JPS60500576A - Ethylene bis-stearamide containing polyoxymethylene/polyurethane composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Ethylene his-stearamide containing polyoxymethylene/polyurethane composition Technical field The present invention provides improved mold release properties and reduced mold deposits. The present invention relates to certain polyoxymethylene compositions having distinctive properties. Po The lyoxymethylene composition has at least two adjacent carbon atoms in the backbone. Formaldehyde or a cyclic form of formaldehyde having an oxalkylene group Homogeneous polymers of oligomers, e.g. trioxane, whose end groups are esterified or end-capped by etherification; formaldehyde or a cyclic oligomer copolymer of formaldehyde, and The terminal group of is hydroxyl-terminated or esterified or etherified. It is generally understood that the composition contains a composition that can be end-capped. be understood. The proportion of copolymers can be up to 20% by weight. Relatively high price Pace polyoxy7 methylene with a molecular weight of 20,000 to 100,000. The composition can be processed using techniques commonly used for thermoplastic materials, such as compression molding, injection molding, extrusion. , by blow molding, rotational molding, melt spinning, stamping and thermoforming. Useful for manufacturing semi-processed and processed products. manufactured from such compositions. The processed products are highly desirable, including high stiffness, strength and resistance to common media. M has a desirable physical sexuality. 5-40% by weight of certain thermoplastic polyurethanes and has extremely high toughness and/or impact resistance. Ren compositions have recently been developed. However, polyoxymethylene/polyurethane The rhethane composition exhibits ttticking and/or ttticking properties.

The present invention provides an improved solution in which discoloration and decomposition problems are significantly reduced or eliminated. The present invention relates to lyoxymethylene/polyurethane compositions.

Background technology Related application by E. A. FIGzman dated February 7, 1983, U.S. Pat. Patent Application Circular No. 464,412 and its partially continuation application dated January 16, 1984 No. 570,036, which has an extremely high impact value, i.e. Inch-Bond] Larger Gardner (Gαrdnet) Impact value Ca, 6K Weight of r (s; gnd) and injection molded 7,62XIZ7XO,1 Cut a small piece of 6 cm (3 x 5 x'/,, inch) and test it according to ASTM D-302. 9.Method G...Geometry D measurement] Cimethylene compositions are disclosed, in which case the compositions are essentially (α) below 0°C. at least one thermoplastic polyurethane having a glass transition temperature as low as 5 to 15; weight%, and (b) At least one polymer having a molecular weight of 20,000-100,00 oo It consists of 85 to 95 Mkt% of lyoxymethylene polymer, and the above percentages are for component (α) and and (b) only, and thermoplastic polyurethane is porous as separate particles. dispersed throughout the lyoxymethylene polymer, and the composition is as large as 9J The Gardner impulse value is M.

Related application E, A, F 1 etrnan dated February 7, 1983 , U.S. Patent Application No. 464,411 and its continuation-in-part, 1984-1 U.S. Patent Application No. 570,037, dated May 16, 7,517 m (7,0 ft-lb/in) with a larger notch Notched Izot value (ASTM D-256, Method A A polyoxymethylene composition having a high The product is immaterial (a) has a glass transition temperature lower than −t5°C, is greater than 15% by weight, and is 40% by weight; At least one thermoplastic polyurethane having an M amount of 4 or less, and (6) 20.00 has a molecular weight of 0 to 100,000, is at least 60% by weight, and has a molecular weight of 85% comprising at least one polyoxymethylene polymer less than the above-mentioned is based on the total amount of components (a) and U)), and thermoplastic polyurethane is 0.9 Polyoxymethylene as individual phases with an average cross-sectional diameter of submicron minimum diameter dispersed throughout the polymer and the composition has an Izo of greater than 375 J/lrL. It has a value.

The polyoxymethylene compositions disclosed in these two related applications are #) Improved mold release properties and reduced mold adhesion properties. A composition capable of providing a lyoxymethylene composition.

No. 3,236,929, dated February 22, 1966, by Jwpa et al. Species commonly added to m-compounds to improve the mold release properties of polyoxy7-methylene Various compounds have been disclosed. disclosed as appropriate for this purpose. Such compounds include long chain aliphatic amides such as ethylene bis-stearamide.

However, the polyoxymethylene compositions disclosed in this patent do not contain any thermoplastic Contains no synthetic polyurethane, and does not contain any polyurethane. From cimethylene compositions to additives for improving female mold characteristics and reducing mold stickiness. Regarding 1-1, it is not possible to extrapolate to materials containing 5 to 40% by weight of polyurethane.

This means that for use in polyoxymethylene compositions that do not contain any polyurethane, Many of the vinegar-type agents shown as references contain 5 to 40% by weight of polyurethane. It is clear from the fact that it is not suitable for single-length use in polyoxymethylene compositions. .

detailed description The present invention provides certain potions with improved release properties and reduced mold adhesion properties. The present invention relates to a lyoxymethylene composition. As used herein, The term ``simethylene'' refers to the term ``cymethylene'' in which the end group is removed by esterification or honeytylation. Equalization of formaldehyde or cyclic oligomers of formaldehyde formaldehyde or its terminal group is hydroxyl terminated. or can be end-capped by esterification or etherification. Forms with oxyalkylenes having at least two adjacent carbon atoms in the chain Contains cyclic oligomers of aldehydes.

