CN1045978C - Automotive member of polyacetal resin - Google Patents
Automotive member of polyacetal resin Download PDFInfo
- Publication number
- CN1045978C CN1045978C CN94113081A CN94113081A CN1045978C CN 1045978 C CN1045978 C CN 1045978C CN 94113081 A CN94113081 A CN 94113081A CN 94113081 A CN94113081 A CN 94113081A CN 1045978 C CN1045978 C CN 1045978C
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- Prior art keywords
- polyacetal resin
- zinc
- acid
- weight
- automotive member
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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
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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)
Abstract
The invention provides an automobile related member material comprised of a composition made by blending an antioxidant and a specific metal containing compound into a polyacetal resin and hardly corroding by calcium chloride, sodium chloride, etc., in the presence of a galvanized steel sheet and water. This member material 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. one or more metal-containing compound.
Description
The invention relates to galvanized iron sheet and a kind of corrosion automotive member of polyacetal resin seldom that in the presence of water, causes because of calcium chloride or sodium-chlor.
As everyone knows, polyacetal resin as aspect machinery and the physicals such as electricity, and all very good representational engineering resins of chemical characteristics such as chemical-resistant reagent and thermotolerances, is being utilized by the utmost point in a lot of fields in recent years widely.But,,, also require to do further to improve as the character of this class material along with polyacetal resin utilizes the expansion in field.
Example as such requirement, for example as materials used in auto manufacturing, what thirsted for is, for in the presence of the moisture content because calcium chloride or sodium-chlor are being used for the corrosion that causes in the molding of the polyacetal resin under the equivalent environment, the nonvolatil solidity to corrosion (salt tolerant destructiveness) that can give height with galvanized iron sheet.As improving the destructive means of the anti-salt of polyacetal resin, up to the present also do not have a kind of specific scheme, consistent processing means are to add to cooperate a kind of known stronger alkaline matter.
Yet, means before adopting can't be given sufficient anti-salt destructiveness for polyacetal resin, and the parts that are used for the polyacetal resin system of materials used in auto manufacturing are when making, can find to present on the surface of parts degradation phenomenas such as crackle, so be the thing of earnestly looking forward to its improvement.
Present inventors, for obtaining in a kind of polyacetal molding that under the environment identical, uses with galvanized iron sheet as materials used in auto manufacturing, for in the presence of moisture content, carrying out profoundly result of study discovery, by using a kind of oxidation inhibitor and specific containing metal compound compositions of in polyacetal resin, cooperating because the corrosion that calcium chloride or sodium-chlor cause has the polyacetal molding of the corrosion stability of weather resistance highly.Just can obtain the destructive good automotive member of polyacetal resin of anti-salt, finish purpose of the present invention so just reached.
Promptly the invention relates to a kind of materials used in auto manufacturing of polyacetal system, this material be by
(A) in the polyacetal resin of 100 weight parts, add cooperation
(B) oxidation inhibitor of 0.01-5.0 weight part and
(C) zinc compound of 0.01-10 weight part constitutes with the compound compositions moulding that contains more than one metals that is selected from hydrotalcite.
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, zinc borate, zinc metaborate, organic acid zinc etc., and these zinc compounds can use separately, also can two or more mixing use.In addition, every carbonatoms is that organic acid more than 1 and that have 1 above carboxyl can be as the organic acid that constitutes organic acid zinc.Have as concrete example is specifiable, formic acid, acetate, propionic acid, carbonatoms be more than 4 paraffinic acid and alkenoic acid or chain acetylenic acid, propanedioic acid, citric acid, hexanodioic acid, toxilic acid, oxalic acid, M-nitro benzoic acid, phthalic acid, trimellitic acid, Whitfield's ointment, soak gallate-based, naphthenic acid etc., and their isomer, also have their the replacement capable thing that spreads out.Particularly preferably be carbonatoms and be the lipid acid more than 12, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, docosoic are arranged as preference is specifiable.
In addition, as being used for hydrotalcite of the present invention (C), the hydrotalcite of the following general formula of all usefulness (I) expression all can use,
Logical formula I
AlxMyRz (OH)
6(a/n) AmH
2(x in the formula, y, z are respectively the numbers of 0.6≤x≤3,0≤y≤3,0＜z≤2.4 to O, 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, R is at least a above divalent metal, A is a negatively charged ion, and n represents the valence mumber of negatively charged ion A, and m is the number of 0≤m≤3).
