Classifications

• • 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
• • 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
  • C08K5/13—Phenols; Phenolates
• • 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
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to a polyacetal resin composition having excellent mechanical properties, processability, and stability, and the amount of formaldehyde and the like generated is suppressed by chopsticks.
• the present invention also relates to a polyacetal resin composition imparted with such properties without impairing surface properties.
• Polyacetal resin has excellent mechanical properties, slidability, strength, surface properties, etc., and its molded products are used in a wide range of fields.
• guanamine compounds have been conventionally added to increase the thermal stability of polyacetal resins and suppress the generation of formaldehyde and the like due to the decomposition of the resin, and a guanamine compound should be added as a stabilizer. It has been known for a long time (Japanese Patent Publication No. 40-0 2 1 1 4 8). However, when the addition of guanamine compounds achieves a high degree of thermal stability and the amount of blending is adjusted in order to significantly reduce the generation of gases such as formaldehyde, the excellent mechanical properties inherent in polyacetal resins In some cases, the properties and workability were impaired, and the coexisting part of the synthesis was a factor.
• An object of the present invention is to solve a significant problem and to provide a resin material having these characteristics.
• the present inventor has found that the object can be achieved by selecting the composition of the polyacetal resin as a substrate and the selection of the compounding ingredients, and led to the present invention. It was.
• the present invention relates to polyacetal resin having a substantially linear molecular structure (A1) 99.88 to 70.0% by weight, polyacetal resin having a branched or crosslinked structure (A2) 0.1 to 20.0% by weight. /.
• the polyacetal resin (A1) having a substantially linear molecular structure used in the present invention is a polymer compound having an oxymethylene group (—CH 2 0 —) as a main structural unit, Intentionally introduced It does not have a branched structure or a crosslinked structure.
• the force Cal polyacetal resin (A1) substantially Okishimechiren group repeatedly only from the consisting polyacetal ho Moporima, Okishimechiren group other configuration unit that does not form a branched and cross-linked structure composed mainly of, in particular C 2 - 6 Okishi of A typical example is a polyacetal copolymer (including a block copolymer) having a small amount of an alkylene unit.
• any of these polyacetal resins can be used as the polyacetal resin (A1), and two or more types of polyacetal resins having different characteristics can be blended as required. From the viewpoint of thermal stability, it is preferable to use a polyacetal copolymer.
• Such polyacetal copolymers include trioxane (a) 99.95 to 80.0% by weight and compounds selected from cyclic ether compounds and cyclic formal compounds having no substituents (b) 0.05 to 20.0% by weight Are preferably obtained by copolymerization of trioxane (a) 99.9 to 90.0% by weight with the above compound.
• (b)) includes, for example, ethylene oxide, 1,3-dioxolan, jetylene glycol enore nomarenore, 1,4 butyl taneno enore meranore, 1,3-dioxane, propylene oxide
• one or more selected from ethylene oxide, 1,3-dioxolan, 1,4-butanediole formal and diethylene glycol formal are preferred.
• the method for preparing the polyacetal resin (A1) is not particularly limited, and can be prepared by a known method, but industrially, a continuous bulk polymerization method is preferable.
• the polyacetal copolymer used in the present invention preferably has a melt index (measured at 190 ° C, load 2160 g) of 1 to 50 g / min.
• the melt index can be adjusted by increasing or decreasing the amount of chain transfer agent used for polymerization, for example, methylal.
• the polyacetal copolymer used in the present invention has a hemi-formal terminal group amount of 1.0 mmol / kg or less, a formolene terminal group amount of 2.0 mraol / kg or less, and an unstable terminal group amount of 0.5% by weight or less.
• the amount of hemi-formal end group is 0.6 mmol / k or less, the formyl end group amount is 0.5 thigh ol / kg or less, and the unstable end group amount is 0.3 wt% or less. is there.
• the present invention aims at preparing a polyacetal resin composition with a sufficiently reduced amount of formaldehyde generated. It will contribute effectively.
• the hemiformal end group is represented by one OCH 2 OH, and is also referred to as a hydroxymethoxy group or a hemiacetal end group.
• the formyl end group is represented by one CHO.
• the amount of Mihorumaru end Tanmoto and formyl terminal groups to such can be determined by 1 H- NMR measurement, and the detail determination method, described in JP 2 0 0 1 1 1 1 4 3 No. You can refer to the method.
• the unstable terminal group amount is the amount of a portion present in the terminal portion of the polyacetal copolymer, which is unstable to heat and base and easily decomposes. Such instability terminal group content, a polyacetal copolymer 1 g, 0.
