 2—Hi —Innoprohill 1 6—Methyl benzoic acid 4 6—Nohi troquine 1 2 Perfic acid 2,6—Nohi troquino 4-Methylbenzoic acid 3, 5--No 4-Hydroxyquinobenzoic acid 3-Methyl mono 5--t-Futyl 4-Hyto acid Olysellino acid Nohalic acid Orihetol carbanoic acid Suwe phono acid Methyl lysellino acid 4-Hytrok Norserino acid 6- An benzoic acid compound with lucerino acid 1-Naphthoic acid 2-Naphmethyl-1 Mononaphthoic acid 4-Methyl1-1 Mononaphthoic acid 5-Methylthioic acid 6-Methyl-1-Naphthoic acid 7- Methyl-1 naphtho lu 1 1 naphthoic acid 1 Methyl-2-naphthoic acid 4-Methyl-acid 5-Methyl-2-Naphthoic acid 6-Methyl-2-Naphthoic acid 2-Naphthoic acid 2-Hytroquino 1 Mononaphthoic acid 4-Hydroxy acid 5-Hytroquino 1 Naphthoic acid 7—Hytroquino 1—1—Hytroquino 2—Naphthoic acid 3—Hytroquino 2—Naphtho Mouth quino 2—Naphthoic acid Naphthoacetic acid compounds Power Norenophonic acid 4-Methinole 1-Anthracenoic acid 4-Fenenole 1-Anthracenocaric acid 9 1 Feniruro Cenocarnoic acid 1 0—Phenenolei 9-Anthracenocarnoic acid 1 2-Anthracene Norenoic acid 2-Methinore 9 Hueninolay 1 ー Norenonoic acid 6-Ethenole 9-Phenanotrenocanoreponoic acid 6 8 -—— Anthracene carboxylic acid system with phenanotren carboxylic acid 4-Hitrokinofeninore 4—Historinore system with cyanorenoic acid Mention may be made of sulfonic acid and its derivatives.

 The characteristic structure of the carboxylic acid hydranoto compound (B) used in the present invention is as follows. In the above formula (1), an aromatic ring X or a naphthalene ring is a linear or branched alkyl group, and a is an integer of 0-2. Yes b Lists a number of compounds.

 The sulfonate sulfonate compounds of the present invention may be used alone or in combination of two or more. The ratio of these forceful ruponoacid hydranoto compounds (B) is from 0 to 1 to 50 parts by weight, preferably from 0 to 30 parts by weight, more preferably from 0 to 20 parts by weight If the amount of the sulfanoic acid hydranoto compound (B) is too small, it is difficult to effectively reduce the amount of formaldehyde. If it is too much, moldability and mechanical properties. The use of a specific hydrocarbon compound such as this significantly reduces the amount of resin generated from the resin composition and its molded product, and the molded product has no adverse effect even in a sealed space. Stability of things ["It comes to make it live."

The holiacetal resin composition according to the present invention further includes (C) an anti-oxidation anti-fatigue stabilizer (E) a processability improver (F) a weather resistance (light) stabilizer, an improver, a sliding improver, a gloss control agent, and a filler. Select from agents and colorants ,

It is preferable to add an antioxidant in order to keep the short-term and long-term characteristics and to suppress the formate that accompanies decomposition.

Antioxidants include hinotate phenolic compounds hinotartolino compounds iow compounds nitroquino compounds quinolinos. These antioxidants may be used alone or in combination of two or more. Of these, hinotatofu: ϋnor compounds and hinotates are preferred, particularly preferably hinotatophenol compounds. As hinotatophenol compounds, monocyclic hinotatofus are, for example, 2,6-no-t-butyl-ρ-clenol. Example 2 '—methylene hiss (4-methinole 6—t-futino lefenol) tyrenohis (2,6-t-no tyfino lephenol) 1 1 3—Methyl-4-Hydroxyquinone 5—t-Futylphenyl) Phthano 4, Tenhis (3_Methyl-1-t-Futinorephenol) 1 3 5-2 4 6—Tris (3 5-N t-Futinore 4—Hytroquino Noseno 4, 4 ′ —Thihos (3-Methinore 6-t-Futinorephenol A hinotatophenol compound having an ester group or an amino group Examples Kutadenonore 3— (4 '— Hitroquino 3' 5 '— No t—Futino flochnate n—Octatenor 1 2— (4 ′ — Hetroquino 3 ′ — t-Futinorephenyl) Frohionate 1, 6—Hexanone (3 5--No t-Futinore 4-Hiroquinofenol) Fluoroethylene ethylene glycol 1 [3- (3-T-Futyl 5-Methylquinophenyl) Fluoronate] Hetaerythritol tetra 2-[1 1 (2-Hytrokino 1 3 5-No t-Hentylphenyl)