Particularly preferably be and contain aluminium and magnesium and zinc hydrotalcite as metal ingredient with general formula (2) expression.
General formula (2):
Al
xMg
(z-k)Zn
k(OH)
6(a/2) (CO
3) mH
2O (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≤K≤1.2).
In addition, in order to improve the operability of these hydrotalcites better, the most handy fatty acid treatment surface, class lipid acid is specifiable that lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, docosoic are arranged as this.
In (C) composition, containing as the aluminium of metal ingredient and hydrotalcite, zinc oxide, zinc hydroxide, the zinc carbonate of magnesium and zinc is particularly preferred material.
The amount ranges of (C) composition in the present invention is, is the 0.01-10.0 weight part with respect to the polyacetal resin of 100 weight parts, preferred 0.05-5 weight part, preferred especially 0.10-2.0 weight part.
Being used for oxidation inhibitor of the present invention (B) is Hinered phenols; for example; 2; 2 '-methylene-bis (4-methyl-6-tert-butylphenol); 1; 6-hexylene glycol-two (3; 5-two-tert-butyl-4-hydroxyl hydrogenated cinnamate); four [methylene radical (3; 5-two-tert-butyl-4-hydroxyl hydrogenated cinnamate)] methane; triglycol-two-3-(3-tert-butyl-4-hydroxy-5-methyl base phenyl) propionic ester; 1; 3; 5-trimethylammonium-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 '-methylene-bis (2; 6-two-tert-butyl phenol); 4,4 '-butylidene-two-(6-tertiary butyl-3-methyl-phenol); two-stearyl--3,5-two-tert-butyl-4-hydroxybenzyl phosphonic acid ester; 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) propionyloxy]-1; the 1-dimethyl ethyl }-2,4,8; 10-four oxaspiros [5; 5] ten-(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; 6-tetramethyl-piperazine forms sediment; 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; the stupid oxygen base-2,2 of 4-; 6; the 6-tetramethyl piperidine; 4-benzyloxy-2,2,6; the 6-tetramethyl piperidine; 4-(aniline methanoyl)-2; 2,6, the 6-tetramethyl piperidine; two (2; 2; 6,6-tetramethyl--4-piperidyl) barkite; two (2,2; 6; 6-tetramethyl--4-piperidyl) malonic ester; two (2,2,6; 6-tetramethyl--4-piperidyl) adipic acid ester; two (2; 2,6,6-tetramethyl--4-piperidyl) sebate; two (1; 2; 2,6,6-pentamethyl--piperidyl) sebate; two (2; 2; 6,6-tetramethyl--4-piperidyl) terephthalate; 1,2-two (2; 2; 6,6-tetramethyl--4-piperidyl oxygen) ethane; two (2,2; 66-tetramethyl--4-piperidyl) hexa-methylene-1; the 6-diurethanes; two (1-methyl-2,2,6; 6-tetramethyl--4-piperidyl) adipic acid ester; three (2; 2,6,6-tetramethyl--4-piperidyl) benzene-1; 3,5-tricarboxylic ester etc.
In addition, the condenses of high-molecular weight piperidine derivative, for example, succsinic acid dimethyl 1-(2-hydroxyethyl)-4-hydroxyl-2,2,6,6-tetramethyl piperidine condenses, poly-[(6-morpholino-S-triazine-2,4-two bases) [2,2,6,6-tetramethyl--4-piperidyl) imino-]-hexa-methylene [(2,2,6, the 6-tetramethyl-4-piperidyl) imino-]] 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 radical (3,5-two-tert-butyl-4-hydroxyl hydrogenated cinnamate)] methane, triglycol-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) propionyloxy]-1, the 1-dimethyl ethyl }-2,4,8,10-four oxaspiros [5,5] 11 (carbon) alkane, poly-[(6-morpholino-S-triazine-2,4-two bases) [2,2,6,6-tetramethyl--4-piperidyl] imino-]-hexa-methylene [2,2,6,6-tetramethyl--4-piperidyl) imino-]] be particularly preferred material.
The amount ranges of (B) composition in the present invention is, is the 0.01-5.0 weight part with respect to the polyacetal resin (A) of 100 weight parts.
