CN109233608B - Special polyurethane waterproof coating for underground pipe gallery and production process thereof - Google Patents
Special polyurethane waterproof coating for underground pipe gallery and production process thereof Download PDFInfo
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- CN109233608B CN109233608B CN201811039078.9A CN201811039078A CN109233608B CN 109233608 B CN109233608 B CN 109233608B CN 201811039078 A CN201811039078 A CN 201811039078A CN 109233608 B CN109233608 B CN 109233608B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a special polyurethane waterproof coating for underground pipe galleries and a preparation method thereof, wherein the waterproof coating comprises the following components: hyperbranched block polyether polyol, microcrystalline muscovite powder, flame-retardant polyether amine, powder filler, dodecacarbodiimide, trifunctional oxazolidine copolymer, adhesion promoter, penetration leveling agent and penetrating agent. The polyurethane waterproof coating is specially used for underground pipe galleries, has strong permeability after being sprayed on a concrete base layer, and has the function of blocking and isolating because the coating easily permeates into a multiphase porous structure of concrete; the waterproof adhesive has excellent mechanical property, elastic recovery rate and bonding strength, prevents structural deformation and cracking, and has high waterproof durability.
Description
Technical Field
The invention relates to the field of waterproof coatings, in particular to a polyurethane waterproof coating special for underground pipe galleries and a production process thereof.
Background
The underground pipe gallery is a large underground space used for containing tap water, electric power telecommunication, cold and hot water pipes, fuel gas and other functions, can effectively reduce traffic jam caused by road surface excavation, and is convenient for daily inspection and line maintenance. Underground pipe galleries originate in Europe, have been operated abroad for hundreds of years, have been developed more maturely, and are still in the early development stage in China.
CN201410833840.6 waterborne polyurethane coating containing polyether polyol/nano hybrid material; CN201510813186.7 a high-strength environment-friendly polyurethane flame-retardant waterproof coating and a preparation method thereof; although the prior art has a plurality of polyurethane coatings, the disclosed polyurethane coating is used for underground pipe galleries of urban underground facilities, has obviously poor performance, and has a great number of problems of water leakage, difficult repair and the like.
The underground pipe gallery is used as an urban underground facility arterial engineering, has long-term strategic significance for urban construction, but the problem of water leakage also troubles the construction of the underground pipe gallery. From the partial projects built at present, the construction and maintenance of underground pipe gallery projects are troubled by several difficulties: (1) the pipe gallery is difficult to repair, the pipe gallery is buried underground for a long time, and once leakage occurs, the waterproof layer is difficult to repair; (2) the service life is long, the service life of the structure of the pipe gallery engineering is 100 years, and the requirements on the quality and the service life of the waterproof material are high; (3) the structure is easy to deform, the pipe gallery is generally positioned below a city traffic lane, the structure is easy to deform and crack under the action of long-term dynamic load and the influence of surrounding buildings (structures), and the waterproof material is required to be well suitable for the deformation of the structure; (4) the concrete has the advantages that the number of detail nodes is large, the pipe gallery is an underground slender structure, the number of node positions such as construction joints, deformation joints, wall-penetrating sleeves, wall-penetrating bolts and reserved interfaces is large, the waterproof difficulty is high, and the waterproof material is required to have good permeability and bonding strength; (5) the multiphase porous system of the reinforced concrete of the pipe gallery is easy to be corroded by underground water, the service life is shortened, and high-voltage cables are arranged in the pipe gallery, if wet stains or water seepage exists, the cables are easy to rust and strike fire, so that the wet stains and water leakage on the surface of the structure are not allowed.
Disclosure of Invention
Due to the difficulties, the general waterproof material is difficult to meet the application requirement of the underground pipe gallery, and the invention provides the polyurethane waterproof coating special for the underground pipe gallery and the production process thereof aiming at the severe requirement of the underground pipe gallery engineering.
The technical scheme of the invention is to provide the following special polyurethane waterproof coating for the underground pipe gallery, which comprises the following components in parts by weight:
28-45 parts of hyperbranched block polyether polyol, 6-20 parts of microcrystalline white mica powder, 6-15 parts of flame-retardant polyether amine, 7-13 parts of powder filler, 17-30 parts of dodecacarbodiimide, 8-20 parts of trifunctional oxazolidine copolymer, 0.5-4 parts of adhesion promoter, 1-5 parts of penetration leveling agent and 0.3-2 parts of penetrating agent.