4 6—None t — Hetino ref.

5—None t—Futinore 4—Hi troquinohe non-phosphorone N Methylenohis (3 5—None t—Futinore 4—H trokino nochitomit NN '—Ethylene hiss [3— (3 5—No t —Futyl I Nophenyl) Fluoroamino] NN '—Tetramethylene hiss

5—No toff chinore 4—hetroquinofenore) Flohyanoamito] Hexamethylene hiss [3— (3 5—None t—Futinore 1—4-toluene) furohinoamito] NN —Ethylene hiss [3-(3—t -Methyl-4-Hitroquinophenyl) Fluoroamito] NN 'Tylene hiss [3— (3— t-Futyl 1 5--Methyl 1 4-Hytroquino lohioamito] NN ′ — His [3— (3 5—No 1 t-Futino Mouth Quinophenyl) prohynol] hitranono N, N '— hiss [3 fuchinole 1-methinole 1 4-hitrokinofenore) furohinore]

3 5-Tris (3 5-N-t-Futyl 4-Hirokinohenonourate 1 3 5-Tris (41 t-Futinoley 3-Hirokino methylhennor) Innoanurate.

Examples of the hinotamino compounds include ester group-containing helicopters such as 4-acetoquinone 2 2 6 6-tetramethylhihelino iroloquino 1 2 2 6 6-tetramethylhihelinone 4-oxoquino 1 2 2 6 6-te tramethinoleheli Non 4 Ihenono 2 6 6-Tetramethylhihelinono hiss (2 2 6 6-Te 4-Helinor) Oxalate His (2 2 6 6-Tetrame (2, 2 6, 6-Tetramethyl-4-hyhelinol) Henosenotricarloquinolate and ether group-containing hihelino derivatives Examples Tokino 1 2 2 6 6-Tetramethylhihelinone 4-nochrome-2, 2, 6 6—Tetramethylhihelinone 4—Phenenoquino 2 —Tetramethylhihelinone 4—Henonorkino 2, 2 6 6 Ruhihelino 1 2—His (2 2 6 6—Tetramethyl 1 4 oquino) Containing hyherino derivatives For example, [Lucal hamolukino) 1, 2, 2 6 6-tetramethylhihelin 2, 6 6-tetramethylolene 4-hihelinol) hexamethylene 1-1. Also included are high molecular weight hyhelinono derivatives.

 These antioxidants (C) are used alone or in combination of two or more, and the blending ratio when blending the antioxidant (C) is preferably 0 to 1 to 50 parts by weight with respect to the holiacetal tree. 0 parts by weight Particularly preferably, the amount is 0 0 3 to 20 parts by weight.

 (D) Anti-stabilizer

 Whether or not the Holacetal resin composition of the present invention is blended with a weathering stabilizer in order to maintain the various properties of the resin by suppressing the decomposition of the extrusion process and the molding process, and to suppress the generation of the minute component of the resin. Stabilizers include organic carboxylic acid metal salts, basic nitrogen-containing compounds, alkaline earth metal compounds, high-mouth talcite, zeolites, and the like.