• the polyacetal copolymer having terminal properties as described above can be obtained by adjusting the polymerization step, adjusting the catalyst deactivation step, adjusting the stabilization step by decomposing and removing unstable ends, and a combination of these adjustment methods.
• the monomer used for the polymerization is a method in which impurities such as moisture, methanol, formic acid and the like that cause unstable terminals are reduced, and the polymerization is performed using the monomer having few impurities.
• a polyacetal copolymer having more preferable terminal characteristics by, for example, a method in which the polyacetal copolymer is dissolved in a solvent containing a basic compound by heating and heat-treated in a solution state, or by combining these methods. Can do.
• the polyacetal resin (A2) having a branched or crosslinked structure used in the present invention can be copolymerized with formaldehyde or trioxane in the production of the polyacetal homopolymer or polyacetal copolymer as described above. It is obtained by further adding a compound capable of forming a branch unit or a crosslinking unit by copolymerization and copolymerizing.
• trioxane (a) with a compound (b) selected from a cyclic ether compound having no substituent and a cyclic formal compound, a monofunctional glycidyl compound having a substituent (for example, phenyldaricidyl) Ether, butyl glycidyl ether, etc.) and copolymerization to obtain a polyacetal resin having a branched structure, and addition of a polyfunctional glycidyl ether compound and copolymerization to obtain a polyacetal having a bridge structure.
• a resin is obtained.
• a polyacetal resin (A2) having a cross-linked structure it is preferable to use a polyacetal resin (A2) having a cross-linked structure.
• trioxane (a) 99.89 to 88.0% by weight, resin having no substituent, monofunctional cyclic A compound selected from ether compounds and monofunctional cyclic formal compounds (b) 0.1 to 10.0% by weight and polyfunctional glycidyl ether compound (c) 0.01 to 2.0% by weight are copolymerized.
• a crosslinked polyacetal resin having a melt index of 0.1 to 10 g / rain Is preferable.
• Examples of the compound (b) include the same compounds as described above, and in particular, ethylene oxide, 1,3-di-year-old xoxolan, 1,4-peptanedio-renolemenore and diethylene group. One or more selected from recall formal are preferred.
• Polyfunctional glycidyl ether compounds include ethylene glycol diglycidyl etherenole, propylene glycolinoresigrisidinoatenole, 1,4-butanedioresinglycidinoatenetole, hexamethyleneglycono Resiglycidyl ether, Resonoresinol diglycidinoreatenore, Bisphenol A Diglyci dizinoreatenore, Polyethylene glycolinoresiglycinoreatenore, Polypropylene glyconoresiglycidie / leetenore, Polybutyleneglycone Regiglycidinole ether, glycerol triglycidyl etherate, trimethylol propanto glycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycol Jill ether, port Rigurise port over
• those having 3 to 4 glycidyl ether groups in one molecule are particularly preferable, and specific examples include trimethylolpropane triglycidyl ether, dariceol triglycidyl ether, and pentaerythritol tetraglycidyl ether. .
• the polyacetal resin (A2) a polyacetal copolymer in which a crosslinked structure is formed using a glycidyl ether compound having 3 to 4 glycidyl ether groups in one molecule, further mechanical properties are obtained. This is an excellent polyacetal resin composition.
• the method for preparing the polyacetal resin (A2) having the branched or crosslinked structure as described above is not particularly limited, and can be prepared by a known method in the same manner as the preparation of the polyacetal resin (A1). .
• the blending amount of the polyacetal rice cake (A2) having a branched or crosslinked structure as described above is 0.1 to 20.0% by weight in the total composition, and more preferably 2. 0 to 20% by weight. If the blending amount is small, a polyacetal resin composition with excellent mechanical properties cannot be obtained, and if the blending amount is excessive, the processability of the polyacetal resin composition is impaired, resulting in mechanical properties. Characteristic Will be insufficient.
• the hindered phenol antioxidant (B) used in the present invention includes a monocyclic hindered phenol compound, a hydrocarbon group or a polycyclic hindered phenol linked with a group containing a thio atom. Examples thereof include hindered phenol compounds having a compound, an ester group or an amide group.
• these compounds include 2,6-di-tert-butylenole p-cresonore, 2,2, -methylenbis (4-methyl-6-t-lepti / refenol), 4,4, -methylenebis (2,6- 1, 2, 3—Tris (2-Methyl / Lee 4-Hydroxy 5-—T-Butino Refenore) Butane, 4, 4′-propylidene bis (3-Methyl 6— t 1-butylphenol), 1, 3, 5-trimethyl-2 4, 6-tris (3,5-di-tert-butinoleol 4-hydroxybenzenole) benzen, 4,4'-thiobis (3-methigre 6- n-octadecinole 1), n-octadecinole 1- (4'-hydroxyl 3 ', 5, zy-t-butylfel) propionate, n-octadecinole 1- (4, mono-hydroxy 3',
• hindered phenolic antioxidants (B) can be used alone or in combination of two or more.
