CN104910850A - High-strength water-resistant and mildew-proof glass cement - Google Patents

High-strength water-resistant and mildew-proof glass cement Download PDF

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Publication number
CN104910850A
CN104910850A CN201510287510.6A CN201510287510A CN104910850A CN 104910850 A CN104910850 A CN 104910850A CN 201510287510 A CN201510287510 A CN 201510287510A CN 104910850 A CN104910850 A CN 104910850A
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glass cement
mildew
resistant
strong water
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饶玉明
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Abstract

The invention discloses high-strength water-resistant and mildew-proof glass cement, which is prepared from the following components in parts by weight: 60-64 parts of a silicane terminated polyurethane prepolymer, 7-9 parts of a plasticizer, 18-20 parts of talcum powder, 15-25 parts of kieselguhr powder, 4-8 parts of lithium-based bentonite, 8-10 parts of bamboo charcoal granule powder, 2-4 parts of -200-mesh cerium oxide powder, 1.2-1.4 parts of an antioxidant, 0.8-1.2 parts of an ultraviolet absorbent, 0.2-0.4 part of a thixotropic agent, 1-2 parts of benzimidazole carbamate, 1-2 parts of benzyltrimethylammonium chloride, 2.5-3.5 parts of an adhesion promoter and 0.2-0.4 part of a catalyst.