L i N a K is the metal that forms the organic carbonate metal salt It may have a nitroquinol group. The organic carboxylic acid that forms the organic carbonic acid may be a copolymer with a polymerizable unsaturated carboxylic acid (such as (meth) acinoic acid fumaric acid hydrolyzed maleic acid monoethyl maleate). Ingredients of such organic carboxylic acids and lithium quinoate potassium quenoate sodium quinoate lithium 12-alkali phonate with lithium humanloquinostearate acne macneum acetic acid carnoum acetic acid macnoic acid carnoum stearino acid carnoum stearino acid matanentro Alkaline earth metal organic carbonates such as quinostearino acid, noum 12-hytroquinostearino, etc. Of the organic carbonate metal salts such as ionomer resins Preferred is a metal salt such as McInnoum stearino acid carnoum 12 2-hytronoic acid mac or nitroum 12-hytroquinostearino acid carnoum.

 Examples of the basic nitrogen-containing compound include amino trianinated non-compounds, urea compounds, amino acid compounds, amino alcohol compounds, amino compounds, and hyranone compounds.

Amino trianone compounds include melamino or its derivatives, quaana derivatives, amino trianone resins and the like. Examples include melamino derivatives and melems, and examples of quaamino derivatives include alkyl quanamino alkyl substituted quamino amino guanhon guanamino reno-hysqua amino amino acid hexano calqua guanamino and fatty acid heno quanoamino phenyl Nonoguanamino HI Torokino Examples include Mualthite resin. In addition, the melamino derivative qua has a hydrogen or methylol group or an alkoxyquinomethyl group of the amino group (for example, mono-hexamethylol melamino mono-hexa melamino mono-tetramethylquinomethyl henoquaminoamino) is also converted to a guanino compound. Is an acyclic guaninono (Cryconoamino quinanono anano guaninonoto) Cyclic guaninono (Criconoathininooxalyl guaninono 2 4-Ninominoharahanic acid group-substituted uranol compound (Iminouranool guananone) Ruic acid iminoto Rino Nato) Malonyl Tartro Yulukanin Menoxalyl Quaninone The urea compound is a non-cyclic urea compound [N-substituted urea substituted with a non-urea alkyl group a non-cyclic urea condensate ( Hiureno to Hurea Urea Cyclic nitrogen compound [alkylene urea urea nocarphonic acid ureate] 3—arteic acid ureate α uret (Hitanotino 5-methinolehitantoino 5-fuenino 5-henenorehitano Toino 5 5—Nometinorechitatoino 5—Fuenorehitano Toino 5 5—Noueno Rehitano Toino 5 5 Hitanotino Hentametyreno Hisitatoino alanotoino or uric acid Alkyl-substituted uric acid Acetylene urea Chilethenourea α-Oxinoic acid nourate Norphonic acid nourate, etc.

Examples of amino acid compounds include amino acids, amino acids and amino acids. Amino acid compound is D-body L 1,3-Flohanoneol tris (Hytroquinomethyl) Amino memino aliphatic mono- or horiool.

 As the imitating compound, aromatic polyhydric carboxylic acid and phthalic acid, trimellinotic acid, and imitation acid are used. The aliphatic compounds include aliphatic carboxylic acid cyclic carboxylic acids aromatic carboxylic acid amides and oliato resins (for example, HOLIAMITO 3 4 6 HOLIAMITO 6 HOLIAMITE 6 6 HOLIAMITO 1 1 MXD 6 Horiamit 6— 1 0 Horiamit 6— 1 1 Hoolito 6 Holyamito 6— 6 6— 6 1 0 Holyamito 9 T Nato] Holy Tomi Tori Toriuri Tano Hori (Meth) Acrylic Acid Mix Holi (Hynyl lactam) Homo (N-Hinamito) N-Hinyl carboxylic acid and other hinyl monomers.

