CN1113181A - Waterworks-related member of polyacetal resin - Google Patents
Waterworks-related member of polyacetal resin Download PDFInfo
- Publication number
- CN1113181A CN1113181A CN94112753A CN94112753A CN1113181A CN 1113181 A CN1113181 A CN 1113181A CN 94112753 A CN94112753 A CN 94112753A CN 94112753 A CN94112753 A CN 94112753A CN 1113181 A CN1113181 A CN 1113181A
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- China
- Prior art keywords
- polyacetal resin
- zinc
- waterworks
- acid
- hydrotalcite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/04—Copolyoxymethylenes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to an aqueduct related component material comprising a polyacetal resin compounded with an antioxidant and a metal containing compound and having excellent durability under a condition exposed for a long time to tap water bactericidally treated with chlorine and a chlorine containing compound. This material is made by molding a composition which comprises (A) 100 pts.wt. polyacetal resin added and compounded with (B) 0.01-5.0 pts.wt. antioxidant and (C) 0.01-10 pts.wt. metal containing compound selected from a zinc containing compound and a hydrotalcite and a molded article of the same has >=95% weight retention when immersed in 10 ppm concentration chlorine water at 60 deg.C for 60 days.
Description
The invention relates to chlorine and chlorine-containing compound sterilization processing running water in also have good durability under the condition of being shone for a long time waterworks-related member of polyacetal resin.
As everyone knows, polyacetal resin, as aspect the physical properties such as mechanical performance, electric property, and all very good representational engineering resins of chemical characteristics such as chemical-resistant reagent and hear resistance, utilized extremely widely in a lot of fields in recent years.But,,, also require to do further to improve as the character of this class material along with polyacetal resin utilizes the expansion in field.
As the example of this generic request, for example, thirst for giving the durability to the height of the chlorine water under the extensive concentration range (anti-chlorine water) for being used for water supply pipe for formed products.Yet the means as the anti-chlorine water that improves polyacetal resin also do not form a specific scheme up to now, and consistent processing means are to add to cooperate a kind of known stronger alkaline matter.
But, method before adopting can not be given sufficient anti-chlorine water for polyacetal resin, and the parts that are used for the polyacetal resin system that water supply pipe uses can not nonvolatilly be used, and must change parts in the short time, are therefore expecting this improvement.
Present inventors, be found that of obtaining that a kind of polyacetal resin formed body that also has durability in the running water of chlorine and chlorine-containing compound sterilization processing under for a long time by the solarization condition studies deeply, by using a kind of specific containing metal compound compositions that in polyacetal resin, cooperates antioxidant, just can obtain the good waterworks-related member of polyacetal resin of anti-chlorine water, reach and finished purpose of the present invention.
That is, the invention relates to waterworks-related member of polyacetal resin, it is characterized in that, this material be by
(A) in the polyacetal resin of 100 weight portions, add cooperation
(B) antioxidant of 0.01～5.0 weight portion and
(C) zinc compound of 0.01～10 weight portion and be selected from the formed body of the compound compositions moulding that contains more than one metals of hydrotalcite, it is that 60 ℃ of weight conservation rates that soaked 60 days down are more than 95% in the chlorine water of 10ppm in concentration.
Below, be described in detail for the composition of the material that constitutes polyacetal resin system of the present invention.
As being used for zinc compound of the present invention (C), specifiable example has, zinc oxide, zinc hydroxide, zinc carbonate, Firebrake ZB, zinc metaborate, organic acid zinc etc., and these zinc compounds can use separately, also can two or more mixing use.In addition, every carbon number is that the organic acid with 1 above carboxyl more than 1 can have as concrete example is specifiable as the organic acid that constitutes organic acid zinc, formic acid, acetate, propionic acid, carbon number are alkanoic acid more than 4 and alkenoic acid or chain acetylenic acid, malonic acid, citric acid, adipic acid, maleic acid, oxalic acid, benzoic acid, phthalic acid, trimellitic acid, salicylic acid, gallic acid, aphthenic acids etc., and their isomers, their substitutive derivative in addition.Particularly preferably be carbon number and be the aliphatic acid more than 12, laurate, myristic acid, palmitic acid, stearic acid, mountain Yu acid are arranged as preference is specifiable.
