CN103224602A - Aqueous polyurethane film forming agent for glass fiber and preparation method thereof - Google Patents
Aqueous polyurethane film forming agent for glass fiber and preparation method thereof Download PDFInfo
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- CN103224602A CN103224602A CN2013101417116A CN201310141711A CN103224602A CN 103224602 A CN103224602 A CN 103224602A CN 2013101417116 A CN2013101417116 A CN 2013101417116A CN 201310141711 A CN201310141711 A CN 201310141711A CN 103224602 A CN103224602 A CN 103224602A
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Abstract
The invention discloses an aqueous polyurethane film forming agent for glass fiber and preparation method thereof, and macro-molecule polyol and aliphatic diisocyanate are used as raw materials for catalytic polymerization, and after twice chain extensions, a performed polymer is prepared, and after neutralization, the performed polymer is dispersed in water for obtaining an aqueous polyurethane film forming agent emulsion. The aqueous polyurethane film forming agent has excellent mechanical properties. The emulsion has good storage stability, and can be stored for more than 6 months at room temperature with stability, and the emulsion has moderate viscosity, and can be used as a film forming agent for formula of impregnating compounds for fiber glass. The prepared aqueous polyurethane film forming agent can be applied in the basalt fiber, so that the basalt fiber has excellent mechanical properties and wide development prospect.
Description
Technical field
The present invention relates to fine chemical technology field and glass technical field, be specifically related to class glass use polyurethane film-forming agent and preparation method thereof.
Background technology
Treating compound starting material and formula technique are the most critical technology that embodies all kinds of fiberglass products (comprising yarn, cloth, felt) inner quality, also are requisite industrial consumption product during glass is produced." chip fabrication techniques " that often its importance is equal to the IT industry in the industry.These two technology and product belong to two industries (fine chemistry industry industry and glass industry) respectively in the world.Its technological core is divided into two portions: the one, and the synthetic manufacturing technology of most important component membrane-forming agent-" chip fabrication techniques " in the treating compound starting material component; The 2nd, prescription utilisation technology-" the chip portfolio technology " that each component is selected in the treating compound.Above-mentioned two technology are specialized at home, the seriation degree is all not high, and two technology intersect mutually, cause domestic treating compound starting material and formula technique only to be in the situation of international low and middle-grade levels.Along with fast development and a large amount of export trades of product at home of tank furnace technology, More and more factories recognizes that the competition of fiberglass product depends on treating compound starting material and formula technique to a great extent, because this technology is directly connected to all kinds of fiberglass products (comprising yarn, cloth, felt) inner quality, become each big glass manufacturing enterprise and kept one of core competitiveness of Sustainable development.
From treating compound formula technique aspect; domestic each big glass factory; especially large tank furnace used production line; the existing accumulation of production experience for many years; possessed comparatively perfect exploitation, development treating compound prescription; debug the ability for the treatment of compound prescription, can satisfy the needs of glass productive specialization, mass-producing preferably.But be subject to the research and development of glass product seriation treating compound starting material and make bottleneck, show as high-end membrane-forming agent material dependence on import, be not formed into the raw-material autonomous innovation of film as yet or specially control channel, the share of market of high-end glass product is very low.It is further perfect that minority has the enterprise of starting material research and development throughput to await, and the dynamics of research and development throughput and the degree of depth await further to strengthen.And a considerable amount of middle-size and small-size glass fiber enterprises also do not possess the ability of research and development, debugging treating compound prescription, and old prescription such as paraffin sizing material, 711,811 treating compounds is persevered for several decades as if it were one day, and is still using, and the glass quality product is at low-level scope internal recycle.And some market in urgent needs and promising high-end glass product still exist than big gap with external product with the kinds such as winding roving of roving, high-quality short yarn cutting, injection, SMC yarn, enhancing high pressure epoxy pipeline as LFTP.Batch is little, the replacing kind is fast though have on middle-size and small-size crucible method glass is produced, and does not need advantages such as beam splitting, branch draw, and the formula technique bottleneck that is subject to treating compound temporarily can't be produced the glass product of many kinds, high profit, short run.