 The hydranono compounds include aliphatic or cycloaliphatic carboxylic acid hydranoto hydranoto stearino acid hydranoto anonoic acid turkey thranoto tecanodioic acid nitro acid tranoto norhino acid hydranoic unsaturated fatty acid hydranoto quinoline Aromatic fatty acid hydranoto and aromatic benzoic acid hydrano nitro thionotino

Alkali or alkaline earth metal compounds include metal oxides (C a O and) metal hydroxides (L i ○ HC a (OH) ₂ Mg (OH) ₂ acid salts (L i ₂ C0 ₃ N a ₂ C0 ₃ K ₂ C0 ₃ C a C0 ₃ M g C 0 ₃ (M ^{2 +} is wherein ^{Mg 2+ Mn 2+ F e 2+ C} o 2 + Do and 2 Ataikin M ^{3 +} is ^{A l 3+ F e 3+ C r} 3 + Do and trivalent metal ions A ⁿ OH—HP〇 ₄ ² — S〇 ₄ ² —N valence (especially monovalent or divalent) X is 0 <x 0 5 and m is 0 ^ m <l )

 Theite is the smallest unit cell, or Z or Al force crystalline aluminosilicate, for example, A type X or ZSM type zeolite, moorite zeolite, honyaite celite, etc. The

 Phosphino compounds include alkyl phosphines (triethylphos flohinolephosphine trifinorephosphino and nocroanorequinos) and arylphosphines norephosphino p-trinolenofenorephosphino no p-trinolefin Aminophenylphosphinotori (2 4—Norole) Phosphinotori (2 4 6—Trimethinolevenore) Phosph

(o-m- or p-tolyl) phosphine and aralkylkilli (o-m- or p-aninol) phosphino and arreia hininos (nofuenorehininorephosphino arenolenofeninorephos pharyl aralkylphosph Inos (p-anynornophenylphosphine-aninore) Hueninolephosphino Methinolefeinole 1 p-aninore and Hisphosphines (14-His (nophenylphosphino) and other phosphine compounds .

The blending ratio in the case of blending an anti-fog stabilizer is preferably 0 01 to 50 parts by weight or more preferably 0 with respect to 1 holacetal resin. In order to suppress the formation of formaldehyde, a processability improver is recommended.

 Such processing improvers include long-chain fatty acids or derivatives thereof, holanol, noricone compounds, and various sonox.

 Such long-chain fatty acids include monovalent saturated acids or acids having a silicon number of 10 or more (for example, lauric acid, myristino acid, halmitino acid, stearic acid, monotanoic acid, oleino acid, linoleic acid, erucic acid, etc.) silicon, divalent saturation Or an unsaturated fatty acid (for example, sehanonic acid totecanodiic acid nonic acid totesenonic acid). Long-chain fatty acids also include fatty acids that are partially substituted with a substituent such as a hydroxy group (such as 12-hydroxy acid).

 For long-chain fatty acid derivatives, the fatty acid ester and fatty acid amino acid and the alcohol constituting the long-chain fatty acid ester may be either a -valent alcohol or a polyhydric alcohol. An example of an ester of a long fatty acid and a monohydric alcohol is stearate stearylhalmitate.

Examples of esters of long-chain fatty acids and polyhydric alcohols include: Cole mono or Noharmitino acid ester Ethylene glycol mono Phosphoric acid estero retinocricornole mono or Nohenoic acid esterolic mono or nomonotanoic acid ester Chryselino mono to tri Esters Criselinomono to tristearino acid esters Crises Trihenoic acid estenoles Criselino mono to trimonotanoic acid esters Lisli Tonomono to tetrahalmitinoic acid esters Mono- or nolaurate mono- or mono-mono or no stearate mono- or mono-hetenoate mono- or mono-nolate mono- or nolinoleate.

 As fatty acid amines, capryno acid, laurino acid, amino acid, halmitino acid acid, stearic acid amino acid, henoic acid amino acid amino acid, and saturated fatty acid primary acid acid. Torayino acid Amino acid Fatty acid primary acid amino acid Stearyl stearate amino acid Stearate amino acid Saturated and Z or unsaturated fatty acid amino acid secondary mono tyrenone amino amino halmitino acid amino acid Ethylenenoamino mononosomito (ethylene histearylamito) Hexamethylenonoamino acid Amino ethyleneaminoamino Henoic acid Amino ethylene acid Amino acid Ethylenenoamino mononoreino acid Amine Ethylene erucic acid Something such as amito is listed. Furthermore, it is also used as a hysteresis having a structure bonded to the amino moiety of alkylenenoamino such as ethylenenone amino (smit) oleino acid. Of these, hysamine compounds are particularly preferred.

