CN1251854A - High-performance canned polyurethane paint and its preparing process - Google Patents
High-performance canned polyurethane paint and its preparing process Download PDFInfo
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- CN1251854A CN1251854A CN 99119979 CN99119979A CN1251854A CN 1251854 A CN1251854 A CN 1251854A CN 99119979 CN99119979 CN 99119979 CN 99119979 A CN99119979 A CN 99119979A CN 1251854 A CN1251854 A CN 1251854A
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Abstract
A canned high-performance polyurethane paint is prepared from hydroxy-terminated polyurethane as filming substance, and amino resin and its derivatives as solidifying agent. Said hydroxy-terminated polyurethane is synthesized from long-chain dibasic alcohol and aliphatic diisocyanate through a certain control process. Said paint can be used for airplane, car, plastic products and fine instruments and has the advantages of simple synthesis process, easily available raw materials, and excellent corrosion, chemial, UV, weather, scrape and wear resistance, and flexibility.
Description
The invention belongs to chemical technology field, relate to a kind of high-performance canned polyurethane coating and preparation method thereof.
Many high-performance coatings are to be main film forming substance with polyacrylate polyol or polyester polyol, with terpolycyantoamino-formaldehyde resin or polyisocyanates is the one-pot or the two-pack system of solidifying agent preparation, as car paint, industrial coating, plastic paint and decorative paint etc.But for polyacrylate polyol/terpolycyantoamino-formaldehyde resin or polyester polyol/terpolycyantoamino-formaldehyde resin system, in its cured paint film ester bond a little less than, meet sour facile hydrolysis, promptly the acidproof rain of paint film is relatively poor; Make solidifying agent with polyisocyanates, though can improve the acidproof rain of paint film, shortcoming has (1) time limit of service short, and general about 2 hours, the time one was long, and then the viscosity of system raises fast; (2) because isocyanic ester is poisonous, system needs special processing and storage; (3) isocyanate group/hydroxyl needs the strict metering ratio preparation of pressing, and goes wrong easily.
In recent years, existing research report can address the above problem preferably with synthetic hydroxyl-terminated polyurethane/terpolycyantoamino-formaldehyde resin system.In patent EP 0409300A2 and US4731289, synthetic hydroxyl-terminated polyurethane is with the symmetry of two hydroxyl spacing≤3 or asymmetric dibasic alcohol such as ethylene glycol, isoamyl glycol, 2,3-butyleneglycol, 2,4-pentanediol, 1, ammediol, 2-ethyl-2-butyl-1, ammediol, 1,2-hexylene glycol 2-ethyl-1,3 hexylene glycol, 1,2-propylene glycol, 1,3-butyleneglycol, 1,2-hexylene glycol, 1,2-certain herbaceous plants with big flowers glycol, 2,2,4-trimethylammonium-1,3-pentanediol etc. and with the aliphatic polyisocyante be main form synthetic.And dibasic alcohol should excessive greatly polyisocyanates.
But in the above-mentioned dibasic alcohol, the pendant hydroxyl group group of some low molecular weight diol is not because of being shielded by enough carbon atoms, and the resistance to acid attack of its urethane is relatively poor, as ethylene glycol, 1,2-propylene glycol, 1, ammediols etc. are though the pendant hydroxyl group group of some dibasic alcohol is by enough uncommon being easy to get of carbon atom shielding, as 2-ethyl-2-butyl-1, ammediol, 1,2-hexylene glycol 2-ethyl-1,3 hexylene glycol, 1,2-hexylene glycol, 1,2-certain herbaceous plants with big flowers glycol.And the dibasic alcohol that is easy to get for existing enough shielding effects is as 1,4-butyleneglycol, 2,5-hexylene glycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,10-certain herbaceous plants with big flowers glycol etc., then because of two hydroxyl spacing 〉=4, the reactive behavior of oh group is lower, when synthesizing hydroxyl-terminated polyurethane with aliphatic polyisocyante, the carbamate that isocyanic ester and hydroxyl reaction generate can be preferentially further with the isocyanate groups reaction not with the hydroxyl reaction of dibasic alcohol, easily gelation, thereby be difficult to use in synthetic hydroxyl-terminated polyurethane.