Said above-mentioned (B) and (C) polyacetal resin of composition (A) of having cooperated is with oxygen methylene radical (CH
2O-) as the macromolecular compound of main composition unit, the Copolyacetal, terpolymer, segmented copolymer etc. that wherein also contain a small amount of other component unit beyond the polyacetal homopolymer, deoxygenation methylene radical all are available, in addition, not only molecule be line style and also band Zhi Jian's or the macromolecular compound of crosslinking structure is arranged also is useful.Also have,, then do not have special restriction for its polymerization degree 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 formaldehyde reaction amino, amide group and hydroxyl of the composition among the present invention (D).This be because, the polyacetal molding 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 formaldehyde reaction amino, amide group, the material of hydroxyl, but example has, trimeric cyanamide, the phenyl diamino triazine, the condenses of dicyano diamide and they and formaldehyde, polymine, PAH, the homopolymer of acrylamide, multipolymer and cross-linked polymer, polyglycine, poly-(β-An Jibingsuan), poly-, nylon-6,6, nylon-6,10, PA-12, polyoxyethylene glycol, polyglycerol, the fatty acid monoester of glycerol and two glycerol, glycerol monostearate for example, two glycerol monostearates, the single isostearate of glycerol, the single isostearate of two glycerol, the glycerol monopalmitate, two glycerol monopalmitates, fatty amide, ethylidene-two (stearylamides) for example, hexa-methylene-two (stearylamide), two (stearyl amido ethyl) sebacoyl amine etc., at least wherein a kind of can be used, also two or more mixtures can be used.
In the middle of these, the fatty acid monoester of the condenses of trimeric cyanamide, trimeric cyanamide and formaldehyde, the homopolymer of acrylamide, multipolymer and cross-linked polymer, glycerol and two glycerol is particularly preferred materials.
Be somebody's turn to do (D) composition,, add the 0.01-3.0 weight part, preferably add the 0.05-1.0 weight part with respect to the polyacetal resin (A) of 100 weight parts.
The amount that is used for various additive of the present invention (B)-(D) can not get enough performances under the situation below the specified amount scope, yet when addition was superfluous, the mechanical and physical performance of resin molded body descended, and was undesirable therefore.
In polyacetal resin molding of the present invention, according to its purpose also can (but optional) and with more than one except that above-mentioned oxidation inhibitor, zinc compound, hydrotalcite, have the compound that contains organic and inorganic metal the material of more than one formaldehyde reaction amino, amide group, hydroxyl.
In the materials used in auto manufacturing of aldehyde resin system of the present invention, can also cooperate various known additives, for example, various tinting materials, lubricant, releasing agent, nucleator, antistatic agent, weather-proof (light) stablizer, other tensio-active agent and various polymkeric substance etc.In addition, in the scope that the performance that does not make purpose molding of the present invention descends significantly, can be composite the weighting agent 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 fiber, hollow glass ball, talcum, mica, white mica, wollastonite etc., and this wherein any all can use and do not have any restriction.In addition, adopt the currently known methods that is generally used for making resin forming product in the past, can make the molding of polyacetal resin of the present invention at an easy rate.For example, after various compositions mixing, employing single shaft or biaxial extruder carry out mixing and extrude, make section (particle), the amount of should cutting into slices is in accordance with regulations mixed (dilution), so that supply with moulding, and the method etc. that obtains the molding of purpose composition after moulding all can be used.In addition in the modulation of the composition that is used for this molding, for pulverizing as part or all of the polyacetal resin of essentially consist, and with it with after other composition mixes, process such as extrude again, preferably select those methods that make the additive good dispersity for use.
Resin molded body of the present invention exists for moisture and to worry down also can use because of calcium chloride or sodium-chlor cause those purposes of corrosive, and particularly the part of materials used in auto manufacturing and/or parts is applicable to it is the machine of galvanized iron sheet.Gear, cam, clasp, folder, handle, lever, support plate, underground pipeline, brake shoe, junctor, pad framework, grid etc. are arranged as concrete molding is specifiable.
Embodiment
Below, by embodiment, specifically describe the present invention, but the present invention is not limited to this.