As the above-mentioned polyalkylene glycol, Hori Chileno Cricoe, Hleno Cricol, Hori Tetra Methyleno Cricol, Horial, Polioquine Chileno, Helioquinofuro Fureno Copolymer (Lanonoco Copolymer, etc.) Kinofuro Hills Ter Polioquino Ethylenophorio Kinofuro Hillo Monofutyrete Combined examples. Of these, those that have quinoethylene units are Horie Chileno Cricole For example, it is possible to exemplify a copolymer. Lucano Noroxano may be a good Oricama. Organopolyolcananols have a modified product such as ethanoquinone, hydroxyquino group, carboquinol group, amino group or substituted amino group (noah group), ether group, hinyl group (meth) acryloyl group at the molecular terminal or royal chain. Is also included.

 In addition, examples of sonox include low molecular weight polyolefins (for example, low molecular weight copolymers of reethylene ethylene and iorefino) ethylene soot.

 The proportion in the case of incorporating these processing improvers is preferably from 0 to 1 to 50 parts by weight, more preferably from 30 to 30 parts by weight, particularly preferably from 0 to 30 to 20 parts by weight, based on the amount of holacetal. (F) Weather resistance (light) stabilizer

 The horiacetal resin composition of the present invention may be blended with a weather resistance (light) stabilizer in order to impart weather resistance (light) resistance. The weather resistance (light) stabilizer is still a formal formed by a specific hydranoto derivative (Β). There is no damage to the occurrence of tea.

 Weather resistance (light) Stabilizers include henotrianol compounds, heno compounds, aromatic henoate compounds, anoanoacrylate compounds, anilate compounds, nitroquinolyl _ 1 3 5 _ trianononotamino compounds.

Henno Trianol compounds are 2— (2 '— Hitroquino / Lefeninore) Henono Trianole 2 — (2' — Hitrokino 1 3 ' Something like an hanol.

 As Hennov ヱ no-based compounds, non-compounds having a plurality of nitroquinol groups (such as 2 4-nitro quinoquinoeno 2-eno troquino non enoquino phenonono) phenokines (2- troquino 4—Metokinenohenoeno 2— 4—Oktokinenohenoeno 2—Hi Torokino 4 1 Totenoreno Eno 2 2 '—Nhi Trokino 4 —Metokino Henophenone Hi Trokino 4 4 “ 1-5—Sulfohenonophenone).

 Aromatic henoate compounds such as p-t-phthylphenol and p-octyl vinylsalinolate are alkylarylsalinos.

Noanoacrylate-based compounds include 2-ethyl quinolool, 3-nophenyl acrylate, 2-noanol, 3-nofuryl and other noanoyl group-containing noaryl acrylates. N— (2-Ethylphenyl) (2-Ethoxyno-5_t-Futinolephenyl) Nouminate Noruthyl N Ruphenyl) One N ′ ― (2-Ethoxynophenyl) Nouelate Noami Nouroites with 1 or 3 nitroquinols 1 3 5—Trianone compounds are 6- (2-hytroquinophenyl) 1 1 3,5, -trianophenyl _ 6— (2,4-notro troquinophenyl) ) 1 3 2 4—Nofenior 6— (2—Hirokino 4—Metokino 1) 1, 3, 5—Trianono 2 4—Nofeniol 1—— (2—4—Octylquinophenyl) 1 1,3 5—Trianone 2 4 1 6— (2—Hirokino 1) -Tothenoquinophenyl) 1 1 3 Non 2 4—Nophenol 6— (2—Hetroquino 4—Henonol) 1 1, 3, 5—Triano 2 4—No (p—Tolyl or 2 'chinolepheninole)-6-(2—Hitroquino 1—4-Henono Leokinohue 3 5—Trianone 2 4—Neofenolinole 1 —— (2—Hitoroquinotokino) Phenyl) 1 1 3, 5—Trianone 2, 4 Linole 1-6— (2-Hitrokino 4— (2— Hekinolokino Etkino) — 1 3, 5— Trianone.

 The hinotate amino compound is exemplified in the section of antioxidants and is used as an amino compound.