It is epoxy membrane-forming agent, vibrin membrane-forming agent, PVAc class membrane-forming agent, acrylic ester emulsion membrane-forming agent and polyaminoester emulsion membrane-forming agent that membrane-forming agent is broadly divided into five classes.
Wherein, polyaminoester emulsion becomes a kind of novel membrane-forming agent with fastest developing speed in the treating compound membrane-forming agent with its excellent performance, polyaminoester emulsion is normally by polyethers, polyester, dibasic alcohol and isocyanic ester, make performed polymer earlier, and use the chainextender chain extension, add water-dispersion again and make.By adopting the dibasic alcohol of different structure, the isocyanic ester of different varieties and chainextender can be regulated gap size and the soft section hard section ratio, synthetic performance difference very big polyaminoester emulsion of urethano in molecule.
Aqueous polyurethane (WPU) is with the urethane of water as dispersion medium, it can be made into water miscible latex type, emulsion-type, it has excellent properties such as urethane inherent high strength, wear resistance, snappiness.Because it has the urethano group of high polarity and high chemical property, and the big thermoplastic material of relative unreactiveness is had very strong cohesive force and interface binding ability, lack the yarn cutting treating compound with glass so be widely used in reinforced thermoplastics(RTP).Facts have proved simultaneously, in the treating compound prescription,, can effectively improve convergency, choppability and the wear resistance of glass yarn as long as add a spot of polyaminoester emulsion.
Domestic at present also can't the mass production treating compound special-purpose high-quality polyaminoester emulsion, rely on import basically, cost an arm and a leg.
Summary of the invention
In view of this, the object of the present invention is to provide high quality water based polyurethane membrane-forming agent of a class glass special use and preparation method thereof, to satisfy the high-end demand of glass product.
For achieving the above object, the invention provides following technical scheme:
Glass use polyurethane film-forming of the present invention agent has the structure of following general formula (I)～(IV):
Wherein, described E is
Preferably, described A is
The C.O.(Viscotrol C) group,
Or
N wherein
1, n
2, n
3, all to take from the molecular weight that satisfies A be 1000～2000 natural number for x, y;
Preferably, described D is
Or
Preferably, described Q is
Or
The present invention also provides a kind of method for preparing above-mentioned aqueous polyurethane membrane-forming agent, comprises the steps:
(1) one or more macromolecular polyols of fused is put in the vacuum unit that has condenser, stirred and be warming up to 100 ± 3 ℃ and vacuumize dehydration 2～2.5h, be lower than 0.3wt% until the water content of material;
(2) be cooled to 50～60 ℃, slowly add vulcabond, add the back and stir 10～15min, add catalyzer, material slowly is warming up to 80 ± 5 ℃, continue reaction 1～1.5h, near NCO content reaches theoretical value;
(3) the ionic chainextender 1 of containing that will be dissolved in anhydrous N-Methyl pyrrolidone slowly adds in the reaction mass, adds catalyzer, and reaction 1～1.5h is near NCO content reaches theoretical value;
(4) chainextender 2 that will be dissolved in a small amount of solvent slowly carries out chain extending reaction 1～1.5h in the adding reaction system, obtains NCO content and reaches near the prepolymer of theoretical value;
(5) with above-mentioned prepolymer 50～60 ℃ down in and 20～30min, redispersion makes aqueous polyurethane emulsion in water, promptly described aqueous polyurethane membrane-forming agent.
Preferably, the catalyzer described in step (2) and (3) is stannous octoate or dibutyl tin laurate, its add quality be 5/10000ths to 10/10000ths with respect to macromolecular polyol.
Preferably, described macromolecular polyol is Viscotrol C (C.O.), poly adipate succinic acid ester (PCL), polycaprolactone (PBA), polypropylene glycol (PPG) or polytetrahydrofuran (PTMG), and wherein the molecular weight of PCL, PBA, PPG and PTMG is between 1000～2000.
Preferably, described vulcabond is a hexamethylene diisocyanate (HDI), 4,4-hydrogenated diphenyl methane diisocyanate (HMDI) or isoflurane chalcone diisocyanate (IPDI).
Preferably, described chainextender 1 is dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA) or N methyldiethanol amine (MDEA).