Essentially, (σ) At least one thermoplastic polyurethane having a glass transition temperature lower than 0°C 5 to 40% by weight of rethane, and (b) at least one polyester having a molecular weight of 20.000 to 100.000; Oxymethylene polymer 60 to 95% by weight ) based on the total amount of only It has been found that the compositions exhibit mold tack and/or mold sticking properties under certain conditions. It was.

Furthermore, mold adhesion specials and mold adhesion specials of such polyoxymethylene/polyurethane compositions are available. The properties of polyoxymethylene/polyurethane with a small amount of ethylene bis-stearamide Incorporating it into a urethane composition can reduce or eliminate oxidation. It was discovered that More specifically, 0.2 to 1.0ffi amount % of ethylene bis -Polyoxymethylene/polyurethane coated with stearamide? m+, +, y thing Type adhesion of polyoxymethylene/polyurethane compositions caused by blending with It has been found that the properties and mold adhesion properties can be reduced or removed. It was.

Furthermore, this small amount of ethylene bis-stearamide is When incorporated into the urethane composition at any time before forming the composition, It has been found to be effective in reducing the mold tack and mold adhesion properties of such compositions. Served. That is, ethylene bisstearamide is blended with polyoxymethylene, Next, polyurethane is mixed with holoxymethylene/ethylene r-sostearamide. Can be mixed with things. Other methods (7) Ethylene bis-stearamide with polyurethane, followed by polyoxymethylene fs'4 urethane/ethyl Can be formulated with a renbis-stearamide mixture. Alternatively, you can By blending lyoxymethylene with polyurethane, it becomes ethylene bis-steel. Amides can be blended with polyoxymethylene/polyurethane mixtures. other As a method, all three components can be mixed at the same time. necessity It is possible to convert ethylene bis-stearamide into polyoxymethylene/polyurethane. The purpose is to uniformly distribute the composition throughout the composition.

Furthermore, the mold tackiness and mold adhesion of polyoxymethylene, which does not contain polyurethane, is reduced. Among the many and numerous compounds known to be particularly useful, ethylene Polyoxymethylene/polyurethane composition with only bis-stearamide as the top 6 Will significantly reduce or eliminate mold stickiness and mold adhesion of objects I was able to find it.

Furthermore, mold adhesion and/or mold tack in such polyoxymethylene/polyurethane compositions The amount of mold deposition increases as the m: of polyurethane in such compositions increases. , thus significantly reducing or eliminating mold sticking and mold adhesion in such compositions. The amount of ethylene bis-stearamide required to make the polyurethane in such compositions also increases as the amount of water increases.

In the case of Izu male, about 1. The amount of ethylene pith stearamide greater than θ weight i% is Almost no additional benefit is provided. Same・-guni,bo;J　O,24, The amount of ethylene bis-stearamide less than 131% is Provides little improvement in the mold adhesion properties and molding properties of polyurethane/polyurethane compositions. It doesn't look like it will work.

Furthermore, a small amount of ethylene bis-stearamide used in the a-bond of the present invention improves elongation and Increases the toughness of the compositions of Tot et al. as measured by the Izot Standard 1 test. Has additional benefits.

Therefore, the composition of the present invention essentially comprises: (α) At least one building with a soft segment glass transition temperature lower than 0℃ Thermoplastic polyurethane 5-40% by weight, (b) ethylene bis-stearamide 0 ．． 2-1.0 weight fit%, and (c) 20.000-100,000ON weight average Complementary amounts of at least one polyoxymethylene polymer having a uniform molecular weight. It will be. The essential features of the present invention described in this specification may vary without changing too much. Other ingredients, modifiers and/or elephantineants can be included in the compositions of the invention. .

As described in U.S. patent application Ser. Preferably the Gardner impact value is 91 (80 17J (150 inch bond), more preferably 17J (150 inch bond). A dog, most preferably a 25J (225 inch bond), rather large. Related information Polyurethane 15-4 as described in U.S. Pat. No. 464,411 For a composition that says 0% by weight, the preferred Izot value is 375 J,/m. (7,0 ft. bond/inch) Good dog, very good 500 J/m Thicker than (9.4 ft. bond/inch), most preferred l/< is 6501/l It is larger than n (1'2.2 feet/inch).

5 to 15 needle chips, such as those described in related U.S. patent application Ser. No. 464,412. For compositions containing polyurethane; Preferably, bis-stearamide is incorporated. Good weight [~8-12 weight] 02 to 03% by weight based on a composition containing % polyurethane is more preferred [2 Most preferred 1. About 0.0% for a composition containing a polyurethane of 1. Most preferred is 25 anal volume of ethylene bis-stearamide. Related application: U.S. 15 to 40% by weight of polyurethane as described in National Patent Application No. 464,411 [7] 0.3 to 1.0% by weight of ethylene bis- Stearamide, more preferably 20 to 35% by weight of polyurethane. On the other hand, 0.7 to 0.9% by weight is more preferable than seaweed.1. The handle is also nice. Most preferred for compositions containing 25-32% by weight polyurethane (-< about 0 ．． It is preferable to incorporate 8% by weight (7). and economic considerations.

Furthermore, ethylene bis-stearamide 02-1. θ weight% of the above polyoxymethylene Polyurethane/polyurethane compositions have extremely high commercial toughness and/or flexibility. including impact resistance as well as stiffness, strength, chemical stability and stain resistance. adversely affect other important morphological properties of such polyoxymethylene/urethane compositions. A'1 was omitted because it had no effect.