Description

A kind of high strong water resistant mildew-resistant glass cement
Technical field
The present invention relates to sealing material technical field, particularly a kind of high strong water resistant mildew-resistant glass cement.
Background technology
Glass cement is being commonly called as of glass cement stick, is a kind of bonding and multi-usage functional materials that is sealing property of simultaneously having.It both can prevent internal gas or leak of liquid, can prevent the intrusions such as external dust, moisture, moisture, dirt and pharmaceutical chemicals again, and can prevent mechanical vibration, impact injury or reach the effect of sound-insulating and heat-insulating.Glass cement can be out of shape with trim shape, not easily trickles and has certain cementability, is widely used in the sealing of civil construction, electronic apparatus, mechanical means and communications and transportation utensil and other field component.Glass cement is indispensable important materials for solution run, drip, leak, in modern science and technology and national economy, have vital role.
The main species of glass cement has: urethane, poly-sulphur, organosilicon, acrylate, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, pitch and oiliness caulk compound etc., wherein urethane, thiorubber and silicone glass colloidality can be good, application is comparatively extensive, and is called three large spring glass glue.The intensity of polyurethane glass glue is high, the corrosion of anti tear, soft abrasion-resistant, puncture, oil resistant and media-resistant, be widely used, when shortcoming is solidification, terminal isocyanate groups and moisture in air react and discharge carbonic acid gas, glass cement body is made to produce bubble even crackle, easily be clamminess in the comparatively slow and surface of curing speed, can not wet-heat resisting and ageing-resistant for a long time, adopt the urethane (semi-synthetic urethane) of natural matter synthesis then not resistance to mould corrode.
Poly-sulphur glass glue has quite high bonding strength to concrete, metal and other base material, and resistance to air loss is excellent, and the consumption allowed band of solidifying agent is wide, and solidification effect is good, and construction simple and convenient, life-time service temperature range is-30 ~ 110 DEG C.But a large amount of waste water, waste residue can be produced in the process of producing thiorubber, environment is worked the mischief.And glass cement uses easy mould growth in long-term hydrostatic water logging, hygrothermal environment, affects sealing effectiveness.
Silicone glass adhesive curing is non-foaming, can with non-porous material surface secure bond, there are good hydrolytic resistance, the erosion performance of resistance to mould, but it is poor with the adhesiveproperties of the components such as concrete, when glue-line is thick, sulfuration is difficult, easy generation oily dialysis thing, pollute concrete, stone material and other jewelry, and price is more expensive.
When glass cement is used for fuel tanker, boats and ships and need long-term immersion or long-term hygrothermal environment, easy mould growth, along with the procreation of mould is corroded, can make glass cement matrix be destroyed, affect even loss of seal effect.For ensureing long term seal effect, glass cement should possess mildew-resistant ability.More existing relevant reports both at home and abroad.Lin Yanqin etc. report " research of High-efficient Mildewproof Polysulfied Sealant ", thiazoles, organometallic complex, imidazoles 3 kinds of mould inhibitors have been selected to be applied to polysulfide sealant, prepare the poly-sulphur mildew resistant sealant that anti-mold effect is good, have studied the impact of mould inhibitor on sealing agent mechanical property and processing performance, find that the mechanical property of different mould inhibitor on sealing agent has different impacts, and very little on the impact of processing performance.
CN200510045295.5 has invented a kind of Single-component moldproof flame retarded organic silicon sealing agent for machinery, prepares a kind of mildew-proof flame retarded organic silicon machinery glass cement, be mainly used in mechanical seal field by the method for adding mould inhibitor in organic silicon sealant.At present about the research of glass cement mildew-resistant focuses mostly in fields such as aircraft, boats and ships, electronics, machineries, and need long-term immersion for hydro project, water delivery engineering, sewage treatment project etc., but or in hygrothermal environment, apply easy mould growth requires the high rarely seen report of mildew-resistant glass cement product to sealing effectiveness for a long time.If the glass cement applied in these fields does not have antifungal function, easy mould growth, and the growth of mould and spread glass cement inner molecular structure can be made to suffer erosion, it is rotten to produce degraded, affects even loss of seal effect.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of high strong water resistant mildew-resistant glass cement, this glass cement can meet the sealing and mould proof requirement that use under long-term water logging, damp and hot or other easy mould growth conditions, and has excellent mechanical property.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of high strong water resistant mildew-resistant glass cement, described glass cement is made up of following component with parts by weight: silane end capped polyurethane performed polymer 60-64 part, softening agent 7-9 part, talcum powder 18-20 part, diatomite in powder 15-25 part, lithium bentonite 4-8 part, bamboo charcoal particle powder 8-10 part ,-200 order cerium oxide powder 2-4 parts, oxidation inhibitor 1.2-1.4, uv-absorbing agent 0.8-1.2 part, thixotropic agent 0.2-0.4 part, benzimidazole carbamate 1-2 part, benzyl trimethyl ammonium chloride 1-2 part, adhesive accelerant 2.5-3.5 part, catalyzer 0.2-0.4 part, the preparation method of wherein said silane end capped polyurethane performed polymer is: the polytetrahydrofuran diol of molecular mass between 6500-7500 and the polyoxytrimethylene triol of molecular mass between 8500-10000 are mixed, the ratio of the two is 1: 2.5-3, at the temperature of 120 DEG C-130 DEG C, dry 1-1.5 hour under being less than the vacuum of 0.1MPa, then be cooled to 75 DEG C-80 DEG C and add the isocyanic ester accounting for said mixture mass percent 17-19% and the dibutyl tin laurate accounting for said mixture mass percent 0.1-0.3% again, reaction 3-4 hour, obtained polyurethane prepolymer, in above-mentioned obtained polyurethane prepolymer, add the terminated silane coupling agent accounting for above-mentioned polyurethane prepolymer mass percent 17-19%, at 85 DEG C-90 DEG C, react 2.5-3 hour, obtain Silante terminated polyurethane prepolymer.