Preferably, described chainextender 2 is 1,4-butyleneglycol (BDO), propylene glycol, glycerol or TriMethylolPropane(TMP) (TMP).
Aqueous polyurethane membrane-forming agent mechanical property excellence of the present invention, the stability in storage of emulsion is good, at least can at room temperature stablize and preserve more than 6 months, the modest viscosity of emulsion, the membrane-forming agent that is suitable as very much the glass fiber treating compound prescription uses, the present invention is applied the aqueous polyurethane membrane-forming agent that makes in basalt fibre, the mechanical property of basalt fibre is outstanding unusually, has vast potential for future development.
Embodiment
Below in conjunction with the embodiment of the invention, technical scheme of the present invention is described in detail, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, the every other embodiment that those of ordinary skills are obtained under the prerequisite of not making creative work belongs to the scope of protection of the invention.
Each used in embodiment of the invention raw material all can be buied by market.
Embodiment 1
1, with fusion poly adipate succinic acid ester (PBA) 50g, Viscotrol C (C.O.) 5g puts in the reactor that has condenser, thermometer, vacuumizes, begin to stir, be warming up to 100 ± 3 ℃ and vacuumize dehydration 2～2.5 hours, be lower than 0.3wt% until the water content of material;
2, then be cooled to 50～60 ℃, be added dropwise to 4,4-hydrogenated diphenyl methane diisocyanate (HMDI) 46.81g, dripping the back stirred 10 minutes, after stirring, add 0.025g catalyzer dibutyl tin laurate, material is slowly risen to 80 ± 5 ℃, continue reaction 1～1.5 hour, until NCO content near theoretical value;
3, when NCO content reaches theoretical value, the ionic chainextender 1 dihydroxy methylpropane 6.48g that contains that will be dissolved in anhydrous N-Methyl pyrrolidone is added dropwise in the reaction mass, add 0.025g catalyzer dibutyl tin laurate, reacted 1～1.5 hour, near NCO content reaches theoretical value;
4, will be dissolved in the chainextender 21 of a small amount of solvent then, 4-butyleneglycol 4.5g is added dropwise to and carried out chain extending reaction in the reaction system about 1.5 hours, and the NCO content in the sampling analysis material is near theoretical content;
5, with hydrophilic chain extension in the above-mentioned prepolymer that obtains in 50～60 ℃ of following triethylamines and 20～30 minutes, prepolymer is scattered in makes aqueous polyurethane emulsion in the water again.
Embodiment 2
1, fusion polytetrahydrofuran (PTMG) 50g is put in the reactor that has condenser, thermometer, vacuumizes, begin to stir, be warming up to 100 ± 3 ℃ and vacuumize dehydration 2～2.5 hours, be lower than 0.3wt% until the water content of material;
2, then be cooled to 50～60 ℃, be added dropwise to isoflurane chalcone diisocyanate 32.33g, drip the back and stirred 10 minutes, after stirring, add the inferior tin of 0.05g octoate catalyst, material is slowly risen to 80 ± 5 ℃, continue reaction 1～1.5 hour, until NCO content near theoretical value;
3, when NCO content reaches theoretical value, the ionic chainextender 1 dihydroxy methylpropane 3.87g that contains that will be dissolved in anhydrous N-Methyl pyrrolidone is added dropwise in the reaction mass, add the inferior tin of 0.05g octoate catalyst, reacted 1～1.5 hour, near NCO content reaches theoretical value;
4, the chainextender 2 TriMethylolPropane(TMP) 3.0g that will be dissolved in a small amount of solvent then are added dropwise to and carried out chain extending reaction in the reaction system about 1.5 hours, and the NCO content in the sampling analysis material is near theoretical content;
5, with hydrophilic chain extension in the above-mentioned prepolymer that obtains in 50～60 ℃ of following triethylamines and 20～30 minutes, prepolymer is scattered in makes aqueous polyurethane emulsion in the water again.