• the amount of hindered phenolic antioxidant (B) added is 0.01 to 5.0 weight as a percentage of the total yarn and composition. / 0 , preferably 0.03 to 3.0% by weight. If the amount added is small, the effect will be insufficient, and if it is large, problems such as coloring and bleeding may occur.
• the guanamine compound (C) used in the present invention may be an aliphatic guanamine compound, an alicyclic guanamine compound, an aromatic guanamine compound, a heteroatom-containing guanamine compound, or the like.
• Aliphatic guanamine compounds include: monoguanamines such as acetoguanamine, valerologamine, caproguanamine, heptanoguanamine, capriloganamin, stealoganamin, succinoguanamine, daruma guanamine, adipoguanamine, pimeloganamin, Examples include alkylene bisguanamines such as belog anamin, xeroguanamine, and sebacoguanamine.
• Examples of the alicyclic guanamine compounds include cyclohexan carboguanamine, norbornenene canoleboguanamine, hexaxencarboguanamine, norbonolena.
• Monoguanamines such as N-carboguanamine, and their cycloalkane residues, alkyl tombs, hydroxyl groups, amino groups, acetoamino groups, nitrile groups, force noroxy groups, alkoxycarbonyl groups, force rubamoyl groups, alkoxy groups Derivatives substituted with 1 to 3 functional groups such as phenyl group, Tamyl group, and hydroxyphenyl group.
• Aromatic guanamine compounds include benzoguanamine and its residue of the alkyl group, hydroxy group, amino group, acetoamino group, nitrile group, strong ruxoxy group, alkoxycarbonyl group, strong rubermoyl group, alkoxy group, phenylol group.
• Derivatives substituted with 1 to 5 functional groups such as cumyl group and hydroxyphenyl group (for example, tolguanamine, xyloganamine, phenylbenzoguanamine, hydroxybenzoguanamine, 4- (4, -hydroxyphenyl) ⁇ ) Benzoguanamine, nitrinolevenzoguanamine, 3,5-dimethinole 4-hydroxybenzoguanamine, 3,5-di-t-petit-re-4-hydroxybenzoguanamine, etc.), naphthoguanamine and its naphthyl residue
• functional groups such as Polyalkylamines such as anamins, phthalologamines, isophthalologamines, terephthalologamines, naphthalene guanamines, biphenylenediguanamines, aralkyl such as phenylacetoguanamines, monophenylpropioguanamines, and xylylenebisguanamines
• Heteroatom-containing guanamine compounds include 2,4-diamino-6- (3,
• Examples thereof include imidazole ring-containing guanamines such as guanamine compounds described in JP 33766 and guanamine compounds described in JP-A No. 2000-154181.
• the compounding quantity of this guanamine compound (C) is 0.01 to 5.0 weight as a ratio in the whole composition. /. Preferably, it is 0.03 to 3.0% by weight.
• the amount of the guanamine compound (C) is small, the polyacetal resin composition is inferior in heat stability I 1 and the amount of gas such as formaldehyde is increased.
• the amount of the guanamine compound (C) is excessive, the mechanical properties are deteriorated, the molding processability is deteriorated, and the surface property of the molded product is also deteriorated.
• the polyacetal resin composition of the present invention may further contain various known stabilizers and additives as long as the object of the present invention is not impaired.
• the stabilizer include one or more of nitrogen-containing compounds such as melamine, hydrazide and urea, hydroxides of alkali metals or alkaline metals, inorganic salts, carboxylates and the like. be able to.
• Additives include general additives for thermoplastic resins such as dyes, colorants such as glazes, lubricants, nucleating agents, mold release agents, antistatic agents, surfactants and various inorganic fillers. Etc.
• the blending of an aliphatic bisamide compound is preferable because it contributes to improvement of molding processability, and thereby contributes to maintenance of mechanical properties and reduction of formaldehyde generation.
• the amount of the aliphatic bisamide compound added for the purpose is strong.
• the proportion in the composition is preferably 0.01 to 2.0% by weight. If the amount is too large or too small, moldability is impaired.
• the present invention is a particularly preferred embodiment because it is colored with 0.01 to 2.0% by weight (in the whole composition) of the colorant and exhibits a great effect in the polyacetal resin composition. That is, most of the colorants are active and often have an undesirable effect on the stability of the polyacetal resin and the generation of formaldehyde, but the composition of the present invention functions effectively to suppress it. For this reason, the effect is remarkable in a colored molded product that is particularly required to have excellent surface properties.