In addition, all can use as the hydrotalcite that is used for hydrotalcite of the present invention (C), the following general formula of all usefulness (I) expression,
General formula (I):
(X in the formula, Y, Z are respectively 0.6≤X≤3.0≤Y≤3, the number of 0＜Z≤2.4, and be the number of Y+Z＞0, a is the number of 0≤a≤6, M is at least a 1 above valency metal, and R is at least a above divalent metal, and A is an anion, n represents the valence mumber of anion A, and m is the number of 0≤m≤3).
Particularly preferably be with general formula (2) expression contain aluminium and magnesium, and zinc is as the hydrotalcite of metal ingredient.
(X in the formula, Z are respectively the number of 0.6≤X≤3,0＜Z≤2.4, and m and a similarly are the numbers of 0≤m≤3.0≤a≤6, and in addition, K is the number of 0≤X≤1.2).
In addition, in order to improve the operability of these hydrotalcites better, the most handy fatty acid treatment surface, and class aliphatic acid is specifiable that laurate, myristic acid, palmitic acid, stearic acid, mountain Yu acid are arranged as this.
In (C) composition, contain as the zinc of metal ingredient and the hydrotalcite of aluminium and magnesium, zinc oxide, zinc hydroxide, zinc carbonate are particularly preferred materials.
The amount ranges of (C) composition in the present invention is, is 0.01～10.0 weight portion with respect to the polyacetal resin of 100 weight portions, preferred 0.05～5 weight portion, preferred especially 0.10～2.0 weight portion.
Being used for antioxidant of the present invention (B) is Hinered phenols; for example; 2; 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol); 1.6-hexylene glycol-two (3.5-two-tert-butyl-4-hydroxyl hydrogenated cinnamate); four [inferior (methyl (3.5-two-tert-butyl-4-hydroxyl hydrogenated cinnamate)] methane; triethylene glycol-two-3-(3-tert-butyl-4-hydroxy-5-methyl base phenyl) propionic ester; 1; 3; 5-trimethyl-2; 4; 6-three (3; 5-two-tert-butyl-4-hydroxyl-benzyl) benzene; n-octadecyl-3-(4 '-hydroxyl-3 '; 5 '-two-tert-butyl phenol) propionic ester; 4; 4 '-di-2-ethylhexylphosphine oxide (2; 6-two-tert-butyl phenol); 4; 4 '-butylidene-two-(6-tert-butyl-3-methyl-phenol); two-hard ester acyl group-3; 5-two-tert-butyl-4-hydroxybenzyl phosphonates; 2-tert-butyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-aminomethyl phenyl acrylate; 3; 9-pair 2-[3-(3-tert-butyl-4-hydroxy-5-methyl base phenyl) and propionyloxy]-1,1 dimethyl ethyl }-2,4; 8; 10-four oxaspiros [5,5]+-(carbon) alkane etc., hindered amines; for example; 4-acetoxyl group-2,2,6; the 6-tetramethyl piperidine; 4-stearoyl-oxy-2; 2,6, the 6-tetramethyl piperidine; 4-acryloxy-2; 2; 6, the 6-tetramethyl piperidine; 4-methoxyl group-2,2; 6; the 6-tetramethyl piperidine; 4-benzoyloxy-2,2,6; the 6-tetramethyl piperidine; 4-cyclohexyloxy-2; 2,6, the 6-tetramethyl piperidine; 4-phenoxy group-2; 2; 6, the 6-tetramethyl piperidine; 4-benzyloxy-2,2; 6; the 6-tetramethyl piperidine; 4-(aniline formyloxy) 2,2,6; the 6-tetramethyl piperidine; two (2,2,6; 6-tetramethyl-4-piperidyl) oxalate; two (2; 2,6,6-tetramethyl-4-piperidyl) malonate; two (2; 2; 6,6-tetramethyl-4-piperidyl) adipate ester; two (2,2; 6; 6-tetramethyl-4-piperidyl) sebacate; two (1,2,2; 6; 6-pentamethyl-piperidyl) sebacate; two (2,2,6; 6-tetramethyl-4 piperidyl) terephthalate; 1; 2-two (2,2,6; 6-tetramethyl-4-piperidyl oxygen) ethane; two (2; 2,6,6-tetramethyl-4-piperidyl) hexa-methylene-1; the 6-diurethane; two (1-methyl-2; 2,6,6-tetramethyl-4-piperidyl) adipate ester; three (2; 2; 6,6-tetramethyl-4-piperidyl) benzene-1,3; 5 ,-tricarboxylic ester etc.