The object of the present invention is to provide a kind of with long chain diol cheap and easy to get be raw material, synthetic easily, have high performance polyurethane coating of excellent in resistance acid etching, chemical resistant properties etc. and preparation method thereof.
The high performance polyurethane coating that the present invention proposes is to be wherein a monomer component by raw material long chain diol cheap and easy to get, with aliphatic diisocyanate synthetic hydroxyl-terminated polyurethane be filmogen, be that solidifying agent is formed with aminoresin and derivative thereof.Wherein, consisting of of hydroxyl-terminated polyurethane: the C of (1) at least a hydroxyl spacing 〉=4
4～C
20The symmetry or asymmetric long chain diol; (2) at least a C
6～C
25Aliphatic diisocyanate.The equivalence ratio of vulcabond/dibasic alcohol was controlled at 1: 1.15～1: 8.0, and preferred proportion is 1: 1.25～1: 3.33.The weight ratio of hydroxyl-terminated polyurethane and solidifying agent is 1: 9～1: 0.11, and preferred proportion is 1: 1～1: 0.18.Here, solidifying agent adopts aminoresin, as terpolycyantoamino-formaldehyde resin or urea-formaldehyde resin or their derivative, preferentially select the terpolycyantoamino-formaldehyde resin or derivatives thereof for use, comprise part or all of methyl-etherified, butyl etherization, isobutyl etherificate terpolycyantoamino-formaldehyde resin such as Cymel 303, Cymel 1135, Cymel 325 etc.
Among the present invention, above-mentioned hydroxyl-terminated polyurethane can preferentially use following component in forming:
(1) C of hydroxyl spacing 〉=4
5～C
10The symmetry or asymmetric long chain diol, preferentially select C for use
5～C
10The symmetry or asymmetric long chain diol, as 1,6-hexylene glycol, 1,4-hexylene glycol, 2,5-hexylene glycol, 1,10-certain herbaceous plants with big flowers glycol, 2,6-certain herbaceous plants with big flowers glycol.
(2) C
6～C
18Aliphatic diisocyanate, preferentially use C
6～C
18Aliphatic diisocyanate, as hexamethylene diisocyanate (HDI), HDI biuret, HDI tripolymer or isoflurane chalcone diisocyanate (IPDI), 2-methyl amyl-1,5-vulcabond, 2,2,4-trimethylammonium hexyl 1,6-vulcabond, 1, biuret, tripolymer or the polymer of 12-dodecyl vulcabond, methyl two (4-hydroxyl hexyl) isocyanic ester or these isocyanic ester.
The preparation method of the high performance polyurethane coating that the present invention proposes is as follows:
Synthesizing of hydroxyl-terminated polyurethane
Reactor uses the 1000mL four neck round-bottomed flasks that have agitator, heating platform, reflux condensing tube and rare gas element ingress pipe.
By above-mentioned consumption proportion, take by weighing long chain diol and aliphatic diisocyanate, dibasic alcohol, corresponding solvent and catalyzer are added in the reactor, heating is stirred and is warming up to 50～250 ℃ of design temperatures, drips the solution of aliphatic diisocyanate again; After dropwising, continue stirring reaction 40～60 minutes, to IR spectrum, no longer show 2250cm
-1Absorption peak, represent that promptly isocyanate groups reaction finishes.Remove heating platform, product is cooled to room temperature.
The catalyzer that uses among the above-mentioned preparation method can be 1. organic tin compound such as dibutyltin diacetate, dibutyl tin laurate, stannous octoate; 2. or naphthenate such as zinc naphthenate, cobalt naphthenate, lead naphthenate; 3. or the salt of some metal of some lipid acid such as caproic acid, acetic acid, linolenic acid such as strontium, bismuth, calcium, magnesium, barium etc., preferentially select organo-tin compound such as dibutyltin diacetate, dibutyl tin laurate etc. for use.Catalyst levels accounts for the 0.5-2.0% of aliphatic diisocyanate and long chain diol gross weight.