Extremely high single needle impact properties for #I compositions containing 5 to 15 units of polyurethane. The polyoxymethylene polymer may be branched or linear for compositions containing and from 20,000 to too, ooo, preferably 1d25. oo o~90,000, more preferably 30,000~7Q,000, most preferably must have a weight average molecular weight in the range of 3 to 40,000 E7 It should be noted that there is no

Instead of characterizing polyoxymethylene by its molecular weight, its melt flow It can be characterized by speed. Good for compositions with extremely high impact resistance New polyoxymethylene has a melt flow rate of 01-30 r/l 0 min 1 sj degree [A, STM I using an orifice with a diameter of 1.0 mm (0.0413 inches) )-1238, proCedure A, C’oncLitionG ( 41] Definite]. Melt flow rate of polyoxymethylene is homogeneous polymerization Press gently against the body for 0.5 to 10 minutes/10 minutes, most preferably about 0.5 to 10 minutes. M’/l o minutes, and for the copolymer (7) about 92/lO minutes.

As mentioned above, polyoxymethylene can be a homopolymer, a copolymer, or a mixture thereof. It can be either. The copolymer has a quinethylene composition vlJ May contain one or more comonomers commonly used to produce vomiting. Wear. Comonomers used for more on-roads include A/L-kylene with 2 to 12 longitudinal atoms. Contains oxy and do. If a comonomer is selected, the amount of comonomer should be 20 wt. % or less, preferably 15% by weight or less, and most preferably about 2% by weight. Dew. The most preferred comonomer is ethylene oxide, and the preferred comonomer is ethylene oxide. Cimethylene copolymer is a polymer of formaldehyde and ethylene oxide (di In the case of polymer, the amount of ethylene oxide is about 2% by weight.

Generally, polyoxymethylene homopolymers are preferred over copolymers. extremely high A homogeneous polymer suitable for use in impact-resistant composite materials is about 38,000 those with a molecular weight of 0, and those that are end-capped by chemical reactions to form esters. or an ether group, an acetate or methoxy group, respectively. It has a terminal hydroxyl group.

・Thermoplastic polyurethane suitable for use in compositions that are delicious when brewed and have good impact properties can be selected from those commercially available or the number one in the field. It can be manufactured by the following method. [For example, Maurice J Liorton Edited (1973), RqtbbeγTechlbn,ology, 2nd edition, 7th Grass, Urethane Ela, stormers, D, A, Me? /er, (See especially 453-6 Tei.) Polyurethane is polyester or polyether polyester. The reaction of lyols with soisocyanates and, in some cases, further combinations of such components with low Molecular weight polyols, dexterity (also derived from the reaction with diol chain lengthening agents) be guided. Polyurethane distomers generally have soft segments. gment), such as polyether or polyester polyols, as well as low It consists of hard segments derived from the reaction of molecular weight diols and diisocyanates. Ru. Uses polyurethane elastomers without hard segments (7 obtain, most Useful are those that contain both soft and hard segments.

Thermoplastic polyurethane suitable for use in compositions with extremely high impact resistance. In production, the hydroxyl groups per molecule must be at least 2; Both 500, preferably 1 to about 550 to about s, ooo, most preferably about L000 A polymeric soft segment having a molecular weight of ~2,500, e.g. Esther'-! , bamboo polyalkylene ether diol with some degree of branching. The organic diisosilane may be present at a ratio that results in a substantially linear polyurethane polymer. React with anate. Diol chain extender with total molecular weight less than about 250 It is also possible to combine. Motion of incyanate to hydroxyl in polymer The ratio is preferably about 0.95 to 1.08, more preferably 0.95 to 1.05, And most preferably it is 0.95-1.00.

Suitable polyester polyols include one or more dihydric alcohols and one Polyesterification products with one or more dicarbonate modifications are included. Appropriate Socarboxylic acids include adipic acid, succinic acid, sebacic acid, speric acid, and methyl adipic acid. Pinic acid, glutaric acid, pimelic acid, azelaic acid, thiodipropionic acid and cyto Contains laconic acid and mixtures thereof. Ethylene is a suitable dihydric alcohol. recall, propylene glycol, 1,4-butanediol, 1,3-butanediol ol, 2-methylpentanediolu-1.5, diethylene glycol, venta diol, hexane diol and mixtures thereof.

Additionally, 1-hydroxycarginic acid, lactones, and cyclic carbonates such as capro Lactone and hydroxyl degradation can be used in the production of polyesters.

Suitable polyesters include poly(ethylene adipate), poly(1,4-petite), (ren adipate), mixtures of these adipates and polycaprolactone. Ru.

Suitable polyether polyols include one or more alkylene oxides and Small amounts of one or more compounds with active hydrogen-containing groups, such as water, ethylene, etc. glycol, l,2- or 1,3-propylene glycol, l,4-butane Condensation products with diol and 1,5-bentanediol and mixtures thereof are included. be caught. Suitable alkylene oxide condensates include ethylene oxide, l,2-propylene Included are pyrene oxide and butylene oxide and mixtures thereof. Also Suitable polyalkylene ether glycols can be prepared from tetrahydrofuran. . In addition, suitable polyether polyols include comonomers, especially random or Block comonomers, ethylene oxide and zolopyrene oxide are derived from May contain ether dalicol and/or tetrahydrofuran (THF) can. In addition, using a THF polyether copolymer with a small amount of 3-methylTHF, You can also

Suitable polyethers include polytetramethylene ether glycol (PTMEG) , polyglopylene oxide, zolopyrene oxide and ethylene oxide copolymer and copolymers of tetrahydrofuran and ethylene oxide.