In addition, the condensation product of the piperidine derivative of HMW, for example, butanedioic acid dimethyl 1-(2-ethoxy)-and 4-hydroxyl-2,2,6,6-tetramethyl piperidine condensation product, poly-[(6-morpholino-S-triazine-2,4-two bases) [(2,2,6,6-tetramethyl-4-piperidyl] imino group] hexa-methylene [((2,2,6,6-tetramethyl-4-piperidyl) imino group]] etc. also be effectively, can use more than at least a or two in the middle of these.
In the middle of these materials, four [methylene (3,5-two-tert-butyl-4-hydroxyl hydrogenated cinnamate)] methane, triethylene glycol-two-3-(3-tert-butyl-4-hydroxy-5-methyl base phenyl) propionic ester, 3,9-pair 2-[3-(3-tert-butyl-4-hydroxy-5-methyl base phenyl) and propionyloxy]-1, the 1-dimethyl ethyl }-2,4,8,10-four oxaspiros [5,5]+-(carbon) alkane, poly-[(6-morpholino-S-triazine-2,4-two bases) [2,2,6,6-tetramethyl-4-piperidyl] imino group]-hexa-methylene [2,2,6,6-tetramethyl-4-piperidyl) imino group]] be particularly preferred material.
The amount ranges of (B) composition in the present invention is, is 0.01～5.0 weight portion with respect to the polyacetal resin (A) of 100 weight portions.
Said above-mentioned (B) and (C) polyacetal resin of composition (A) of having cooperated is with oxygen methylene (CH
2O-) as the high molecular compound of main composition unit, the Copolyacetal, terpolymer, block copolymer etc. that wherein also contain a small amount of other component unit beyond the polyacetals homopolymers, deoxygenation methylene all are available, in addition, not only molecule is line style but also branched or the macromolecular compound of cross-linked structure is arranged also to be useful.Also have,, then do not have special restriction for its degree of polymerization as long as can moulding.
When suitably using as auxiliary agent, the effect of zinc compound and hydrotalcite is brought into play fully as the material with more than one formolite reaction amino, amide groups and hydroxyl of the composition among the present invention (D).This be because, the polyacetals formed body comprises the formic acid that a part is generated by oxidation of formaldehyde in resin forming because it reacts with the application's zinc compound and hydrotalcite, thereby those make the former effect that dies down that produces effect be subjected to inhibition.Said have more than one such formolite reaction amino, amide groups, the material of hydroxyl, but example has, melamine, the phenyl diamino triazine, the condensation product of dicyano diamides and they and formaldehyde, polymine, PAH, the homopolymers of acrylamide, copolymer and cross-linked polymer, polyglycine, poly-(Beta-alanine), nylon-3, nylon-6,6, nylon-6,10, PA-12, polyethylene glycol, polyglycerol, the fatty-acid monoester of glycerine and two glycerine, glycerine monostearate for example, two glycerine monostearates, glycerine list isostearate, two glycerine list isostearates, the glycerine monopalmitate, two glycerine monopalmitates, fatty acid amide, ethylidene-two (stearmides) for example, hexa-methylene-two (stearmide), two (stearoyl amido ethyl) decanedioyl amine etc., at least wherein a kind of can be used, also two or more mixtures can be used.
In the middle of these, melamine, the fatty-acid monoester of the condensation product of melamine and formaldehyde, the homopolymers of acrylamide, copolymer and cross-linked polymer, glycerine and two glycerine is particularly preferred materials.
Be somebody's turn to do (D) composition,, add 0.01～3.0 weight portion, preferably add 0.05～1.0 weight portion with respect to the polyacetal resin (A) of 100 weight portions.
The amount that is used for various additive of the present invention (B)～(D) can not get enough performances under the situation below the ormal weight scope, yet when addition was superfluous, the mechanical and physical performance of resin molded body descended, and was undesirable therefore.
In polyacetal resin formed body of the present invention, according to its purpose also can (but optional) and with more than one except that above-mentioned antioxidant, zinc compound, hydrotalcite, have the compound that contains organic and inorganic metal the material of more than one formolite reaction amino, amide groups, hydroxyl.
