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

Definitions

• the present invention relates to a polyacetal resin composition having excellent mechanical properties.
• Patent Document 1 JP-A-49-98458 (Claims)
• Patent Document 2 JP-A-60-219252 (Claims)
• Patent Document 3 Japanese Patent Application Laid-Open No. 61-236851 (Claims 118, 913)
• Patent Document 4 Japanese Patent Application Laid-Open No. 62-91551 (Claims 1, 2)
• An object of the present invention is to provide a polyacetal resin composition capable of solving a powerful problem and responding to higher mechanical properties required in recent years as the field of use of polyacetal resin is expanded. I do.
• the present invention provides a polyacetal resin composition
• a polyacetal resin composition comprising 100 parts by weight of a polyacetal resin component (A) and 3 to 200 parts by weight of a glass-based inorganic filler (B).
• (A) is characterized by comprising 99.9 to 80 parts by weight of a polyacetal resin having a substantially linear molecular structure (A1) and 0.1 to 20 parts by weight of a polyacetal resin having a branched or crosslinked structure (A2). Is a polyacetal resin composition.
• the present invention incorporates a glass-based inorganic filler.
• the polyacetal resin component (A) comprises a polyacetal resin (A1) having a substantially linear molecular structure and a polyacetal resin (A2) having a branched or crosslinked structure. It is characterized by.
• the polyacetal resin (A1) having a substantially linear molecular structure used in the present invention is a high molecular compound having an oxymethylene group (one CH0-) as a main structural unit, and is a polyoxymethylene homopolymer, an oxymethylene group.
• a copolymer including block copolymers
• Copolymers are high molecular weight compounds having a weight average molecular weight of 5000 or more, in which oxyalkylene groups having 2 to 6 carbon atoms are dispersed in repeating units mainly composed of oxymethylene groups (one CH 0—). In general, it is produced by copolymerizing trioxane, which is a cyclic trimer of formaldehyde, with a compound selected from a cyclic ether compound and a cyclic formaldehyde compound. Removed and stabilized against thermal decomposition.
• trioxane which is a cyclic trimer of formaldehyde
• a copolymer obtained by copolymerizing 99.9 to 90.0% by weight of trioxane (a) and 0.1 to 10% by weight of a compound (b) selected from a cyclic ether compound and a cyclic formal compound is preferable.
• a copolymer obtained by copolymerizing 99.9 to 90.0% by weight of trioxane (a) and 0.1 to 10% by weight of a compound (b) selected from a cyclic ether compound and a cyclic formal compound is preferable.
• the effects of the present invention are particularly prominent.
• cyclic ether compound or cyclic formal compound for copolymerization for example, ethylene oxide, 1,3-dioxolan, diethylene glycol formal, 1,4-butanediol formal, and the like are used. These do not form a branched or crosslinked structure.
• a component for adjusting the molecular weight is generally used in combination to adjust the molecular weight of the obtained polymer.
• a component for adjusting the molecular weight a chain transfer agent that does not form an unstable terminal, that is, a compound having an alkoxy group such as methylal, methoxymethylal, dimethoxymethylal, trimethoxymethylal, or oxymethylenedi_n_butyl ether One or two or more are exemplified.
• the polyacetal resin (A1) as described above used in the present invention preferably has a melt index (Ml) measured at 190 ° C and a load of 2160 g of 1 to 50 g / min. Ml is small If the amount is too large, the workability is poor.
• the polyacetal resin (A2) having a branched or crosslinked structure used in the present invention can be copolymerized with formaldehyde or trioxane and the like in the production of the polyacetal resin (A1) as described above. Then, a compound capable of forming a branched or crosslinked unit is further added and copolymerized.
• a polyacetal resin (A2) having a branched or crosslinked structure is a compound (b) 0 selected from trioxane (a): 99.99 90% by weight, a cyclic ether compound and a cyclic formali conjugate. It is obtained by copolymerizing 10% by weight and 0.011.0% by weight of a polyfunctional glycidinole ether compound (c).
• the compound (b) selected from the group consisting of trioxane (a), cyclic ether compound and cyclic formal compound used in the production of the branched or crosslinked polyacetal resin (A2) described above is the same as that of the polyacetal resin (A1).
• the compound is as described in detail above.
• the compound (b) used for producing the branched or crosslinked polyacetal resin (A2) may be the same as or different from the compound used for producing the polyacetal resin (A1).
• such a compound (b) is not particularly essential as a component of the strong polyacetal resin (A2) having a branched or crosslinked structure, but stably produces the branched / crosslinked polyacetal resin (A2).