Suitable organic diisocyanates include 1,4-butylene diisocyanate), 1.6 -Hexamethylene diinocyanate, cyclopentylene-l.

3-diiso7ane), 4,4'-dicyclohexylmethane diincyanate , isophorone diisocyanate, cyclohexylene-1,4-diincyanate , 2.4-) toluylene diisocyanate), 2.6-toluylene diisocyanate , 2.4- and 2.6-toluylene diinocyanate isomer mixture, 4.4' -methylenebis(phenyl incyanate), 2,2-diphenylpropane-4 , 4'-diisocyanate, p-phenylene diinocyanate, m-phenylene diisocyanate, xylene diisocyanate), l,4-naphthylene diisocyanate Anate, 1゜5-naphthylene diisocyanate, 4.4'-diphenyl diisocyanate socyanate, azobenzene-4,4'-diisocyanate, ordinary or p-te Tramethylxylene diisocyanate and l-chlorobenzene-2,4-diiso There's cyanate. 4,4'-methylenebis(phenylisocyanate), 1. 6-hexamethylene diisocyanate, 4.4'-dicyclohexylmethanez Incyanate and 2,4-toluylene diincyanate are preferred.

and secondary amide bonds, including those derived from adipyl chloride and piperazine; and pTHEG and/or bis-chloroformate of butanediol. It is possible to have secondary urethane bonds, including those that lead to Wear.

Dihydric alcohols suitable for use as chain extenders in the production of thermoplastic polyurethanes A polymer that is either free or contains oxygen or sulfur bonds. Contains a carbon chain, l,2-ethanediol, l.

2-propanediol, isopropyl-a-glyceryl ether, 113-propanediol Pandiol, l,3-butanediol, 2,2-dimethyl-1,3-propane diol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-g methyl-1,3-propanediol, 2-methyl-2,4-bentanediol, 2 ．． 2.4-) riftyl-1,3-bentanediol, 2-ethyl-1,3-hex Sandiol, l, 4-butanediol, 2,5-hexanediol, ■, 5- Bentanediol, dihydroxy 7 clopentane, 1,6-hexanediol, l, 4-cyclohexanediol, 4,4'-cyclohexanedimethylol, Thiodiglycol, diethylene glycol, diethylene glycol, 2-methyl -1,3-propanediol, 2-methyl-2-ethyl-1゜3-prono(diol) ol, so-hydroxyethyl ether of hydroquinone, hydrogenated soot bisphene Nol A1 dihydroxyethyl terephthalate and dihydroxymethylbenze and mixtures thereof. 1.4-butanediol, 1.2 -ethanediol and 1,6-hexanediol are preferred.

In the production of thermoplastic polyurethanes, the ratio of incyanate to hydroxyl The ratio should be close to l, and the reaction can be a one-step or two-step reaction. Ru. By using a catalyst, the reaction can be carried out as is or in a bath medium. I can.

Apart from Kamiike's regarding the selection of polyurethane, it has extremely high impact resistance The most important characteristic of a thermoplastic sealing urethane with respect to obtaining a composition is its glass content. is at the transition temperature (Tg). Whenever a glass transition temperature is referred to herein, DL attached to Model 990 Thermal Analyzer L pont Model 981 DynamicIdttchanical It is measured using Analysis Ce11. This cell is cold Use liquid nitrogen as a solvent and take a sample of &2L7n (1-25 inches). It has been modified to use a gap for attaching. Thread motion amplitude is 0.2noi Set. Heating rate depends on signal amplitude from -25℃ to 170℃ to 0-40℃ /minute. The continuation is performed for each 1°C increase. increase (storag) e) and loss modulus peaks are soft segment glass transitions. Defined as temperature. Compositions with extremely high impact resistance are made from thermoplastic polyurethane. Soft segments of tongues are best produced when the glass transition temperature is below 0°C.

If tL<, the soft segment glass transition temperature of polyurethane is lower than -10°C. , more preferably 1: 15°C or less [7, most preferably 7: 30°C or less] Should. It is also possible to use blends or mixtures of thermoplastic polyurethanes. can.

For compositions with extremely flat impact resistance (7, soft segments of heat-repellent polyurethane) The molecular weight of the ment is between about 500 and about 5000, preferably between about 850 and 3000. , more preferably an average value of about 1000-2500, most preferably Polyureta/ is a soft segment with an average molecular weight of approximately 2000. Ru.

Similarly, for compositions with very high impact resistance, The moisture content should be 0.2, especially if there is no opportunity to remove the water during injection molding, for example. The moisture content should be lower, preferably less than 0.1%.

For compositions that command extremely high impact resistance, polyurethane is best It must first be mixed and dispersed in polyoxymethylene and then processed. The condition must be maintained during the formation of the biological yield.

Polyurethane is dispersed in polyoxymethylene and polycarbodiimide is dispersed in polyoxymethylene. In order to incorporate into the lyoxymethylene/polyurethane composition, Any heavy-duty mixing device that produces high shear forces can be used.