The special polyurethane waterproof coating for the underground pipe gallery is a single component, does not need to be weighed and stirred, can be directly used, and adopts a spraying mode during product construction.
The molecular weight of the hyperbranched block polyether polyol is 1800-3000, and the hydroxyl value is 38.5-42.0 KOHmg/g;
the microcrystalline muscovite powder and SiO2The content of the magnetic material is more than or equal to 42 percent, and the content of the magnetic material is more than or equal to 280 multiplied by 10-6The water content is less than or equal to 0.5 percent, and the granularity is 800-2500 meshes.
The flame-retardant polyether amine is halogenated polyether amine, the bromine content is about 24-31%, the chlorine content is about 7.5-12%, and the hydroxyl value is about 120-150 mgKOH/g.
The powder filling agent is polyether amine modified montmorillonite which is modified by polyether amine D230, and the amine value is 0.35-0.56 meq/g.
The adhesion promoter is a monoalkoxy titanate coupling agent, and is a pyrophosphoric acid type DNZ-201.
The penetration leveling agent is a fluorine-containing acrylate copolymer, the fluorine content is 46%, and the surface tension is 8-15.5 dyn/cm.
The penetrant is fatty alcohol-polyoxyethylene ether, the carbon chain R value of the penetrant is C7-C9, the n value is 5, the water content is less than or equal to 0.1%, and the HLB value is 6.5-8.
A production process of a special polyurethane waterproof coating for underground pipe galleries comprises the following steps:
(1) adding 6-15 parts of flame-retardant polyether amine and 7-13 parts of powder filler into a No. 1 reaction kettle, heating to 115 +/-5 ℃, dehydrating for 3 hours under the vacuum degree of-0.09 to-0.1 MPa, introducing nitrogen for replacement for 2 times, cooling to 50-55 ℃, adding 17-30 parts of dodecacarbodiimide, slowly heating to 80-85 ℃, and stirring for 2.5 hours at constant temperature to obtain the isocyanate-terminated polymer.
(2) Adding 28-45 parts of hyperbranched block polyether polyol and 6-20 parts of microcrystalline muscovite powder into a No. 2 reaction kettle, heating to 115 +/-5 ℃, dehydrating for 2 hours under the vacuum degree of-0.09 to-0.1 MPa, cooling to 65-70 ℃, introducing nitrogen, then putting a copolymer prepared by the No. 1 reaction kettle into the No. 2 reaction kettle, heating to 83-88 ℃, reacting for 2 hours, cooling to 75-78 ℃, adding 8-20 parts of trifunctional oxazolidine copolymer, starting high-speed dispersion, adding 0.5-4 parts of adhesion promoter, 1-5 parts of permeation leveling agent and 0.3-2 parts of penetrating agent after 40min, stirring for 30min, closing nitrogen, defoaming for 20min in vacuum, and discharging.
Has the advantages that:
the polyurethane waterproof coating produced by the production process of the special polyurethane waterproof coating for the underground pipe gallery has the following properties: the tensile strength is 6.8-7.7MPa, the elongation at break is 920-980%, the tear strength is 30-34N/mm, the solid content is 99%, the low-temperature bending property is-40 ℃ and has no crack, the water impermeability is 0.4 MPa, the water impermeability is 120min, the bonding strength is 3.0-3.6MPa, the elastic recovery rate is 93-96%, the coating insulation resistance is 1100-1200M omega/km, the coating flame retardant property is B1 grade, and the concrete penetration is 0.43-0.46kg/M2The retention rate of acid treatment tensile strength is 98-99%, the retention rate of alkali treatment tensile strength is 98-99%, the retention rate of heat treatment tensile strength is 100%, and the retention rate of salt treatment tensile strength is 98-99%.
After the polyurethane waterproof coating produced by the method is sprayed on a concrete base layer, the excellent permeability of the polyurethane waterproof coating can ensure that the coating is easy to permeate into a multi-phase porous structure of concrete, and the polyurethane waterproof coating plays a role in blocking and isolating; the excellent mechanical property, elastic recovery rate and bonding strength of the composite material can well adapt to structural deformation and cracking, and the requirement of the waterproof durability of the underground pipe gallery is met; the special polyurethane waterproof coating for the underground pipe gallery is a waterproof coating which has good insulativity, bonding strength, permeability and flame retardance, strong bonding force with a base layer, water resistance and corrosion resistance and can meet the requirements of underground pipe gallery engineering projects.