Waterworks-related member of polyacetal resin of the present invention, can also cooperate various known additives, for example, various colouring agents, lubricant, releasing agent, nucleator, antistatic additive, weather-proof (light) stabilizing agent, other surfactant, various polymer etc.In addition, in the scope that the performance that does not make purpose formed products of the present invention descends significantly, can be composite the filler of fibrous, sheet, powdery etc. of one or more known inorganic, organic, metals etc.Example as this class inorganic filler has, glass fibre, potassium titanate fibre, hollow glass ball, talcum, mica, muscovite, wollastonite etc.And this wherein any all can use and do not have any restriction.In addition, adopt the known method that is generally used for making resin forming product in the past, can make polyacetal resin formed products of the present invention at an easy rate.For example, after various compositions are mixed, carry out mixing and extrude with single shaft or biaxial extruder, make section (particle), the amount of should cutting into slices is again in accordance with regulations mixed (dilution), so that supply with moulding, and the method etc. that obtains the formed products of purpose composition after moulding all can be used.In addition, in the modulation of the composition that is used for this formed products, for will pulverizing as part or all of the polyacetal resin of basic composition, and with it with after other composition mixes, process such as extrude again, preferably select those methods that make the additive good dispersion for use.
Resin molded body of the present invention can be used to think that chlorine water can cause among some purposes of harm, is particularly useful for those fields relevant with running water.As concrete formed products, at least a portion is to form the running water utensil that product constitute by polyacetal resin, tap water meter is for example arranged, hopper, purification tank, hot water supply apparatus, water purifier, water regulator, water sprinkler, the attached utensil of washing room, the attached utensil in kitchen, the attached utensil in bathroom, the attached utensil in lavatory, pipe arrangement etc., as what parts more specifically can be enumerated gear is arranged, cam, lever, oil tanker, bearing, underframe, liner, packing ring, feed pipe, joint, shower nozzle, nozzle, ball float, axle, guide rail, block, spherical screw tap, filter screen, delivery port, tap, bucket, water butt etc.
Embodiment
Specifically describe the present invention with embodiment below, but the present invention is not limited to this.
When the evaluation method of the relevant anti-chlorine water of explanation, be that above-mentioned composition is made for ASTM1 dumb-bell shape tension test sheet, this formed products is adjusted under 60 ℃ of temperature in the chlorine water solution that concentration is 10ppm soaks, in the official hour interval, take out.The formed products that stands this processing was dried under 105 ℃ 3 hours, then, measured the weight and the tensile properties of formed products.For whole formed products, measure its weight before handling, the weight difference before and after handle at last, and calculate weight conservation rate after the chlorine water solution-treated with following formula.Similarly, go out stretching strength retentivity from the tensile strength calculation of handling front and back again.
(the formed products weight (hot strength) * 100 after the processing)/(the formed products weight hot strength before handling)
Weight conservation rate (stretching strength retentivity) after=processing (%)
Embodiment 1-11 and comparative example 1-7
In the Copolyacetal of 100 weight portions, by antioxidant, zinc compound and/or the hydrotalcite shown in the listed proportioning interpolation of table 1 table 1, have a material of more than one formolite reaction amino, amide groups and hydroxyl in addition, and mix, in extruder, obtain granular composition then and carry out above-mentioned evaluation.The results are shown in the table 1.
In addition, as shown in table 1 for relatively, for the occasion that does not add antioxidant or zinc compound and/or hydrotalcite, add the occasion of the compound outside the present invention's regulation etc., similarly press embodiment 1 and prepare granular composition, and carry out above-mentioned evaluation.The results are shown in the table 1.
In addition, used antioxidant, zinc compound, hydrotalcite, material with formolite reaction amino, amide groups and hydroxyl more than a kind are materials as follows:
Notes-1, antioxidant
B-1: triethylene glycol-two-[3-(3-tert-butyl-4-hydroxy-5-methyl base phenyl) propionic ester]
B-2: poly-[(6-morpholino-S-triazine-2,4-two bases) [2,2,6,6-tetramethyl-4-piperidyl] imino group] hexa-methylene [2,2,6,6-tetramethyl-4-piperidyl] imino group]].
C-1: zinc oxide
C-2: zinc carbonate
Notes-3, hydrotalcite
C-3: 39.17g NaOH and 11.16g sodium carbonate under agitation are added in 1.0 premium on currency, and heat up.With the mol ratio of Mg/Al be 2.0 then, NH
3The mol ratio of/Al is that 0.35 magnesium chloride, aluminium chloride, ammonium chloride solution slowly add, and makes the reacting slurry of PH=10.2.Under 40～90 ℃ temperature, stir again and reacted in about 10～20 hours, and to wherein adding about 3.3g stearic acid and under agitation carrying out surface treatment.Filter then, wash and under 70 ℃, carry out drying, use the small sample abrasive dust broken again, make synthetic hydrotalcite at last.