Rows of such equipment include rubber mills, internal mixers 5 such as [Banburyj and [Br abgndgr J mixer, with holes heated externally or by rubbing single or multi-blade internal mixer, [Ko-kngαdars J, multi-barrel mixer e.g. "FarrgL Continuov, s Mizertt J, Injection molding machines, and both single- and double-shaft, co-rotating and counter-rotating There are both rotating extruders. These devices can be used alone or with static mixers, mixing torpedo and/or internal pressure and/or mixing Various devices for increasing strength, such as pulp and dart designed for this purpose. (Can be used in combination with a screw. A twin screw extruder is particularly preferred. <, especially the reverse pitch element (revttrsg pitch, h element) and Preferably those with strong mixing parts, such as kneading elements. . Mixing equipment useful in all embodiments herein includes a total of 5 kneading units, not specified. element, two inverse elements, and a supply port (throatl to die). Contains two working parts with a vacuum port (7) Ort) located at approximately 70% of the distance Corotation IJ’ernst of 28II+l+ using screw design: anti It is a pfleiderer twin screw extruder. All zones are set to 190℃ Wear. The high temperature of Gui is about 220-200°C. To lower the temperature in some cases A low flow rate of cooling water was used for this purpose. 1 hour to Shiro, 8 to 13.6 to 9 (15 to 30 bits) The extruder can be operated at a speed of 1200 to 250 rpm relative to the feed rate of oxygen The supply port can be kept under a nitrogen atmosphere to remove and keep the components dry. The strands (strana) that come out of the gui are cooled in water and then covered. Can be cut into strips. It is also possible to depart from these conditions. for example When adjusting to compensate for the supply amount, do not heat the pipe below 190°C or above 260°C. Melting temperature is also possible. However, for melt mixing, 170-260℃ is required. Preferably, 185-240°C is more preferable, and 200-230°C is most preferable. 1[7].

For compositions with extremely high impact resistance [7, thermoplastic polyurethane as separate particles] Conditions such as drying a dusting composition that distributes urethane in polyoxymethylene It is important to maintain the condition in the steam mixture.

Molded products manufactured from the compositions of the invention can be compression molded, injection molded, extrusion blow molded. by any of several conventional methods including rotomolding, thermoforming, and stamping. can be manufactured by Such molded products are subject to orientation, Stretching, coating, heat treatment (a, nnea Ling) ), coating, lamination, and plating can be performed. Ru. Unused molded products, defective molded products or waste compositions of the invention are crushed and It can be reshaped.

In general, of molded products! ! ! The conditions used for manufacturing are the same as those for melt mixing above. It would be like that. More specifically, the melting temperature and residence time are set to It can be used up to the point where it ends. Preferably the melting temperature is about 170-250°C; More preferably about 185-240°C, and most preferably about 200-230°C. It would be °G. When injection molding the composition of the present invention, the complexity of the shape produced can be minimized. It is preferable to cool the mold as much as possible. However, the passage was hidden from my sister. If the squid or shape is complex, the colder the mold, the harder it will be to lighten. in general, The mold temperature is 10-120°C, preferably 10-100°C, and The mold temperature is approximately 50-90°C. Similarly, the overall hold-up during melting The cycle time that determines the amount of water can be adjusted to match the special electric conditions.

Wear. For example, if too much total hold-up time during melting is used, the composition I can understand it. If the cycle time is short or fast, molding can be performed even when the mold is under high pressure. The product cannot solidify completely. Generally, the total hold up time is approximately 3 to 15 minutes. ...and in doing so, shorter times are preferred in order to give high-quality molded products. Yes.

A composition containing 5 to 15% polyurethane and having extremely high cutting impact properties. The above preferred embodiments for manufacturing include polyurethane>, 15-40 itt, and Except as noted below, this will prevent the production of compositions with extremely high toughness. . Certain additional preferred examples below include >15-40 wt.% boron/tan; and It may be applied to the production of compositions with extremely high toughness.

For compositions with extremely high toughness [~, polyoxymethy-17 polymer is 0,000-100,000. Preferably 25,000 to 90,000°, more preferably Preferably from 30,000 to 7o, ooo, and most preferably from 60,000? (It is preferable to have a weight average molecular weight in the range of 1,000.

y+'e instead of characterizing lyoxymethylenede by its weight average molecular weight, It can be characterized by its melt flow rate. Has extremely good toughness The preferred polyoxymethylene for the composition has a melt flow rate of O1-30 f/10 minutes. -Speed [Gong diameter 1.0. (0,0413 inch) using an orifice of ASTM I)-1238, procedure A, Condition G M is set]. Preferably, the polyoxymethylene used in the composition of the present invention The melt flow rate will be between 0.5 and 1Or/lo minutes. Most preferred point Limoxymethylene is a straight line with a melt flow rate of = 'Jtr/lO min 1i3J. linear polyoxymethylene, or melt melt less than 19/10 min. A branched polyomodimethylene homopolymer having a low MW is preferred. extremely fine Is it used in compositions that have strong properties? The most preferred purchase price is i65. (J The molecular weight of OO is /f4, and the wood ends are capped and varnished by chemical reaction. Each acetate is an ether group, preferably each acetate is a mer-oxy group. It forms a wood end hydroxyl group. Extremely strong Note 2 city For the composition VC, the polyoxymethylene compound (continuous phase of the composition example) The thermoplastic polyurethane is dispersed throughout the continuous phase polyoxymethylene. swerve.