Detailed Description
For convenience of explanation, the polyurethane waterproof coating special for underground pipe galleries and the production process thereof are explained in detail.
Example 1:
the special polyurethane waterproof coating for the underground pipe gallery comprises the following components in parts by weight:
36 parts of hyperbranched block polyether polyol, 10 parts of microcrystalline white mica powder, 11 parts of flame-retardant polyether amine, 9 parts of powder filler, 25 parts of dodecacarbodiimide, 14 parts of trifunctional oxazolidine copolymer, 1.5 parts of adhesion promoter, 2.5 parts of permeation and leveling agent and 1 part of penetrating agent.
The molecular weight of the hyperbranched block polyether polyol is 1800-3000, and the hydroxyl value is 38.5-42.0 KOHmg/g;
the microcrystalline muscovite powder and SiO2The content of the magnetic material is more than or equal to 42 percent, and the content of the magnetic material is more than or equal to 280 multiplied by 10-6The water content is less than or equal to 0.5 percent, and the granularity is 800-2500 meshes.
The flame-retardant polyether amine is halogenated polyether amine, the bromine content is about 24-31%, the chlorine content is about 7.5-12%, and the hydroxyl value is about 120-150 mgKOH/g.
The powder filling agent is polyether amine modified montmorillonite which is modified by polyether amine D230, and the amine value is 0.35-0.56 meq/g.
The adhesion promoter is a monoalkoxy titanate coupling agent, and is a pyrophosphoric acid type DNZ-201.
The penetration leveling agent is a fluorine-containing acrylate copolymer, the fluorine content is 46%, and the surface tension is 8-15.5 dyn/cm.
The penetrant is fatty alcohol-polyoxyethylene ether, the carbon chain R value of the penetrant is C7-C9, the n value is 5, the water content is less than or equal to 0.1%, and the HLB value is 6.5-8.
A production process of a special polyurethane waterproof coating for underground pipe galleries comprises the following steps:
(1) adding 11 parts of flame-retardant polyether amine and 9 parts of powder filler into a No. 1 reaction kettle, heating to 115 +/-5 ℃, dehydrating for 3 hours under the vacuum degree (-0.09 to-0.1) MPa, introducing nitrogen for replacement for 2 times, cooling to 50 to 55 ℃, adding 25 parts of dodecacarbodiimide, slowly heating to 80 to 85 ℃, and stirring for 2.5 hours at constant temperature to obtain the isocyanate-terminated polymer.
(2) Adding 36 parts of hyperbranched block polyether polyol and 10 parts of microcrystalline muscovite powder into a No. 2 reaction kettle, heating to 115 +/-5 ℃, dehydrating for 2 hours under the vacuum degree of (-0.09 to-0.1) MPa, and cooling to 65-70 ℃;
then, nitrogen is introduced; and (2) putting the isocyanate-terminated polymer prepared in the No. 1 reaction kettle into the No. 2 reaction kettle, heating to 83-88 ℃, reacting for 2h, cooling to 75-78 ℃, adding 14 parts of trifunctional oxazolidine copolymer, starting high-speed dispersion, adding 1.5 parts of adhesion promoter, 2.5 parts of permeation and leveling agent and 1 part of penetrating agent after 40min, stirring for 30min, then closing nitrogen, defoaming for 20min in vacuum, and discharging.
Example 2:
compared with the example 1, under the condition that other conditions are completely the same as those in the example 1, the polyurethane waterproof coating special for the underground pipe gallery is prepared by only changing the parts of the flame-retardant polyether amine, taking 8 parts of the flame-retardant polyether amine in the example 2 and not changing the parts by weight of other components according to the production process of the polyurethane waterproof coating special for the underground pipe gallery, which is described in the example 1.
Example 3:
compared with the example 1, under the condition that other conditions are completely the same as those in the example 1, the polyurethane waterproof coating special for the underground pipe gallery is prepared by only changing the parts of the flame-retardant polyether amine, taking 14 parts of the flame-retardant polyether amine in the example 3 and not changing the parts by weight of other components according to the production process of the polyurethane waterproof coating special for the underground pipe gallery, which is described in the example 1.