Embodiment 3
1, fusion polypropylene glycol (PPG) 52g is put in the reactor that has condenser, thermometer, vacuumizes, begin to stir, be warming up to 100 ± 3 ℃ and vacuumize dehydration 2～2.5 hours, be lower than 0.3wt% until the water content of material;
2, then be cooled to 50～60 ℃, be added dropwise to hexamethylene diisocyanate (HDI) 24.28g, drip the back and stirred 10 minutes, after stirring, add the inferior tin of 0.05g octoate catalyst, material is slowly risen to 80 ± 5 ℃, continue reaction 1～1.5 hour, until NCO content near theoretical value;
3, when NCO content reaches theoretical value, the ionic chainextender 1N-methyldiethanolamine 3.97g that contains that will be dissolved in anhydrous N-Methyl pyrrolidone is added dropwise in the reaction mass, add the inferior tin of 0.05g octoate catalyst, reacted 1～1.5 hour, near NCO content reaches theoretical value;
4, will be dissolved in the chainextender 21 of a small amount of solvent then, 4-butyleneglycol 4.1g is added dropwise to and carried out chain extending reaction in the reaction system about 1.5 hours, and the NCO content in the sampling analysis material is near theoretical content;
5, with hydrophilic chain extension in the above-mentioned prepolymer that obtains in 50～60 ℃ of following triethylamines and 20～30 minutes, prepolymer is scattered in makes aqueous polyurethane emulsion in the water again.
Embodiment 4～7 Comparative Examples transitivities are estimated
Embodiment 4: macromolecular polyol be polycarbonate (PC-1000) and Viscotrol C (C.O.) (80%:20%), chainextender 1 is dimethylol propionic acid (DMPA), vulcabond is 4,4-hydrogenated diphenyl methane diisocyanate (HMDI), triethylamine (TEA) neutralization, chainextender 2 is 1,4-butyleneglycol (BDO), reaction conditions is according to embodiment 1, and the gained sample is designated as sample 1.
Embodiment 5: macromolecular polyol be polytetrahydrofuran (PTMG-1000) and Viscotrol C (C.O.) (80%:20%), chainextender 1 is dimethylol propionic acid (DMPA), vulcabond is 4,4-hydrogenated diphenyl methane diisocyanate (HMDI), triethylamine (TEA) neutralization, chainextender 2 is 1,4-butyleneglycol (BDO), reaction conditions is according to embodiment 1, and the gained sample is designated as sample 2.
Embodiment 6: macromolecular polyol be benzoic anhydride polyester polyol and Viscotrol C (C.O.) (80%:20%), chainextender 1 is dimethylolpropionic acid (DMBA), vulcabond is 4,4-hydrogenated diphenyl methane diisocyanate (HMDI), triethylamine (TEA) neutralization, chainextender 2 is TriMethylolPropane(TMP) (TMP), and reaction conditions is according to embodiment 1, and the gained sample is designated as sample 3.
Embodiment 7: macromolecular polyol is poly adipate succinic acid ester (PBA-1000), chainextender 1 is dimethylol propionic acid (DMPA), vulcabond is isoflurane chalcone diisocyanate (IPDI), triethylamine (TEA) neutralization, chainextender 2 is TriMethylolPropane(TMP) (TMP), reaction conditions is according to embodiment 1, and the gained sample is designated as sample 4.
One, mechanical property
The polyurethane aqueous dispersion of preparation is placed tetrafluoro dish drying and forming-film at room temperature, put into 80 ℃ of baking oven insulation 4h again, promptly prepare glass fiber treating compound use polyurethane film, the aqueous polyurethane film of preparation is tailored the batten that becomes to carry out Mechanics Performance Testing with cut-off knife carry out Mechanics Performance Testing, test result is as follows:
The Mechanics Performance Testing of table 1 polyurethane film
In general for mechanical property with a kind of polyester polyol synthetic water based polyurethane film, the mechanical property that how much influences the aqueous polyurethane film and the elongation at break of the relative consumption by regulating the pure and mild isocyanic ester of polyester polyols.Usually, for using the different proportioning synthetic of same materials aqueous polyurethane film, tensile strength is big more, and elongation at break is more little.Can suitably regulate proportioning to satisfy service requirements according to the difference of working conditions.