Thermoplastic polyurethane is made of polyurethane, which is made of discrete particles that are dispersed throughout the slow-stretching phase. and this configuration is determined by the proportion of polyurethane in the composition. It is most often found in Ondo at relatively low levels of threat. These particles of polyurethane are almost shape (i.e., this particle has an aspect ratio of approximately 1.0) or casing or elongated (i.e. the particle has an aspect ratio significantly greater than 1.0). Yes, the particle size distribution may be Gaussian, binomial or multinomial, truncated or other. Something can happen. If #l is the boss, these things are a little bit bossy, so [7 can be roughly oval in shape, or large and elongated, with a pointed Strands of thermoplastic polyurethane flowing through a continuous phase of lyoxymethylene can be similar. In fact, such strands are products manufactured from such compositions. can flow continuously over its entire length. Also, such strands Forming a network of thermally resonant polyurethane throughout the continuous phase of lyoxymethylene can be linked together to form a composition, and this configuration It is most often found in the onion when the proportion of urethane is relatively high.

If the polyurethane phase is 1 long, the direction of stretching is generally the same for all phases. (7) Even in the tsuba state, it is given during the final stage of production of the composition. It is the direction of shear force. For example, external melt mixing in a twin-screw extrusion mode followed by round ( The composition is passed through a round die (7) and cooled in water. When manufacturing rods, thermoplastic polyurethane daughter extensions, if present, are generally added to the shaft of the rod. Push in parallel. The results of L2 drawing are also useful for the purpose of characterizing such compositions. The average cross-sectional shape of the polyurethane phase perpendicular to the direction and at the center of the resulting product It was found that the condition can be measured.

The average cross-sectional shape is measured by the following method. Pair 1 to the rod axis. vertically formed 0 , 32X1.27X12.7L: Inside of Tn (34X34X5 inches) rod> Operated at -90 °C to cut a 200 nm thick section from the , diamond knife and [Sorval 1-Ch, list sense tt J F T 5-LTC-2UJ [5orvall JMT -213 Ultra-microtome Use. Using ethanol as a knife self-extinguisher, collect a large number of sections, and then Place in a Petri dish wrapped in distilled water. One cut was made due to the mixed action of ethanol and water. The sections are separately Vc spread 9 and floated on the water surface. Cut, (, cut the cut section to 20 The top of the grid for the 4-microscope, which is fitted with a 0-piece steel casing, has been reassembled. 70 low 80KV with film camera and Eastman 5302 film Electron images of representative sections at 2500X using a Zeiss system and a Qf10A electron microscope. E'珀5. t-3 and 7 to take nine.

This microscope negative was enlarged in a dark room, and finally 1lj(00, 3　＞ζ254ω (8XjO inches) The key to the key is the samurai.

If present, most polyurethanes are distributed (-2 traps). l Z 7 t, * (5 in. h), each 20.3 x 25.4 on (8 x l 0 inch) offshore gorge: # Two small pieces of 102XI Z7cmrn (4X5 inner) were cut from A. Almost JJμ has such a direction. Flying spot scanner (f lying spot 5 canner) 200 square microns I made a tanshi in one line at the same time in the short direction of the imitation mirror copy field. Shun 1 of this WW copying spot C') Appears in a light and dark pattern with varying levels of gray between 17.

Calculate the average density of this thorn. All images (darker than this average value) are thermoplastic. It is thought to be a plastic polyurethane phase. On the other hand, all the bright images on this line are polygons. It is believed to be a simethylene matrix (rnatrix). up pulse (up Calculate the average length of the pulses (dark area or thermoplastic polyurethane phase).

This measured value will hereinafter be referred to as the average cross-sectional diameter at the small diameter.

A composition with extremely high toughness has a thermoplastic polyurethane with an average cross-sectional particle size of It can be manufactured if the thickness is 0.9 microns or less. Preferable (7) Heat-repellent poly The average cross-sectional diameter of urethane is smaller than 0.7 microns, the most preferred (7 is 0.5 microns) is smaller than the In practice, [7] the urethane phase should be at least 0.01 mic. It should also have an average cross-sectional diameter of 100 mm.

Apart from the above regarding the selection of polyurethane, it has extremely high toughness The most important feature of thermoplastic polyurethane with regard to obtaining compositions is its soft se... and glass transition if (Tg). Compositions with extremely high toughness When the soft segment glass transition temperature of thermoplastic polyurethane is lower than 115°C can be manufactured in the best way. Preferably the soft segment glass transition temperature of the polyurethane is below -20°C, and most preferably below -30°C. Also thermoplastic Blends or mixtures of polyurethanes can be used. Extremely tough for compositions having an intrinsic viscosity of 0.7 or higher (dimethyl 0.1 T4 polyurethane in formamide using a ``Sc, ottJ automatic viscometer'' Thermal radiation properties of polyurethane (measured by ASTM I)-2851) should generally be used. Thermoplastic polyurethane with intrinsic viscosity up to 2-7 Tan has been usefully used in such compositions, but generally has a hardness of 0.75 to 2-5. Those with a viscosity of 1 bar are preferred, and those with an intrinsic viscosity of 1.0 to 1.7 are preferred. preferable. In addition, we developed it using polyurethane with an extremely low intrinsic viscosity, and this modified during the compounding operation, for example by further combining or combining again. , thus increasing the effective viscosity of the polyurethane to the desired degree or This is also possible if the intrinsic viscosity of the polyurethane is quite low. Also, high specific V Start with polyurethane that has 5 degrees and decompose this during mixing or could be hydrolyzed to achieve the desired effective viscosity.