The special polyurethane waterproof coating for the underground pipe gallery prepared according to the three embodiments is subjected to performance detection, and the detection results are shown in table 1:
TABLE 1
As can be seen from table 1, the addition amount of the flame-retardant polyetheramine has the following effects on the prepared special polyurethane waterproof coating for underground pipe corridors: the elongation at break, the elastic recovery rate and the concrete penetration are improved along with the increase of the addition amount of the flame-retardant polyether amine; the tensile strength, tear strength and bond strength decrease with increasing addition; the change of the addition amount of the flame-retardant polyether amine has little influence on the low-temperature bending property and the water impermeability of the special polyurethane waterproof coating for the underground pipe gallery and the tensile strength after acid-base hot salt treatment.
The data obtained by detection shows that the addition amount of the flame-retardant polyether amine plays a critical role in the performance of the special polyurethane waterproof coating for the underground pipe gallery, and the addition amount of the flame-retardant polyether amine influences the chain extension degree of the isocyanate terminated polymer in the step 1, so that the synthesis reaction of a subsequent prepolymer is influenced, and various performances of the coating after film forming are influenced.
The three embodiments can meet the current industry standard and the use requirement of the underground pipe gallery, particularly the permeability and the flame retardance. However, by comprehensively considering the use environment, construction conditions, construction modes and the like of the special polyurethane waterproof coating for the underground pipe gallery, the comprehensive performance of the special polyurethane waterproof coating for the underground pipe gallery prepared in the embodiment 1 is superior to that of the special polyurethane waterproof coating for the underground pipe gallery prepared in the embodiments 2 and 3, the polyurethane waterproof coating described in the embodiment 1 belongs to the optimal technical scheme, and the prepared special polyurethane waterproof coating for the underground pipe gallery has the best comprehensive performance.
It should be noted that, unless otherwise stated, the ingredients are calculated according to the weight parts.
In the above embodiments, the best mode of the present invention has been described, and it is apparent that many changes can be made under the inventive concept of the present invention. It should be noted here that any changes made under the inventive concept of the present invention shall fall within the protective scope of the present invention.
Claims (6)
1. The utility model provides a special polyurethane waterproof coating of underground pipe gallery which characterized in that:
the waterproof coating comprises the following components in parts by weight: 28-45 parts of hyperbranched block polyether polyol, 6-20 parts of microcrystalline white mica powder, 6-15 parts of flame-retardant polyether amine, 7-13 parts of powder filler, 17-30 parts of dodecacarbodiimide, 8-20 parts of trifunctional oxazolidine copolymer, 0.5-4 parts of adhesion promoter, 1-5 parts of penetration leveling agent and 0.3-2 parts of penetrating agent;
the molecular weight of the hyperbranched block polyether polyol is 1800-3000, and the hydroxyl value is 38.5-42.0 mgKOH/g;
the microcrystalline muscovite powder and SiO2The content of the active carbon is more than or equal to 42 percent, the water content is less than or equal to 0.5 percent, and the granularity is 800-2500 meshes;
the flame-retardant polyether amine is halogenated polyether amine, the bromine content is 24-31%, the chlorine content is 7.5-12%, and the hydroxyl value is 120-150 mgKOH/g;
the powder filler is polyether amine modified montmorillonite modified by polyether amine D230, and the amine value is 0.35-0.56 meq/g;
the adhesion promoter is a monoalkoxy titanate coupling agent, is pyrophosphoric acid type, and is DNZ-201;
the penetration leveling agent is a fluorine-containing acrylate copolymer, the fluorine content is 46%, and the surface tension is 8-15.5 dyn/cm;
the penetrant is fatty alcohol-polyoxyethylene ether, the carbon chain R value of the penetrant is C7-C9, the n value is 5, the water content is less than or equal to 0.1%, and the HLB value is 6.5-8.
2. The special polyurethane waterproof coating for underground pipe galleries according to claim 1, wherein the special polyurethane waterproof coating comprises the following components in percentage by weight: the waterproof coating comprises the following components in parts by weight: 36 parts of hyperbranched block polyether polyol, 10 parts of microcrystalline white mica powder, 8 parts of flame-retardant polyether amine, 9 parts of powder filler, 25 parts of dodecacarbodiimide, 14 parts of trifunctional oxazolidine copolymer, 1.5 parts of adhesion promoter, 2.5 parts of permeation and leveling agent and 1 part of penetrating agent.