The solvent that uses is the common solvent of synthesis of polyurethane: 1. as aromatics, comprise toluene, dimethylbenzene, ethylbenzene, diethylbenzene, isopropyl benzene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene etc.; 2. ketones solvent comprises 2-butanone, 2 pentanone, 2-heptanone, methyl iso-butyl ketone (MIBK), methyl isoamyl ketone, methyl heptyl ketone, ethyl pentyl group ketone, diisopropyl ketone, diisobutyl ketone, methylcyclohexanone, dimethylcyclohexanon etc.; 3. esters solvent comprises C
3～C
20Acetic acid alkyl ester and lactate breast propyl acetate, N-BUTYL ACETATE, capryl acetate, Diethylene Glycol acetates, ethyl lactate, n-Butyl lactate etc.Solvent load accounts for the 30-75% of aliphatic diisocyanate and long chain diol gross weight.
The temperature of reaction of using is 50～250 ℃, preferentially selects 80～150 ℃ for use.
Above-mentioned synthetic hydroxyl-terminated polyurethane hydroxyl value is 60～200, and molecular weight is 500～3000, molecular weight distribution＜2.0.
The preparation of polyurethane coating
Coating of the present invention consists of: (1) hydroxyl-terminated polyurethane 10～90% (weight percent meter, down together), preferentially use 50～85%; (2) solidifying agent is aminoresin such as terpolycyantoamino-formaldehyde resin or urea-formaldehyde resin or their derivative, preferentially select the terpolycyantoamino-formaldehyde resin or derivatives thereof for use, comprise part or all of methyl-etherified, butyl etherization, isobutyl etherificate terpolycyantoamino-formaldehyde resin such as Cymel 303, Cymel 1135, Cymel 325 etc.Consumption is 10～90%, preferentially uses 15～50%.
Catalyzer is selected acid catalyst such as sulfonic acid class for use, comprises tosic acid, dinonylnaphthalene disulfonic acid, Witco 1298 Soft Acid and substitution product thereof etc.; The phosphoric acid class comprises phosphoric acid, alkylphosphonic acid carboxylic acid etc. and sulfuric acid, carbonic acid etc.Preferentially select dinonylnaphthalene disulfonic acid, Witco 1298 Soft Acid, tosic acid etc. for use.Consumption accounts for 0.05～1.5% of weight resin.
The solvent that uses in the said process, pigment and relevant auxiliary agent such as wetting dispersing agent, UV absorption agent, tensio-active agent, stablizer etc. are identical with preparation polyurethane coating commonly used.
Above-mentioned component at room temperature is mixed into homogeneous solution, promptly is mixed with the one-pot polyurethane coating.
The polyurethane coating that the present invention makes has excellent resistance to acid attack, chemical resistant properties, anti-UV, weathering resistance, scratch resistance and hinder wear resistance, flexibility and other coating property, and synthesis technique is simple, grasps easily, and raw material is cheap and easy to get.Can be widely used as the topcoating of automobile, aircraft, plastics and other precision instrument.
The performance characterization of above-mentioned resin and coating is as follows:
Molecular weight and molecular weight distribution are measured with GPC, are standard specimen with the polystyrene.Hydroxyl value is pressed ASTM D1957 (88) method and is measured.
Resistance to acid attack is measured by following method:
With above-mentioned varnish membrane on clean aluminium test board, the thickness of control dry film is 25-40 μ m, and 120 ℃ solidified 30 minutes down.Sulphuric acid soln, salpeter solution and the hydrochloric acid soln of 1M concentration are mixed by 65/30/5 volume ratio, the above-mentioned mixed acid solution of 0.5ml is dripped on the aluminium test board of filming, room temperature is placed.Acid solution was added at every interval in 2 hours, and test is last, embathed film aluminium test board and drying at room temperature with distilled water and spent the night, and observed also record and filmed lost hours.