C-4: except the mol ratio of (Mg+Zn)/Al is 2.25, MgCl
2: ZnCl
3=9: 1, NH
3The mol ratio of/Al is beyond 0.14, and all the other press the synthetic hydrotalcite of c-3 same procedure preparation.
Annotate-4, have the material of formolite reaction base
D-1: carbamide condensation product
D-2: polyacrylamide
D-3: propylene glycol monostearate
Notes-5, other stabilizing agent
D '-1: 12-hydroxy stearic acid calcium
Annotate) when stretching strength retentivity 100% is above, be expressed as 100%.In addition, 50% when following, the deviation of data is big, is difficult to accurate mensuration.So become [-].
Above explanation and embodiment show, the formed products that constitutes based on the resin combination by previous method was through 20 days, formed body weight conservation rate is lower than 95% or below it, and when soaking in the chlorine water of formed products under 10ppm concentration that resin combination of the present invention constitutes, under 60 ℃ after 60 days the weight conservation rate of formed products more than 95%, so be applicable to above-mentioned various uses.
Claims (4)
1, a kind of waterworks-related member of polyacetal resin is characterized in that, this material be by
(A) in the 100 weight portion polyacetal resins, add cooperation
(B) 0.01～5.0 weight portion antioxidant and
(C) 0.01～10 weight portion zinc compound and be selected from the formed body of the compound compositions moulding that contains more than one metals of hydrotalcite, it is that 60 ℃ of weight conservation rates when soaking 60 days down are material more than 95% in the chlorine water of 10ppm in concentration.
2, according to the waterworks-related member of polyacetal resin of claim 1 record, antioxidant wherein (B) is to be selected from Hinered phenols and the hindered amines more than one.
3, according to the waterworks-related member of polyacetal resin of claim 1 or 2 records, containing metal compound (C) wherein is to be selected from hydrotalcite, zinc oxide, zinc hydroxide and the zinc carbonate that contains zinc more than one.
4, according to the waterworks-related member of polyacetal resin of any one record of claim 1-3, wherein said polyacetal resin formed body is to have cooperated being selected from of 0.01-3.0 weight portion to contain the formed body that composition molding that more than one (D) in the material of more than one formolite reaction amino, amide groups, hydroxyl form forms in the polyacetals with respect to 100 weight portions.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP302609/1993 | 1993-12-02 | ||
| JP302609/93 | 1993-12-02 | ||
| JP5302609A JPH07150005A (en) | 1993-12-02 | 1993-12-02 | Aqueduct related component material made of polyacetal resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1113181A true CN1113181A (en) | 1995-12-13 |
| CN1063705C CN1063705C (en) | 2001-03-28 |
Family
ID=17911047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94112753A Expired - Lifetime CN1063705C (en) | 1993-12-02 | 1994-12-01 | Waterworks-related member of polyacetal resin |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH07150005A (en) |
| KR (1) | KR0142504B1 (en) |
| CN (1) | CN1063705C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19943178A1 (en) * | 1999-09-09 | 2001-03-15 | Ticona Gmbh | Polyoxymethylene with improved stability against acids and its use |
| KR20040061720A (en) * | 2002-12-31 | 2004-07-07 | 주식회사 코오롱 | Polyoxymethylene Composition |
| US6974849B2 (en) * | 2003-03-03 | 2005-12-13 | Ticona Llc | Polyacetals with improved resistance to bleach |
| JP6006590B2 (en) * | 2012-09-06 | 2016-10-12 | 三菱エンジニアリングプラスチックス株式会社 | POLYACETAL RESIN COMPOSITION, MOLDED ARTICLE, AND WATER ARTICLE |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03290459A (en) * | 1990-04-06 | 1991-12-20 | Asahi Chem Ind Co Ltd | Polyacetal resin composition |
-
1993
- 1993-12-02 JP JP5302609A patent/JPH07150005A/en active Pending
-
1994
- 1994-11-25 KR KR1019940031190A patent/KR0142504B1/en not_active IP Right Cessation
- 1994-12-01 CN CN94112753A patent/CN1063705C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1063705C (en) | 2001-03-28 |
| KR0142504B1 (en) | 1998-07-15 |
| KR950018245A (en) | 1995-07-22 |
| JPH07150005A (en) | 1995-06-13 |
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Expiration termination date: 20141201 Granted publication date: 20010328 |