• polyfunctional glycidyl ether conjugate (c) those having 3 or 4 daricidyl ether groups in one molecule are particularly preferred, specifically, trimethylolpropane triol.
• Preferred compounds include glycidinole ether, glycerol triglycidyl ether and pentaerythritol tetraglycidyl ether.
• the copolymerization ratio of the polyfunctional glycidyl ether compound (c) is 0.01 to 1.0% by weight, particularly preferably 0.02 to 0.5% by weight.
• the branched or crosslinked polyacetal resin (A2) used in the present invention is generally the same as the polyacetal resin (A1), except that an appropriate amount of a molecular weight modifier is added thereto, and a cationic polymerization catalyst is used. And the like.
• polymerization equipment, polymerization conditions, polymerization The subsequent catalyst deactivation treatment and subsequent post-treatment may be performed according to the method for producing the polyacetal resin (A1).
• the polyacetal resin (A2) as described above used in the present invention is preferably one having a melt index (Ml) force S of 0.1 to 10 g / min measured at 190 ° C and a load of 2160 g. If Ml is too small, processability is poor, and if it is too large, the effects of the present invention are less likely to be produced.
• Ml melt index
• the glass-based inorganic filler (B) used in the present invention includes fibrous (glass fiber), granular (glass bead), powder (milled glass fiber), plate (glass flake) and the like. And a hollow (glass balloon) filler. Any known filler having no particular restriction on the particle size, fiber length and the like can be used.
• one or more kinds selected from these fillers can be used in combination according to the purpose.
• these glass-based inorganic fillers can be used even if they have not been treated.
• inorganic materials that have been subjected to a surface treatment with a surface treatment agent such as a silane-based or titanate-based coupling agent can be used. It is better to use a filler.
• silane coupling agent examples include vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, and arylalkoxysilane.
• vinylalkoxysilanes include, for example, burtriethoxysilane, burtrimethoxysilane, burtris ( ⁇ -methoxyethoxy) silane, and the like.
• Ripyltriethoxysilane and the like can be mentioned.
• Examples of aminoalkoxysilanes include, for example, ⁇ -c- , 7-T-diethoxysilane, ⁇ -ami y
• titanate-based surface treatment agent examples include titanium-i-propoxyotatilene glycolate, tetra- n -butoxytitanium, and tetrakis (2-ethylhexoxy) titanium.
• the amount of the surface treatment agent to be used is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight based on 100 parts by weight of the inorganic filler.
• the glass-based inorganic filler (B) is a glass fiber
• those using a polymer binder, an adhesion promoter, other auxiliaries and the like as a sizing agent are preferably used.
• the polymer binder generally known materials such as organic materials, for example, water-dispersible / water-soluble polyvinyl acetate, polyester, epoxide, polyurethane, polyatalylate or polyolefin resin, and mixtures thereof are preferably used.
• the blending amount of the glass-based inorganic filler (B) is 3200 parts by weight, preferably 5150 parts by weight, particularly preferably 10 1 to 100 parts by weight, per 100 parts by weight of the polyacetal resin component (A). Parts by weight. If the amount is less than 3 parts by weight, the mechanical properties are not sufficiently improved, and if the amount exceeds 200 parts by weight, the molding force becomes difficult.
• the polyacetal resin composition of the present invention may further contain various known stabilizers' additives.
• stabilizers include hindered phenol compounds, nitrogen-containing compounds such as melamine, guanamine, hydrazide, and urea, hydroxides of alkali or alkaline earth metals, and inorganic compounds.
• One or more kinds of salts, carboxylate salts and the like can be mentioned.
• the additives used in the present invention include general additives for thermoplastic resins, for example, coloring agents such as dyes and pigments, lubricants, nucleating agents, release agents, antistatic agents, and surfactants. One or more of the agents can be mentioned.
• fibrous or plate-like materials such as known inorganic, organic, and metal other than the glass-based inorganic filler can be used. It is also possible to compound one or more kinds of fillers such as powders and the like. Examples of such fillers include, but are not limited to, talc, my strength, wollastonite, carbon fiber, and the like.
• the addition of a boric acid compound described in JP-A-9-1151298 and the addition of a hydroxycarboxylic acid compound described in JP-A-2002-371168 Further, addition of a conventionally known organic acid or inorganic acid can be carried out at the same time, and further improvement in mechanical properties can be achieved.