 These weather resistance (light) stabilizers may be used alone or in combination of two or more of the same weather (light) stabilizers. In particular, when it is preferable to use a phenol compound and a hinotate amino compound in combination, the ratio (weight ratio) of the two compounds is determined as follows: Henotrianol compound Toamino compound = 99 5/0 5-0 5Z99 5 More preferably, goZl OSO / O, particularly preferably 80-60.

In the present invention, when the weather resistance (light) stabilizer is blended, the blending ratio is 0 01 to 50 parts by weight, preferably 0 05 to 30 parts by weight, particularly preferably 0 1 to 2 parts per 100 parts by weight of the resin. 0 weight (other additives) Tomaline olefin Elastoma Toria Holyamito Elastoma Com. In the case of adding an impact resistance improver, 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 3 to 20 parts by weight with respect to 100 parts by weight of the acetal resin. As a sliding improver, olefinino-based polymer (polyethylene-no-ethylene and _α -olefino-copolymer, these acid and water) ヮ -nox (Hori-Chileno ヮ -no-kun) Noricorn Such as a noricono compound exemplified in the above), a benzoic acid trafluoroetileno, and a fatty acid ester. The property improvers may be used alone or in combination of two or more. The ratio in the case of slidability is preferably 0 parts by weight or more preferably 100 to 10 parts by weight, and even more preferably 0 to 5 parts by weight with respect to 100 parts by weight of the horiacetal resin.

 Gloss control agents include acrylic corenoel polymers, plastics, plastic polyester elastomers, elastomers, elastomers homopolymers or copolymers (polymethyl methacrylates, carbonate resins, styrene resins (with cholestero AS resins) Olefino-based lunar effect (Polyfloureno is a cyclic fluoreino. The blending ratio when the gloss control agent is blended is preferably 0 to 30 parts by weight, more preferably 0 parts by weight, more preferably 0 parts by weight with respect to parts by weight of holaceter. 5 to 10 parts by weight.

As the filler, crow fiber, carbon fiber, holono fiber, titanium metal fiber, aluminum fiber, or organic fiber-like filler, crow More preferably, it is 1 to 80 parts by weight.

 As dyes, various dyes are used. As the dyeing dye, an anthraquinono dye, a lid mouth anano dye, and a naphthoquino dye are used. As pigments, either machine pigments or organic facial pigments have been used. Titanium pigments Zinc pigments Carhonofuranoc Iron-based facials; H facial strength Tomi-based facial pigments Lead-based pigments Kohalt facial facial materials and alumini Organic facials include anano-based pigments, anthraquinono-based, non-anino-based facial wisteria, quinacritino-based pigments, helylene-based facial moths, helino-ininotrino-based pigments, oxanono-based pigments, and threno-based facials. Carhonofuranoc acid, which is a high colorant, Taronoanino-based face When using a Helylene face face, the weather resistance (light) is also good. When blending with a colorant, the blending ratio is preferably holacetal resin 1◦ 0 weight 0 0 1-5 parts by weight Preferably, it is 0 2 to 3 parts by weight, preferably 0 3 to 2 parts by weight.

 In the polyacetal resin composition of the present invention, other examples of κ may include a release agent, a nucleating agent, an antistatic agent, a hardener, a foaming agent, a surfactant, a caustic agent, an aromatic agent, and a fragrance. .

 (Method of manufacturing Holacetal resin composition / Left)

The production method of the holacetal resin composition according to the present invention is not particularly limited. (1) All components constituting the composition are combined / combined with each other. (2) Components constituting the ancestral composition Residual components are fed from the site feet through the site feet. In the preparation of a composition using an extruder, it is preferable to use one or more devolatilization extruders. Further, water or low-boiling alcohols are added to the location of the oleacetal resin from the king foot opening to the devolatilization f. 1 0 0 weight 0 1 to 10 parts by weight Formarte generated by extrusion process Preference is given to removing volatiles from low pressure distilling alcohols together with low boiling alcohols. It is possible to further reduce the amount of hot water generated from water. In addition, it is preferable to use feet after devolatilization when supporting a thiolanone compound.