When describing, above-mentioned composition is made the ASTM1 dumb bell specimen, soak in the solder(ing)acid with this molding furnishing 40 weight % concentration under 60 ℃ of temperature, in the specific time interval, take out for the destructive evaluation method of anti-salt.The molding that will stand this processing is washed, after the drying, measure the weight and the tensile properties of molding.Measure the weight of whole molding before it is processed, the weight difference before and after handle calculates weight conservation rate after solder(ing)acid is handled by following formula.In addition, similarly go out stretching strength retentivity from the tensile strength calculation of handling front and back.
Weight conservation rate (stretching strength retentivity) after=processing is embodiment 1-9 and comparative example 1-7 (%)
Oxidation inhibitor shown in the table 1, zinc compound and the material that contains more than one formaldehyde reaction amino, amide group and hydroxyl are added in the ratio shown in the table 1 in the Copolyacetal of 100 weight parts and mix, and in forcing machine, obtain the granulous composition, carry out above-mentioned evaluation again.It the results are shown in the table 1.
In addition, as shown in table 1 for relatively, for the occasion of not adding oxidation inhibitor or zinc compound, add the occasion of regulation of the present invention compound in addition etc., make the granulous composition with embodiment the samely, and carry out above-mentioned evaluation.The results are shown in the table 1.
Employed oxidation inhibitor, zinc compound, the material of more than one formaldehyde reaction aminoacyl amidos and hydroxyl such as following listed is arranged: annotate-1, oxidation inhibitor b-1: glycol ether-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-]-hexa-methylene [2,2,6,6-tetramethyl--4-piperidines] imino-]] annotate-2, zinc compound
C-1: zinc oxide
C-2: zinc carbonate
C-3:(Mg+Zn)/mol ratio of Al is 2.25, MgCl
2: ZnCl
2=9: 1, NH
3The mol ratio of/Al is 0.14.Annotate-3, have the material of formaldehyde reaction base
D-1: carbamide condenses
D-2: polyacrylamide
D-3: the glycerol monostearate annotates-4, other stablizer
D '-1:12-hydroxyl calcium stearate
Table 1
(notes) stretching strength retentivity is 100% when above, is expressed as 100%.50% when following, the deviation of data is big, is difficult to accurate mensuration, so become [one].
| Embodiment | Comparative example | |||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | |
| Oxidation inhibitor (annotating-1) (weight part) | b-1 0.5 | b-1 0.5 | b-1 0.5 | b-1 1.0 | b-2 0.5 | b-1 0.5 | b-1 0.5 | b-1 0.5 | b-1 0.5 | b-1 0.5 | b-2 0.5 | b-1 0.5 | b-1 0.5 | b-1 0.5 | ||
| Zinc compound (annotating-2) (weight part) | c-1 0.05 | c-1 0.5 | c-1 5.0 | c-1 0.5 | c-1 0.5 | c-1 0.5 | c-1 0.5 | c-1 0.5 | c-1 0.5 | c-1 0.5 | ||||||
| Hydrotalcite (annotating-3) (weight part) | c-3 0.5 | |||||||||||||||
| The material (annotating-4) (weight part) that contains the formaldehyde reaction base | 4-1 0.3 | d-2 0.7 | d-3 0.3 | d-1 0.3 | d-1 0.3 | d-3 0.3 | ||||||||||
| Other stablizer (annotating-5) (weight part) | 4-1 0.5 | |||||||||||||||
| Weight conservation rate (%) is after 20 days | 98.9 | 99.5 | 100 | 99.7 | 99.6 | 99.9 | 99.9 | 99.8 | 99.9 | 90.3 | 88.4 | 83.3 | 83.0 | 98.6 | 98.1 | 98.4 |
| After 30 days | 97.8 | 99.0 | 99.8 | 99.4 | 99.2 | 99.6 | 99.5 | 99.5 | 99.6 | 81.7 | 78.5 | 74.1 | 72.6 | 96.4 | 95.2 | 95.6 |
| After 40 days | 95.7 | 96.9 | 98.9 | 97.4 | 96.9 | 98.5 | 98.2 | 98.1 | 98.5 | 62.6 | 59.2 | 50.9 | 48.7 | 88.9 | 85.7 | 86.9 |
| Stretching strength retentivity is (%) after 20 days | 99.2 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 84.2 | 82.2 | 77.6 | 76.8 | 95.4 | 95.0 | 94.8 |
| After 30 days | 97.1 | 98.5 | 99.4 | 98.7 | 38.4 | 33.3 | 93.0 | 99.1 | 99.3 | 60.7 | 55.5 | - | - | 90.9 | 89.3 | 90.5 |
| After 40 days | 90.7 | 93.2 | 95.6 | 83.5 | 93.2 | 95.0 | 94.8 | 94.7 | 950 | - | - | - | - | 82.8 | 79.7 | 81.1 |
Above explanation and embodiment show, the molding that constitutes based on resin combination by previous method, after 20 days, the weight conservation rate of molding is lower than 95%, and after in the solder(ing)acid that 60 ℃ of following concentration are 40 weight %, soaking 40 days by the molding that resin combination of the present invention constitutes, the weight conservation rate of molding is more than 95%, therefore is applicable to above-mentioned various uses.