• the composition of the present invention can be easily prepared by known facilities and methods generally used as conventional resin composition preparation methods, which are not particularly limited. For example, i) a method of mixing each component, kneading and extruding with an extruder to prepare pellets, and then molding, and ii) once preparing pellets having a different composition, mixing a predetermined amount of the pellets and molding. Any of the following methods can be used: a method of obtaining a molded article having a desired composition after molding; m) a method of directly charging one or more of each component to a molding machine. Mixing and adding a part of the resin component as a fine powder with other components is a preferable method for uniformly blending these components.
• the resin composition according to the present invention can be molded by any of extrusion molding, injection molding, compression molding, vacuum molding, blow molding, and foam molding.
• Melt index (Ml) is 190 according to ASTM D-1238.
• C load of 2160g Measured under the following conditions:
• a tensile test piece according to IS03167 was heated at a temperature of 23 ° C and a humidity of 50. The sample was left for 48 hours under the condition of / o, and measured according to IS0527.
• a paddle is attached using a continuous mixing reactor consisting of a barrel that has a jacket through which a heat (cold) medium passes and a cross section of two circles partially overlapped, and a rotary shaft with paddles.
• Table 1 shows trioxane (a), a compound selected from cyclic ether compounds and cyclic formal compounds (b), and a polyfunctional daricidyl ether compound (c) while rotating the two rotating shafts at 150 rpm.
• methylal as a molecular weight regulator was continuously supplied, and boron trifluoride as a catalyst was continuously added and supplied in an amount of 0.005% by weight based on trioxane to perform bulk polymerization.
• the reaction product discharged from the polymerization machine was immediately passed through a crusher and added to a 60 ° C aqueous solution containing 0.05% by weight of triethylamine to deactivate the catalyst. Further, after separation, washing and drying, a crude polyacetal resin was obtained.
• Toryechiruamin 5 wt% aqueous solution 3 wt 0/0, pentaerythrityl over tetrakis [3_ (3, 5_ di tert- butyl-4-hydrin Rokishifueniru) Propionate] was added in an amount of 0.3% by weight, and the mixture was melt-kneaded at 210 ° C. in a twin-screw extruder to remove unstable portions, to obtain a polyacetal resin in pellet form, which was used for preparing a polyacetal resin composition.
• Table 1 shows the compositions and melt indexes of these polyacetal resins. The abbreviations in the table are as follows.
• Example 1 99 A2-1 1 B1 35 121 2.6
• Example 2 97 A2-1 3 B1 35 138 2.9
• Example 3 95 A2-1 5 B1 35 141 3.1
• Example 4 97 A2-2 3 B1 35 132 2.6
• Example 5 97 A2-3 3 B1 35 130 2.4
• Example 6 97 A2-1 3 B2 35 128 2.4
• Comparative example 1 100 B1 35 113 1.9 Comparative Example 2 100 B2 35 110 1.8 Comparative Example 3 100 B3 35 119 2.0
• Example 8 97 A2-1 3 B4 35 57 16 Example 9 99 A2-1 1 B5 35 53 15 Example 10 97 A2-1 3 B5 35 62 18 Example 11 95 A2-1 5 B5 35 64 19 Example 12 97 A2-2 3 B5 35 59 16 Example 13 97 A2-3 3 B5 35 60 17 Example 14 97 A2-1 3 B6 35 60 17 Example 15 97 A2-1 3 B7 35 59 17 Comparative example 4 100 B4 35 45 11 Comparative example 5 100 B5 35 47 12 Comparative example 6 100 B6 35 48 13 Comparative example 7 100 B7 35 48 13
• a linear polyacetal resin (manufactured by Polyplastics Co., Ltd., trade name: DURACON MO) was blended with the following milled glass fibers (B8, B9) and a branched 'crosslinked polyacetal resin in the proportions shown in Table 4, The mixture was melt-kneaded with an extruder at a cylinder temperature of 200 ° C to prepare a pellet-shaped composition. Next, test pieces were molded from the pellet-like composition using an injection molding machine, and physical properties were evaluated. Table 4 shows the results.
• the following glass flakes and branched 'crosslinked' polyacetal resins (A2-1-A2-3) are blended with a linear polyacetal resin (manufactured by Polyplastics Co., Ltd., trade name: DURACON M90) in the proportions shown in Table 5. Then, the mixture was melt-kneaded with an extruder having a cylinder temperature of 200 ° C to prepare a pellet-shaped composition. Next, test pieces were molded from the pellet-shaped composition using an injection molding machine, and physical properties were evaluated. Table 5 shows the results.
• BIO Glass flakes surface-treated with y-aminopropyltriethoxysilane

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