Two, the package stability of aqueous polyurethane dispersing liquid
Whether aqueous polyurethane dispersing liquid is placed airtight test tube, place 60 ℃ constant temperature oven 72 hours, observing has precipitation to produce.Do not produce if there is precipitation, then think that according to time temperature equivalence principle this dispersion liquid of wakeing up can at room temperature stablize preservation more than 6 months.Test result is as follows:
Table 2 package stability test result
Test result shows that except sample 3, other aqueous polyurethane dispersing liquid all has better package stability.General experience, if at room temperature stable existence is more than one week for the dispersion liquid of anion aqueous polyurethane, so actual the preservation is absolute no problem more than 1 year.Wherein, sample 1,2 and 4, does not have precipitation and occurs more than 1 year in the laboratory room temperature preservation.
Three, the pH value of aqueous polyurethane dispersing liquid and viscosity
The viscosity of each aqueous polyurethane dispersing liquid is as shown in table 3:
The viscosity of table 3 aqueous polyurethane dispersing liquid
Sample 3 is not surveyed for storing instability, compare according to range estimation with other emulsions, the pH value of the viscosity of emulsion and emulsion, the content of DMPA, solid content have bigger relation, can control the viscosity of emulsion by the content of adjusting pH value and the DMPA that adds, promptly the viscosity of emulsion is adjustable in certain scope.Wherein the solid content of sample 4 still has lower viscosity up to 40% o'clock.
Can stable existence under alkaline condition as anion aqueous polyurethane.With the pH test paper pH value of aqueous polyurethane dispersing liquid is tested, the pH value of aqueous polyurethane dispersing liquid that obtains 4 samples is all between 7～9.This is to form powerful water-wetted surface because anion aqueous polyurethane mainly relies on alkaline condition under the carboxylic acid ion of formation at the latex ion surface, makes latex particle stable existence in water.
Embodiment 8 aqueous polyurethane membrane-forming agents are applied in the evaluation of physical property in the basalt fibre
Embodiment 4～7 prepared aqueous polyurethane membrane-forming agents are mixed use as treating compound prescription and basalt fibre, the content of basalt fibre is 50wt%～60wt%, and the basalt fibre of the aqueous polyurethane membrane-forming agent that used the foregoing description 4～7 carried out physical property measurement, main its tensile strength of examination and flexural strength, basalt fibre content is consistent, be all the addition of 55wt%, test result is as shown in table 4:
The Mechanics Performance Testing of table 4 basalt fibre
From The above results as can be seen, except sample 3, added the basalt fibre behind the aqueous polyurethane membrane-forming agent, tensile strength is all greater than 200MPa, and flexural strength is all greater than 250MPa, and mechanical property is very outstanding.
In sum, aqueous polyurethane membrane-forming agent mechanical property excellence of the present invention, the stability in storage of emulsion is good, at least can at room temperature stablize and preserve more than 6 months, the modest viscosity of emulsion, the membrane-forming agent that is suitable as very much the glass fiber treating compound prescription uses, and the present invention is applied the aqueous polyurethane membrane-forming agent that makes in basalt fibre, the mechanical property of basalt fibre is outstanding unusually, has vast potential for future development.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and under the situation that does not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, therefore is intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in the scope.
In addition, be to be understood that, though this specification sheets is described according to embodiment, but be not that each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets only is for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme among each embodiment also can form other embodiments that it will be appreciated by those skilled in the art that through appropriate combination.
Claims (10)
1. a class glass use polyurethane film-forming agent is characterized in that having the structure of following general formula (I)～(IV):
Wherein, described E is
2. glass use polyurethane film-forming according to claim 1 agent, it is characterized in that: described A is
The C.O.(Viscotrol C) group,
Or
N wherein
1, n
2, n
3, all to take from the molecular weight that satisfies A be 1000～2000 natural number for x, y.