In the following examples, specific examples of the special electricity of the present invention and polyurethane-free polyurethane. Commonly used to reduce mold tackiness and scarring properties of oxymethylene compositions The set Iy containing the compounds to be compared with the control center, Ogi's example, except that the compound is other than ethylene bis-stearamide. Book The compositions of the invention may be significantly reduced, shredded or removed during the bath melt mixing and molding process. The control composition was found to have different characteristics in terms of mold viscosity and mold adhesion. You will understand. P4 Unless otherwise noted, all parts and numbers are by weight. And all the temperatures are at Mr. Setsu's feet. Measurements that are not originally in Sl units are It was converted into a sea urchin, and rounded if appropriate.

In the following examples, formulation formulations for measuring mold tolerance and mold attachment are shown. The shape is HPH, Inc, HtD l 25 door S partan injection molding This was done using a molding machine. This device uses a screw with a diameter of 4.5α (1.75 inches). It was equipped with a screw injection device. Thickness o, azcrn (3A inches) The break (PLE QWG) at a cylinder temperature of 176-197℃, 15 /15 seconds, 20/Ls seconds and 30/15 seconds cycles (injection/holding). Ta. During the entire process, the machines used in each example are purged and all types of deposits are removed with water. The machine must be stopped to clean with alumina slurry inside and then remove all parts. As long as the parts do not stick so severely that they must be ot), and if it sticks badly, do not mold that example any further. It was.

Examples 1 to 25 all have an intrinsic viscosity of 1.33 and a glass transition temperature of -35°C. 30% by weight of plastic polyurethane, 37% by weight of asobic acid, 39% by weight of butanediol] ii% and methylene bisphenyl incyanate 24 weight skin chemical composition, po Lyamide stabilizer (about 38% polycaprolactam/polyhexamethylene aziboamide Terpolymer of 35% polyhexamethylene sepadiamide 27%) 0.75% Amount %, 2.2'-methylenebis(6-6-butyl-4-methylphenol) acid 0.11% by weight of antioxidant, lubricants and polycarbodiimide specified in Table 1, and and complementary amounts of acetate end caps having a weight average molecular weight of about 63,000. polyoxymethylene homopolymer (as described in U.S. Pat. No. 2.99 & 40j) The paste was prepared using the following formulation. For the various lubricants and types shown in Table 1. In addition, certain compositions v (shown in Table 1) have a molecular weight of about 1000, and A formula with an average value of about 3 Polycarbodiimide (-! or mixture of polycarbodiimides) containing Q unit 0 ．． 1% by weight (except for control example 2 which had 0.3% by weight).

In Table 1, all data are based on mold surface temperature Wi, 0.32α (%) at 100°C. Inch) break molded products. [is<M Cde-1αminα tion) The term J refers to parts that stick to the surface of the mold, which are ejected and machined from the mold into a bottle. Represents a surface defect that results in a thin layer that partially peels off when subjected to mechanically forced removal. .

In all of the following examples, the polyurethane used was ethylene bis-stearyl It should be noted that this is a proprietary product containing an amount of 3I. subordinate Therefore, a composition containing 30% by weight of polyurethane can be used in an amount and type of In addition to the lubricant, it will contain about 0.18% by weight ethylene bis-stearamide. cormorant. Thus, the values shown in the "added lubricant" column of the table indicate that The sample composition contains 0.18% ethylene bis-stearamide. I haven't looked at it. Similarly, in Example 26 containing 10% by weight polyurethane, Added via polyurethane to 0.06% Lenbis-stearamide. implementation Example 26 represents only added lubricant. However, the book including the claims The amount of ethylene bis-stearamide shown in all of the specifications was 41J This is the total amount including any amount that may be incorporated via the rethane.

λ 0 Example 26 10% by weight of thermoplastic polyurethane similar to that used in Examples 1-25; 0.75% by weight of polyamide stabilizer, 0.11% by weight of similar antioxidant, similar polyamide. 0.1% by weight of lycarbodiimide, 0.0% added ethylene bisnistearamide. 2]i% and about 38. Complementary amounts of acetate with a weight average molecular weight of o 00 Evaluating Samples Containing Terminated Polyoxymethylene Homopolymers Prepared for. The above group without adding this ethylene bis-stearamide The compositions were evaluated for mold tack and adhesion. Both resins have good mold adhesion. Didn't show it. Most samples with chilled ethylene bis-stearamide A sample without ethylene bis-stearamide added while not compromising mold stickiness. The material showed considerable stickiness in thermoformed articles [7].

Examples 27-41 岨FJy of the present invention! Ethylene bisulfate for elongation and isot value of 1/I A series of experiments were conducted to evaluate the effect of thealamide. Except as stated in the following Composition A was prepared substantially as described in Examples 1-25. Tensile strength is ASTM '-D-638; elongation is determined by ASTM-D-638; and , and Izot were measured according to ASTM-1)-256. Antioxidant A is 4. 4'-Butylidene bis(6-6-butyl-3-methylphenol), Antioxidant B is 1,6-hexamethylenebis(3,5-di-t-butyl-4 -hydroxyhydrocinnamate). All compositions have 0.1% oxidation Contains an inhibitor.