The scoring resistance test is measured by following method:
To test aluminium sheet, to have coated the light commercialization pitch-dark, solidified 30 minutes down at 140 ℃, uses varnish or the colored paint of coating the present invention's preparation with quadrat method on this black-out test plate then, solidified 15 minutes down at 120 ℃, again with this test board exsiccant Bon-Ami
TMClean powder (U.S. Coronado paint company special product) is gone up dirt, and removes unnecessary powder gently.With scratch resistance hinder the instrument probe on test board with 1 back and forth the frequency of scratch/second scrape 10 back and forth, and, dry with wet rag again with tap water flushing.The gloss hygrometer is measured the both sides in not scratch district and scratch district 20 ° glossiness, and every mensuration district repeats 5 times, gets its mean value.Protecting light rate or scoring resistance recently represents with the percentage of scratch district glossiness not with the scratch district.
Embodiment:
Example 1
In the 1000mL four neck round-bottomed flasks that agitator, heating platform, thermometer, reflux condensing tube and rare gas element ingress pipe are housed, add 1 of 146.2g by the consumption requirement, the 6-hexylene glycol, the dimethylbenzene of 150g, 0.18g concentration is 10% dibutyl tin laurate, stir and slowly be warming up to 70 ℃, in 2.5～3 hours, slowly drip hexamethylene diisocyanate (HDI) tripolymer of 108.60g.Continue stirring reaction 45 minutes, and to IR spectrum, no longer showed 2250cm
-1Absorption peak, represent that promptly isocyanate groups reaction finishes.Remove heating platform, product is cooled to room temperature.
With this hydroxyl-terminated polyurethane is that resin binder is made into varnish, and prescription, resistance to acid attack mensuration and scoring resistance are measured the same.The resistance to acid attack time:＞10 hours; Scoring resistance: 100%.
Example 2
In the 1000mL four neck round-bottomed flasks that agitator, heating platform, thermometer, reflux condensing tube and rare gas element ingress pipe are housed, add 1 of 109.65g by the consumption requirement, the 6-hexylene glycol, the dimethylbenzene of 150g, 0.18g concentration is 10% dibutyltin diacetate, stir and slowly be warming up to 70 ℃, in 2.5～3 hours, slowly drip hexamethylene diisocyanate (HDI) tripolymer of 108.60g.Continue stirring reaction 30 minutes, and to IR spectrum, no longer showed 2250cm
-1Absorption peak, represent that promptly isocyanate groups reaction finishes.Remove heating platform, product is cooled to room temperature.
With this hydroxyl-terminated polyurethane is that resin binder is made into varnish, and prescription, resistance to acid attack and scoring resistance are measured the same.The resistance to acid attack time: 12.5 hours; Scoring resistance: 99.9%.
Example 3
In the 1000mL four neck round-bottomed flasks that agitator, heating platform, thermometer, reflux condensing tube and rare gas element ingress pipe are housed, the certain herbaceous plants with big flowers glycol that adds 213g by the consumption requirement, the dimethylbenzene of 150g, 0.23g concentration is 10% dibutyl tin laurate, stir and slowly be warming up to 85 ℃, in 2.5～3 hours, slowly drip the isoflurane chalcone diisocyanate (IPDI) of 222.5g.Continue stirring reaction 30 minutes, and to IR spectrum, no longer showed 2250cm
-1Absorption peak, represent that promptly isocyanate groups reaction finishes.Remove heating platform, product is cooled to room temperature.
With this hydroxyl-terminated polyurethane is that resin binder is made into varnish, and prescription, resistance to acid attack and scoring resistance are measured the same.Resistance to acid attack: 13 hours; Scoring resistance: 100%.
Example 4
In the 1000mL four neck round-bottomed flasks that agitator, heating platform, thermometer, reflux condensing tube and rare gas element ingress pipe are housed, add 1 of 146g by the consumption requirement, the 6-hexylene glycol, the 2-heptanone of 150g, 0.18g concentration is 10% dibutyl tin laurate, stir and slowly be warming up to 75 ℃, in 2.5～3 hours, slowly drip hexamethylene diisocyanate (HDI) tripolymer of 65g.Continue stirring reaction 45 minutes, and to IR spectrum, no longer showed 2250cm
-1Absorption peak, represent that promptly isocyanate groups reaction finishes.Remove heating platform, product is cooled to room temperature.