3. glass use polyurethane film-forming according to claim 1 agent, it is characterized in that: described D is
Or
4. glass use polyurethane film-forming according to claim 1 agent, it is characterized in that: described Q is
Or
5. a method for preparing the agent of the described glass use of claim 1 polyurethane film-forming is characterized in that, comprises the steps:
(1) one or more macromolecular polyols of fused is put in the vacuum unit that has condenser, stirred and be warming up to 100 ± 3 ℃ and vacuumize dehydration 2～2.5h, be lower than 0.3wt% until the water content of material;
(2) be cooled to 50～60 ℃, slowly add vulcabond, add the back and stir 10～15min, add catalyzer, material slowly is warming up to 80 ± 5 ℃, continue reaction 1～1.5h, near NCO content reaches theoretical value;
(3) the ionic chainextender 1 of containing that will be dissolved in anhydrous N-Methyl pyrrolidone slowly adds in the reaction mass, adds catalyzer, and reaction 1～1.5h is near NCO content reaches theoretical value;
(4) chainextender 2 that will be dissolved in a small amount of solvent slowly carries out chain extending reaction 1～1.5h in the adding reaction system, obtains NCO content and reaches near the prepolymer of theoretical value;
(5) with the prepolymer of step (4) gained 50～60 ℃ down in and 20～30min, redispersion makes aqueous polyurethane emulsion in water, promptly described aqueous polyurethane membrane-forming agent.
6. method according to claim 5 is characterized in that: the catalyzer described in step (2) and (3) is stannous octoate or dibutyl tin laurate, its add quality be 5/10000ths to 10/10000ths with respect to macromolecular polyol.
7. method according to claim 5 is characterized in that: described macromolecular polyol is Viscotrol C, poly adipate succinic acid ester, polycaprolactone, polypropylene glycol or the polytetrahydrofuran of molecular weight between 1000～2000.
8. method according to claim 5 is characterized in that: described vulcabond is a hexamethylene diisocyanate, 4,4-hydrogenated diphenyl methane diisocyanate or isoflurane chalcone diisocyanate.
9. method according to claim 5 is characterized in that: described chainextender 1 is dimethylol propionic acid, dimethylolpropionic acid or N methyldiethanol amine.
10. method according to claim 5 is characterized in that: described chainextender 2 is 1,4-butyleneglycol, propylene glycol, glycerol or TriMethylolPropane(TMP).
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| CN106188478A (en) * | 2016-07-26 | 2016-12-07 | 巨石集团有限公司 | A kind of modified polyurethane emulsion film former and its preparation method and application |
| CN106939071A (en) * | 2017-04-11 | 2017-07-11 | 东莞市雄林新材料科技股份有限公司 | A kind of automobile massage TPU composites and preparation method thereof |
| CN108059366A (en) * | 2017-12-28 | 2018-05-22 | 安徽宏实光机电高科有限公司 | A kind of coating processes of isocyanates enclosed type basalt fibre size |
| CN109796576A (en) * | 2019-01-07 | 2019-05-24 | 泰山玻璃纤维有限公司 | A kind of glass fibre film forming agent and preparation method thereof |
| CN112480360A (en) * | 2020-12-14 | 2021-03-12 | 山东明珠材料科技有限公司 | Waterborne polyurethane film forming agent for glass fibers |
| CN114059720A (en) * | 2021-11-30 | 2022-02-18 | 东北大学 | Preparation method of basalt fiber toughened bamboo reinforcement |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188478A (en) * | 2016-07-26 | 2016-12-07 | 巨石集团有限公司 | A kind of modified polyurethane emulsion film former and its preparation method and application |
| CN106188478B (en) * | 2016-07-26 | 2019-09-20 | 巨石集团有限公司 | A kind of modified polyurethane emulsion film forming agent and its preparation method and application |
| CN106939071A (en) * | 2017-04-11 | 2017-07-11 | 东莞市雄林新材料科技股份有限公司 | A kind of automobile massage TPU composites and preparation method thereof |
| CN108059366A (en) * | 2017-12-28 | 2018-05-22 | 安徽宏实光机电高科有限公司 | A kind of coating processes of isocyanates enclosed type basalt fibre size |
| CN109796576A (en) * | 2019-01-07 | 2019-05-24 | 泰山玻璃纤维有限公司 | A kind of glass fibre film forming agent and preparation method thereof |
| CN112480360A (en) * | 2020-12-14 | 2021-03-12 | 山东明珠材料科技有限公司 | Waterborne polyurethane film forming agent for glass fibers |
| CN114059720A (en) * | 2021-11-30 | 2022-02-18 | 东北大学 | Preparation method of basalt fiber toughened bamboo reinforcement |
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Application publication date: 20130731 |