• the present invention is preferable because it is a characteristic embodiment even when the inorganic fibrous filler is not substantially contained (not blended). That is, such a composition improves the mechanical properties while maintaining the excellent properties such as processability and surface properties inherent in polyacetal resins, and further reduces the generation of gases such as formaldehyde to the utmost limit.
• a resin material can be obtained.
• the polyacetal composition of the present invention is easily prepared by a known method generally used as a conventional resin composition preparation method. For example, after mixing each component, kneading and extruding with a single-screw or twin-screw extruder to prepare pellets, then forming, and preparing pellets (master batches) with different compositions. Any method can be used in which the pellets are mixed (diluted) with a predetermined amount, subjected to molding, and a molded product having the desired composition is obtained after molding.
• part or all of the polyacetal resin as a substrate is pulverized, mixed with this and other components, and then extruded to improve the dispersibility of the additive. This is a preferable method. Examples-The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
• the measurement / evaluation method was as follows.
• a flat specimen (100 mm x 40 mm x 2 mm: weight approximately 11.2 g) is hung on the lid of a polyethylene bottle (capacity 1 000 ml) containing 5 Om 1 of distilled water and sealed tightly. The sample was left in a thermostatic chamber at 60 ° C for 3 hours and then left at room temperature for 1 hour. The amount of formaldehyde generated from a flat plate specimen and absorbed in distilled water in a polyethylene bottle was measured according to JIS K0102.29 (formaldehyde section), and formaldehyde per unit weight of the specimen was measured. The amount generated was calculated.
• a linear polyacetal resin (A1) is blended with a branched / crosslinked polyacetal resin (A2), a hindered phenolic antioxidant (B) and a guanamine compound (C) in the proportions shown in Table 1, and the cylinder temperature
• a pellet-like composition was prepared by melt-kneading with an extruder at 200 ° C.
• a test piece was molded from the pellet-shaped composition using an injection molding machine, and the physical properties were evaluated by the evaluation method described above. The results are shown in Table 1.
• the linear polyacetal resins Al-1 and Al-2 were prepared as follows.
• trioxane and 1,3-dioxolane were continuously supplied, and the molecular weight was adjusted.
• Methylal was continuously supplied as an agent, and boron trifluoride was continuously added as a catalyst at a rate of 15 ppm to all monomers to perform bulk polymerization.
• the mixture of trioxane and 1,3-dioxolane used for polymerization contains 0.03% by weight of pentaerythritol-tetrakis [3— (3,5-deoxybutoxyphenyl) pionate]. Contained.
• the mixture of trioxane and 1,3-dioxolane used for polymerization contained 6 ppm of water, 3.5 ppm of methanol, and 5 ppm of formic acid as impurities.
• the polymer discharged from the discharge port of the polymerizer is immediately added with an aqueous solution containing 1000 ppm of triethylamine, powdered and stirred to deactivate the catalyst, and then centrifuged and dried to obtain crude polyoxymethylene. A copolymer was obtained.
• this crude polyoxymethylene copolymer is supplied to a twin-screw extruder having a vent port, and the unstable end portion is decomposed by melting and kneading at a resin temperature of about 220 ° C., and a decomposition product is obtained. Volatile components contained were devolatilized from the vent port under reduced pressure. The polymer taken out from the die of the extruder was cooled and chopped to obtain a pellet-like polyacetal resin A1-2 from which the unstable terminal portion had been removed.
• the above pellet-like polymer is continuously supplied from the upper part, and a 135 ° C aqueous solution containing 500 ppm of triethylamine is supplied from the lower part. After 8 hours, centrifugation and drying were carried out to obtain polyacetal resin A1-1 in which hemiformal end groups, formyl end groups, and unstable end portions were further reduced.
• the polyacetal resins A1-1 and A1-2 have a hemiformal terminal group amount and a formyl group terminal group amount of A VANC E 400 type FT manufactured by Bruker Co., Ltd. 1 This is a value (mmo 1 / kg) obtained by measuring according to the method described in JP-A-2001-11143 using an NMR apparatus.
• the melt index is a value (gZi 0 min) determined under conditions of 190 ° C and 2160 g according to ASTM-D 1238.
• DO indicated by abbreviation DO is 1,3-dioxolane
• BF is 1,4-pentanediol formal
• TMPTGE is trimethylolpropane triglycidyl etherate.

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• Compositions Of Macromolecular Compounds (AREA)
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