At this moment-and the equivalence ratio of OH/-NCO is 3.33: 1, and gel-free generates, but contains a large amount of unreactedly 1 in the resin, and the 6-hexylene glycol is because its boiling point height is difficult to same resin isolation.These are residual a large amount of unreacted 1, and the 6-hexylene glycol has very big negative impact to resistance to acid attack, water tolerance and the solvent resistance of filming.Further do not prepare varnish and measure scoring resistance.
Example 5
In the 1000mL four neck round-bottomed flasks that agitator, heating platform, thermometer, reflux condensing tube and rare gas element ingress pipe are housed, add 91.4g1 by the consumption requirement, the 6-hexylene glycol, the dimethylbenzene of 150g, 0.18g concentration is 10% dibutyl tin laurate, stir and slowly be warming up to 70 ℃, in 2.5～3 hours, slowly drip hexamethylene diisocyanate (HDI) tripolymer of 108.6g.Continue stirring reaction 45 minutes, and to IR spectrum, no longer showed 2250cm
-1Absorption peak, represent that promptly isocyanate groups reaction finishes.Remove heating platform, product is cooled to room temperature.
At this moment-equivalence ratio of OH/-NCO is 1.25: 1, find to have the minute quantity gel to generate on the stirring rod, on the thermometer and the bottle end, therefore can judge that this equivalence ratio is synthetic minimum unreacted 1, the highest amount ratio that 6-hexylene glycol and don't generation gel can reach of containing.
This batch hydroxyl-terminated polyurethane is made into varnish as resin binder, and prescription, resistance to acid attack and scoring resistance are measured the same.Resistance to acid attack: 13 hours; Scoring resistance: paint film is very coarse because of there being a small amount of microgel to generate the surface in the synthetic resins process, has little particle to protrude undetermined from the surface.
The resistance to acid attack of partial coating of the present invention and scoring resistance test-results see Table 1 and table 2 respectively.
Film resistance to acid attack test of table 1
| Test board # | -OH/-NCO equivalence ratio | By the acid etching time (hour) |
| ?1 | ?1.3∶1 | 13 |
| ?2 | ?1.5∶1 | 12.5 |
| ?3 | ?2∶1 | 10 |
| ?4 | ?3∶1 | ＜10 |
By test as can be seen, when the equivalence ratio of-OH/-NCO at 1.3: 1---in the time of between 2: 1, the resistance to acid attack time of filming is all more than 10 hours, therefore has fabulous acidproof rain, but when the dibasic alcohol consumption further increases, then film because of containing too much unreacted oh group, its resistance to acid attack reduction.
The test of scoring resistance that table 2 is filmed (with the equivalence ratio of-OH/-NCO be 1.5: 1 be example)
| Measure number of times | 1 | ?2 | ????3 | ????4 | ????5 | On average |
| Scratch district not | 88.0 | ?88.6 | ????89.5 | ????89.0 | ????89.8 | ?88.98 |
| The scratch district | 88.9 | ?88.3 | ????89.2 | ????88.8 | ????89.5 | ?88.94 |
| Scoring resistance: 88.94/88.98=99.96% | ||||||
Promptly film and have excellent scoring resistance energy.
Claims (10)
1. polyurethane coating, with the hydroxyl-terminated polyurethane is filmogen, with the aminoresin or derivatives thereof is that solidifying agent is formed, and it is characterized in that hydroxyl-terminated polyurethane is synthetic by long chain diol and aliphatic diisocyanate, and its component is: the C of (1) at least a hydroxyl spacing 〉=4
4～C
20The symmetry or asymmetric long chain diol; (2) at least a C
6～C
25Aliphatic diisocyanate; The equivalence ratio of vulcabond/dibasic alcohol was controlled at 1: 1.15～1: 8.0; The weight ratio of hydroxyl-terminated polyurethane and solidifying agent is 1: 9～1: 0.11.
2. polyurethane coating according to claim 1, the equivalence ratio that it is characterized in that above-mentioned vulcabond and long chain diol is 1: 1.25～1: 3.33.
3. polyurethane coating according to claim 1 and 2 is characterized in that the preferred component of above-mentioned hydroxyl-terminated polyurethane is: the C of hydroxyl spacing 〉=4
5～C
10The symmetry or asymmetric long chain diol; (2) at least a C
6～C
18Aliphatic diisocyanate.