3. The production process of the special polyurethane waterproof coating for the underground pipe gallery according to claim 1, characterized in that:
the method comprises the following steps: preparing an isocyanate-terminated polymer;
the preparation of the isocyanate-terminated polymer: adding flame-retardant polyether amine and a powder filler into a No. 1 reaction kettle, heating to 115 +/-5 ℃, dehydrating for 3h under the vacuum degree of-0.09 to-0.1 MPa, introducing nitrogen for replacement for 2 times, cooling to 50-55 ℃, adding dodecacarbodiisocyanate, slowly heating to 80-85 ℃, and stirring at constant temperature for 2.5h to obtain the isocyanate-terminated polymer.
4. The production process of the special polyurethane waterproof coating for the underground pipe gallery according to claim 3, characterized in that: further comprising the steps of: adding hyperbranched block polyether polyol and microcrystalline muscovite powder into a No. 2 reaction kettle, heating to 115 +/-5 ℃, dehydrating for 2 hours under the vacuum degree of minus 0.09 to minus 0.1MPa, and cooling to 65-70 ℃.
5. The production process of the special polyurethane waterproof coating for the underground pipe gallery according to claim 4, characterized in that: further comprising the steps of: introducing nitrogen, pumping the isocyanate-terminated polymer prepared in the reaction kettle No. 1 into the reaction kettle No. 2, heating to 83-88 ℃, reacting for 2h, cooling to 75-78 ℃, adding the trifunctional oxazolidine copolymer, starting high-speed dispersion, adding the adhesion promoter, the permeation leveling agent and the penetrating agent after 40min, stirring for 30min, then closing the nitrogen, and carrying out vacuum deaeration for 20 min.
6. The special polyurethane waterproof coating for underground pipe galleries according to claim 1, wherein the special polyurethane waterproof coating comprises the following components in percentage by weight: for underground pipe gallery, the polyurethane waterproof coating: the elastic recovery rate is 93-96%, the flame retardant property of the coating film is B1 grade, and the concrete penetration is 0.43-0.46kg/m2The retention rate of the acid-treated tensile strength is 98-99%.
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| CN114621667A (en) * | 2022-03-24 | 2022-06-14 | 北京东方雨虹防水技术股份有限公司 | Wear-resistant polyurethane waterproof coating for field of livestock breeding and preparation method thereof |
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| CN104877542A (en) * | 2015-06-16 | 2015-09-02 | 北京东方雨虹防水技术股份有限公司 | Mono-component PU (Polyurethane) root-resistant waterproof paint and preparation method thereof |
| CN105038565A (en) * | 2015-08-18 | 2015-11-11 | 北京东方雨虹防水技术股份有限公司 | Bi-component polyurethane waterproof coating and preparation method thereof |
| CN106750248A (en) * | 2017-01-24 | 2017-05-31 | 中国科学技术大学 | A kind of hyperbranched flame retardant polyether polyol and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104877542A (en) * | 2015-06-16 | 2015-09-02 | 北京东方雨虹防水技术股份有限公司 | Mono-component PU (Polyurethane) root-resistant waterproof paint and preparation method thereof |
| CN105038565A (en) * | 2015-08-18 | 2015-11-11 | 北京东方雨虹防水技术股份有限公司 | Bi-component polyurethane waterproof coating and preparation method thereof |
| CN106750248A (en) * | 2017-01-24 | 2017-05-31 | 中国科学技术大学 | A kind of hyperbranched flame retardant polyether polyol and preparation method thereof |
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Address after: 262735 Shandong city in Weifang Province, Shouguang City, Taiwan town government West 2000 meters Applicant after: HONGYUAN WATERPROOF TECHNOLOGY GROUP Co.,Ltd. Address before: 262735 Shandong city in Weifang Province, Shouguang City, Taiwan town government West 2000 meters Applicant before: WEIFANG HONGYUAN WATERPROOF MATERIAL Co.,Ltd. |
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| GR01 | Patent grant | ||
| GR01 | Patent grant |