 (Molding)

 The present invention also includes a molded product formed from the resin composition. In this settal molded product, the amount of formartite produced is greatly suppressed by the addition of a specific sulfonate sulfonate compound. Specifically, the amount of formartite produced or less than 2 μg or 1 μg Z g per unit weight of the molded product. Also, the amount of hol generated under dry conditions or 2 μg, or less, preferably 1 μg per table weight of the molded product. / Formed amount of formaldehyde under dry and dry conditions Degree of formaldehyde produced by storing a molded product with a thickness of 2 mm for 3 hours in a sealed space of 60 ° C and saturated ffl degree (2 ) The amount of formaldehyde generated when a thick product is stored for 24 hours in a sealed space at a temperature of 80 ° C is based on the determination method described in the Examples section.

In addition, the holacetal resin molded product of the present invention is held in a severe condition (for example, a high-temperature / highly sealed space) with a molded product made of a resin other than a holica cetal resin such as a holicon phonate steal resin. Other The resin composition of the present invention is not restricted in the field of use as a molded product. Use for reducing or strengthening the amount of generated artifacts * For example, automotive parts, parts, precision machine parts, building materials, piping parts, daily necessities, parts for chemicals, medical equipment, etc. Suitable for use.

Brief description of the 0 side

 0 1 shows a GC chart of the benzoic acid hit b-3 used for the resin composition of Comparative Example 2 10.

 0 2 represents the GC chart of the phosphonic acid hit b-6 used in the resin composition of Comparative Example 5 13. Example

 EXAMPLES The present invention will be specifically described below based on examples. The present invention is not limited by the examples.

 The evaluation items and measurement methods in the examples and comparative examples are as follows. [Hetranone generation amount in GC / MS measurement]

 Henotos made from Anolenotne ^ ^ One Susano Fuller 7694 Mass Selector 5973 is used and 20 ml of hydrated carboxylic acid hydranoto compound is knob-linked to prevent inhalation of the baked quartz wool and 200 sample of the sample in the bottle. C for 10 minutes, and the generated fossil component is kept at GC / MS outlet side for 4 minutes.After holding for 4 minutes, the temperature rise rate is 10 ° C / min. Quantification was performed. In addition

If it is not detected in (S / N), virtually no hitlanone is generated. It was hung on the lid of a Reno bottle (capacity 1 L), sealed, placed in a hot bath at a temperature of 60 °, and allowed to stand at room temperature for 1 hour. The amount of formaldehyde generated from the flat specimen and absorbed in the distilled water in the hori was quantified according to JIS K0102 Muartite section) to calculate the amount of hol generated per unit weight of the specimen (μg / g).

 [Amount of formaldehyde generated from dry-type molded products]

Ten prismatic specimens (2mmX 2mmX 5 Omm) with a holiacetal resin composition prepared in Examples and Comparative Examples were used (form temperature 190 ° C). The scale is closed with a capacity of 20 ml and the temperature is 80. After heating for 24 hours in a C β bath, air was cooled until it was removed from the II bath. Next, 5 ml of distilled water was absorbed into the container by using Norinon to absorb the formaldehyde produced from the pieces into the distilled water. The amount of this water-soluble lute is JIS KO 102 29 (form-artite) and the amount of form-artite generated per unit weight of test piece ( _μg , g).

Polyacetal resin molded product (2 mm length of the above-mentioned prismatic test piece is a total number of 15 g) and water (0 1 ml) in a sealed container (container) Place the molded product of quartz wool and phonate resin (tisk piece) to place the molded product of the resin and the molded product of the non-dried liquor in a non-contact state. Measure the time of corrosion or corrosion by visually observing the occurrence of corrosion that is not unique to HOLIKAHO. A helical composition in which a heliot-like composition is prepared by feeding it to a 3 O mm twin screw extruder (Norinoter temperature 200 ° C) with notro and melting / kneading and extruding. A specific test piece is injection molded using the above-mentioned formartite generation amount Polycarbonate resin molded product corrosion test or the above-mentioned Hetosose GC / MS measurement / decomposition The amount of hydranone generated was measured. these

Shown in ~ 2.