(%) Preventer <HPα) (chi) 17m27 0 A 4ZO20010 15 280,3A 4ZO230961 290,6A 4Z0 205 117530 u A 417135 908 31 0.2 A 4Z7 140 101532 0.4 A 42+0 2 05 112133 0.6 A 40.7 185 128234 0 tJ 44.1 110 53435 0.6 B 40.7245 85436 0 B 4λ7 175 90837 0.6 B 4L0 205 1015 38 0 B 110280 961 39 α6 B 41.4260 96140 0 8 4L7 135 09 3441 0.6 B 4L4 190 1041 Industrial use The polyoxymethylene composition of the present invention has a grade I! L-zuke, Ushio 11 Herme safety helmet, shoe cleat, safety steering wheel Jk (steering column) parts, special zipper-1 railroad track RA#oad tie insulation, ski binding 1. binding), Useful in the manufacture of mechanical transporters and small engine parts. Usually polyoxymethi manufactured from these compositions with other notable properties found in len compositions. Extremely high impact resistance and/or toughness of the product and exceptional abrasion resistance (wg cLτ), these items include gears, moving parts, and fuel tanks. It is particularly well suited for such applications.

best method The best method of the invention, the single best polyoxymethylene composition of the invention is Depends on the particular desired end use and the combination of properties specifically required for that use yields a product that is most favorable for its overall balance of properties. One composition and molding conditions of the present invention are Polykun 2F 30 A composition containing 10% by weight of rethane is detailed in Example 26.

Although not part of the invention, having a molecular weight of about 1000 and an average value of n of about 3 an expression with about 0.1% by weight of polycarbodiimide (or mixture of polycarbodiimides) are preferably included in the formulations of the invention.

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Claims (1)

[Claims] 14 Essentially, (α) At least l birch heat wandering around the soft segment glass transition temperature below 0°C 5-40% by weight of plastic polyurekne, (b) ethylene bis-stearamide 02 ~1.0% by weight, and (C)2o,ooo weight average molecular weight of ~100,000 a thermoplastic comprising complementary amounts of at least one polyoxymethylene polymer having Sex stream oxymethylene composition. 2- The amount of polyurethane is 5 to 15%, and the amount of ethyl and 2. A composition according to claim 1, wherein the content of alumamide is 0.2 to 0.4% by weight. 3. The amount of polyurethane is 15 to 40% by weight, and the amount of polyurethane is 15 to 40% by weight. 1. The composition according to claim 1, wherein the weight of Ruamide maple is 0.3 to 1.0 weight. tyg urethane dispersed throughout the polyoxymethylene polymer as separate particles and the composition has a Gardner impact value greater than 91. Compositions as described. 5. Polyurethane has a soft segment glass transition temperature lower than 115°C, and Individual phases in which the urethane has an average RDR diameter surface with a minimum diameter of 0.9 microns or less L7 is polyoxymethylene dispersed throughout the body]2, and composition S1 is 315 4. A composition according to claim 3, which has an Izodt value greater than 17. 6. Homogeneous polymerization in which polyoxymethylene has a molecular weight of 30,000 to 70,000 The composition according to claim 4, which is a body. 7. Polyoxymethylene has a molecular weight of ao, ooo to 70,0OOi. The composition according to claim 5, which is a song combination. & The composition according to claim 4, having a Gardner impact value greater than 251. 9. The composition according to claim 5, wherein the Izot 1 shift is greater than 651/normal. 10. Claim 4: The thermoplastic polyurethane has a weight base of 8 to 12% by weight of the composition. The composition described in . 11 Claims in which the thermoplastic polyurethane constitutes 25-32N of the composition 5. The composition according to 5. 12-　Thermoplastic polyurethane coated with butylene azide, methylene bis(phenyl Claim 4 derived from the reaction of iso7anate) and 1,4-butanediol Group # listed in: Things. 1 & thermoplastic polyurethane with petite/adipate, methylene bis(phenyl- Claim 5 derived from the reaction of 1,4-butanediol and 1,4-butanediol The composition described in . 14 Essentially, (a) at least one type of heat that sets a soft segment glass transition temperature below 0°C; 5 to 40 i of writable polyurethane, and (b) 20.000-t o o, o　o　　　weight=+at least one polyoxymethylene in a complementary amount to Mold release properties and molding of a thermoplastic IJ oxymethylene composition consisting of a ethylene polymer In addition to improving adhesion properties, ethylene bis-stairs are present in polyoxymethylene compositions. The mold release properties of the composition include blending a coulamide of 0.2 to 1.0. Method for improving properties and mold adhesion properties. 15, the amount of ethylene bis-stearamide is 0.2 to 0.4 ft% by weight; 15. A method according to claim 14, wherein the amount of polyurethane is from 5 to 15% by weight. la The content of ethylene bis-stearamide is 0.3 to 1.0% by weight, and Is the amount of polyurethane 15 to 40 times? The person stated in claim 14 that is Jt% Law. 17. Ethylene bis-stearamide in melt compounded composition under high shear The method according to claim 14, in which the composition is combined. 1. A molded product produced from the composition according to claim 1. 19. Compression molding, injection molding, extrusion, blow molding, rotational molding, melt spinning, thermoforming and The production of molded products according to range 18 of υ, selected from the group consisting of Construction method. 20 A claim that is a type of molding and the molding temperature is 10-120'C The method according to scope 19. 21. Molding temperature is 50. , ~90'C.