4. the preparation method of a polyurethane coating uses the reactor that has agitator, heating platform, reflux condensing tube and rare gas element ingress pipe.It is characterized in that: (1) presses the component proportioning, take by weighing long chain diol and aliphatic diisocyanate, dibasic alcohol, corresponding solvent and catalyzer are added in the reactor, heating, stirring is warming up to 50～250 ℃ of design temperatures, drips the solution of aliphatic diisocyanate again, after dropwising, continue stirring reaction 40～60 minutes, and to IR spectrum, no longer showed 2250cm
-1Absorption peak, represent that promptly isocyanate groups reaction finishes.Product is cooled to room temperature, obtains hydroxyl-terminated polyurethane; (2) take by weighing hydroxyl-terminated polyurethane and solidifying agent by the component proportioning, they are added in the sample bottle with pigment (if needs), solvent, catalyzer and other relevant auxiliary agent, stir into homogeneous solution, obtain the one-pot polyurethane coating.
5. the preparation method of polyurethane coating according to claim 4, it is characterized in that in the above-mentioned preparation hydroxyl-terminated polyurethane process, the catalyzer that uses is the organic tin compound, or naphthenate, or the salt of the strontium of caproic acid, acetic acid, linolenic acid, bismuth, calcium, magnesium, barium.
6. the preparation method of polyurethane coating according to claim 5 is characterized in that in the above-mentioned preparation hydroxyl-terminated polyurethane process, catalyst consumption is 0.5～2.0% of aliphatic diisocyanate and a long chain diol gross weight.
7. the preparation method of polyurethane coating according to claim 4, it is characterized in that preparing in the hydroxyl-terminated polyurethane process, used solvent is the common solvent of synthesis of polyurethane, and consumption is 30～70% of aliphatic diisocyanate and a long chain diol gross weight.
8. the preparation method of polyurethane coating according to claim 4, the temperature of reaction that it is characterized in that preparing hydroxyl-terminated polyurethane is 80～150 ℃.
9. the preparation method of polyurethane coating according to claim 4 is characterized in that catalyzer selects sulfonic acid class or phosphoric acid class for use, and its consumption is 0.05～1.5% of a weight resin.
10. the preparation method of polyurethane coating according to claim 9 is characterized in that used catalyzer is a kind of of tosic acid, dinonylnaphthalene disulfonic acid, Witco 1298 Soft Acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119979A CN1109727C (en) | 1999-11-09 | 1999-11-09 | High-performance canned polyurethane paint and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119979A CN1109727C (en) | 1999-11-09 | 1999-11-09 | High-performance canned polyurethane paint and its preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1251854A true CN1251854A (en) | 2000-05-03 |
| CN1109727C CN1109727C (en) | 2003-05-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99119979A Expired - Fee Related CN1109727C (en) | 1999-11-09 | 1999-11-09 | High-performance canned polyurethane paint and its preparing process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638512B (en) * | 2009-05-25 | 2011-04-20 | 杭州康成皮革有限公司 | Organic silicon-fluorine modified resin and coating preparation method |
| CN101454414B (en) * | 2006-03-24 | 2012-08-29 | 罗地亚管理公司 | Composition polyisocyanate a proprietes anti-chocs ameliorees |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4142816C1 (en) * | 1991-12-23 | 1993-03-04 | Herberts Gmbh, 5600 Wuppertal, De | |
| DE4437841A1 (en) * | 1994-10-22 | 1996-04-25 | Basf Lacke & Farben | Filler component for use in aqueous basecoats |
| KR0167002B1 (en) * | 1994-12-27 | 1999-03-20 | 김충세 | Method of manufacturing polyurethane water disperse resin and coating composition thereof |
-
1999
- 1999-11-09 CN CN99119979A patent/CN1109727C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101454414B (en) * | 2006-03-24 | 2012-08-29 | 罗地亚管理公司 | Composition polyisocyanate a proprietes anti-chocs ameliorees |
| CN101638512B (en) * | 2009-05-25 | 2011-04-20 | 杭州康成皮革有限公司 | Organic silicon-fluorine modified resin and coating preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1109727C (en) | 2003-05-28 |
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