Claims (5)
1. automotive member of polyacetal resin, it is shaped by a kind of composition and forms, and described composition comprises:
(A) in the 100 weight part polyacetal resins, add cooperation
(B) antioxidant of 0.01-5.0 weight part and
(C) zinc compound of 0.01-10 weight part, described zinc compound are to be selected from zinc oxide, zinc hydroxide, zinc carbonate and the zinc borate more than one.
2. automotive member of polyacetal resin according to claim 1 is when this material is being that the weight conservation rate of this shaped material is more than 95% when soaking 40 days in the solder(ing)acid of 40 weight % in concentration under 60 ℃.
3. automotive member of polyacetal resin according to claim 1, wherein, described antioxidant (B) is to be selected from Hinered phenols and the hindered amines more than one.
4. automotive member of polyacetal resin according to claim 2, wherein, described antioxidant (B) is to be selected from Hinered phenols and the hindered amines more than one.
5. according to any one described automotive member of polyacetal resin among the claim 1-4, wherein, be configured as in the composition of described polyacetal resin molding with respect to the polyacetal resin (A) of 100 weight parts, also cooperate being selected from of more than one 0.01-3.0 weight parts to have the material (D) of more than one formaldehyde reaction amino, amide group and hydroxyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30260893A JP3188082B2 (en) | 1993-12-02 | 1993-12-02 | Automotive components made of polyacetal resin |
| JP302608/93 | 1993-12-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1107866A CN1107866A (en) | 1995-09-06 |
| CN1045978C true CN1045978C (en) | 1999-10-27 |
Family
ID=17911036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94113081A Expired - Lifetime CN1045978C (en) | 1993-12-02 | 1994-12-01 | Automotive member of polyacetal resin |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3188082B2 (en) |
| KR (1) | KR0141654B1 (en) |
| CN (1) | CN1045978C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3789555B2 (en) * | 1996-06-19 | 2006-06-28 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| DE19925491A1 (en) * | 1999-06-04 | 2000-12-14 | Ticona Gmbh | Polyoxymethylene molded parts with improved resistance to diesel fuel and aggressive gasoline |
| CN107109029B (en) * | 2014-12-22 | 2021-03-12 | 三菱瓦斯化学株式会社 | Polyacetal resin composition and molded article thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3039351B2 (en) * | 1996-01-25 | 2000-05-08 | 株式会社田村電機製作所 | Detection structure of coin processing device |
| JP3190459B2 (en) * | 1992-11-24 | 2001-07-23 | 松下電工株式会社 | Electrodeless discharge lamp lighting device |
-
1993
- 1993-12-02 JP JP30260893A patent/JP3188082B2/en not_active Expired - Lifetime
-
1994
- 1994-11-25 KR KR1019940031189A patent/KR0141654B1/en not_active IP Right Cessation
- 1994-12-01 CN CN94113081A patent/CN1045978C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3190459B2 (en) * | 1992-11-24 | 2001-07-23 | 松下電工株式会社 | Electrodeless discharge lamp lighting device |
| JP3039351B2 (en) * | 1996-01-25 | 2000-05-08 | 株式会社田村電機製作所 | Detection structure of coin processing device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR0141654B1 (en) | 1998-07-01 |
| JP3188082B2 (en) | 2001-07-16 |
| CN1107866A (en) | 1995-09-06 |
| KR950018244A (en) | 1995-07-22 |
| JPH07150004A (en) | 1995-06-13 |
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Expiration termination date: 20141201 Granted publication date: 19991027 |