Comparative Examples 1 to 1 4

 For comparison, an example in which a carboxylic acid hydranoto compound was not used was evaluated in the same manner as an example in which a carboxylic acid hydranoto compound that did not satisfy the requirements was added. The results are shown in Tables 1-2

 Holiacetal resin used in Examples and Comparative Examples Carboxylic acid compounds Antioxidants Antifouling stabilizers Workability improving agents are as follows. The content of hydranone in the phosphonate hydranoto compound was determined by DMS0-d6 by tono NMR (total of 40, MHz 30 ° C 3 8 4 times). A compound without ヒ indicates that it is a hydranone in NMR detection sensitivity (S / N).

A Holiacetal resin

 -1) Holiacetal resin coholimer (copolymer of trioxane and 1 run 1 3—noquinolane 3 8 wt% copolymer Nox = 9 g / l 0 min)

The above melt intenox is a value obtained under the condition of 2 16 kg in accordance with AS TM-D 1 2 3 8. (b— 3) Anohino acid tranoto

 (b -4) Tris (Hitoranonocarbonylethyl) Inonoannule

(b-5) Anohino acid nohi tranoto (contains 2000 mg hitrano)

(b-6) Tris (Hytramenocarbonylethyl) Inonoannuleone containing 3000ppm)

 (b— 7) 2-Naphthoic acid HITRANOTO (containing 2000 ppm of HITRANONO)

C Antioxidant

 (c— 1) Triethylenecricol hiss [3— (3— t-Futyl -4-hi troquinofenore) propionate]

 (c-2) Hetta erythritol tetrakis [3— (3 5—NO 4—Horokinofenore) furohynate]

D Anti-stabilizer

 (d— 1) Carnoum stearinoate

 (d— 2) 1 2— carnoum troquinostearinoate

 (d-3) Carnoum quenoate

E Processing stabilizer

(e-2) Horie Chileno Kinoto [Molecular weight 35000]

(e-3) Monotanoate [East / Sheep Hetrolite L-EP]

As is clear from the table, the amount of formaldehyde resin produced in the examples is very low, and the molded product is in a sealed space or is a non-contact polycarbonate resin molded product in the sealed space. High quality and reliable.

Claims

The scope of the claims

1 (A) 100 parts by weight of holiocetal resin (B) 1 to 50 parts by weight of the carboxylic acid compound 101 A holothetal resin genus characterized in that the amount of arsenic produced by heating for 10 minutes is less than lOppm.

2. The holacetal resin composition according to claim 1, wherein the content of hydranone of the carbanoic acid hydranoto compound (B) is as follows.

 3. The phosphonophthalate resin composition according to claim 1, wherein the lithophthalate resin composition is at least one selected from the following general formula (1):

[Wherein X represents an aromatic ring, R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms, an elementary atom or an alkyl group or an ananol group having 1 to 30 carbon atoms, an integer of 4 and b represents 0 to Indicates an integer of 4. ]

4. A phosphonohydrophthalo compound (B) General formula (1) Odor ring A ゝ 0 to 2 integer b or 0 to 2 Composition. The acetal resin composition according to any one of claims 1 to 4, which is a holiacetal copolymer.

 7 Antioxidant Stabilizer Workability improver Weather resistance (light) Impact modifier Sliding improver Gloss control agent Filler and coloring agent Any one of claims 1 to 6 The police composition described.

 8. A molded article according to any one of claims 1 to 7, wherein the holacetal resin composition according to claim 1 is used.

 9 (1) The amount of formaldehyde generated when a molded product of two thighs is formed in a sealed / displayed space at a temperature of 60 ° C or 2 degrees or 2 per unit weight of the molded product or (2) Temperature 8 9. The molded product according to claim 8, wherein a molded article having a thickness of 2 mm in a sealed space at 0 ° C. is 2 O per unit weight of the molded article generated at 24:00.

 The molded article according to claim 8 or 9, wherein the molded product is a non-corrosive molded resin in a non-contact state in the sealed space at 20:00 when the molded product is at a temperature of 120 ° C and saturated humidity. Goods.