This glass cement can adopt but be not limited to the preparation of following method:
1) Silante terminated polyurethane prepolymer is prepared as stated above.
2) the Silante terminated polyurethane prepolymer of above-mentioned preparation and dried talcum powder, diatomite in powder, lithium bentonite, bamboo charcoal particle powder ,-200 order cerium oxide, oxidation inhibitor, UV light absorber, softening agent, thixotropic agent, benzimidazole carbamate and benzyl trimethyl ammonium chloride are uniformly mixed mutually, be heated to 90 DEG C-100 DEG C, 3.5-4 hour is stirred under the vacuum being less than 0.1MPa, then adhesive accelerant and catalyzer is added, be uniformly mixed 1.5-2 hour again, obtained glass cement.
Wherein, described isocyanic ester is any one in two-(4-isocyanic ester butylcyclohexyl) methane, '-diphenylmethane diisocyanate, tolylene diisocyanate or 1,6-hexamethylene diisocyanate.
Wherein, described terminated silane coupling agent is that one or more in 3-mercaptopropyl trimethoxysilane, N-cyclohexyl-3-aminopropyltriethoxy dimethoxysilane, N-cyclohexyl-3-aminopropyl trimethoxysilane, N-butyl-3-aminopropyl trimethoxysilane, 3-isocyanic ester propyl trimethoxy silicane, N-ethyl-3-methoxyl group silicon-2-methyl-propyl amine are used in combination with any ratio.
Wherein, described softening agent is: any one in dibutyl phthalate (DBP), dioctyl phthalate (DOP) (DOP), Di Iso Decyl Phthalate (DIDP) or chlorinated paraffinic oil.
Wherein, described oxidation inhibitor is any one in Irganox 1010, Irganox 1076, Irganox 1098 or Irgafos168; Described uv-absorbing agent is that any one or more in Tinuvin 531, Tinuvin 327, Tinuvin622 or Tinuvin770 is used in combination with any ratio.
Wherein, described thixotropic agent is any one in hydrogenated castor oil or aerosil;
Wherein, described adhesive accelerant is 3-aminopropyl trimethoxysilane, the N-(any one in β-aminoethyl-3-aminopropyl trimethoxysilane or 3-mercaptopropyl trimethoxysilane;
Wherein, described catalyzer is that one or more in dibutyl tin laurate, dibutyltin diacetate, stannous octoate or amino dodecane are used in combination with any ratio.
The present invention has following beneficial effect:
1) the present invention is by controlling raw materials and the preparation technology of Silante terminated polyurethane prepolymer, and chooses suitable filler, and the content of conservative control filler is to improve the mechanical property of existing seal gum and resistance to water logging performance.Wherein in filler, mainly through talcum powder 18-20 part, lithium bentonite 4-8 part ,-200 order cerium oxide powder 2-4 parts improve mechanical property; Wherein in filler, diatomite in powder 15-25 part and bamboo charcoal particle powder 8-10 part are mainly used in improving resistance to water logging performance.
2) in the raw materials of above-mentioned improvement polyurethane prepolymer and preparation technology to obtain on the basis of excellent Silante terminated polyurethane prepolymer, have selected benzimidazole carbamate and benzyl trimethyl ammonium chloride is composite as mould inhibitor, these two kinds of mould inhibitor high-efficiency broad spectrums, low irritant, high security, low-bleed rate, the polyurethane prepolymer consistency Silante terminated with body significantly improve, do not affect the finished product stores and uses, therefore, anti-mold effect is excellent.
3) except the optimization design of above-mentioned main component, to all the other components of glass cement, carried out corresponding coordination, made it reach collaborative technique effect, thus prepare the glass cement with excellent snappiness, cementability, water tolerance.
4) this glass cement tensile strength can reach 5.5-6.0MPa, and elongation at break reaches 800-950%, mildew-resistant grade≤1, and high-low temperature resistant is moist and water logging, can long service in fields such as hydro project, water delivery engineering, sewage treatment projects.
5) raw material required for the present invention is easy to get, and production cost is lower; And do not use any poisoned catalyst and easy volatile solvent, without " three wastes " discharge, environmental friendliness.
Embodiment
Embodiment one
A kind of high strong water resistant mildew-resistant glass cement, described glass cement is made up of following component with parts by weight: silane end capped polyurethane performed polymer 60 parts, dibutyl phthalate 9 parts, talcum powder 18 parts, diatomite in powder 25 parts, lithium bentonite 4 parts, 10 parts, bamboo charcoal particle powder ,-200 order cerium oxide powders 2 parts, Irganox 1,010 1.2, Tinuvin 327 1.2 parts, aerosil 0.2 part, benzimidazole carbamate 2 parts, benzyl trimethyl ammonium chloride 1 part, 3-aminopropyl trimethoxysilane 3.5 parts, dibutyl tin laurate 0.2 part, the preparation method of wherein said silane end capped polyurethane performed polymer is: the polytetrahydrofuran diol of molecular mass between 6500-7500 and the polyoxytrimethylene triol of molecular mass between 8500-10000 are mixed, the ratio of the two is 1: 2.5, at the temperature of 130 DEG C, to be less than under the vacuum of 0.1MPa dry 1 hour, then be cooled to 80 DEG C to add again and account for 1 of said mixture mass percent 17%, 6-hexamethylene diisocyanate and the dibutyl tin laurate accounting for said mixture mass percent 0.3%, react 3 hours, obtained polyurethane prepolymer, in above-mentioned obtained polyurethane prepolymer, add the 3-mercaptopropyl trimethoxysilane accounting for above-mentioned polyurethane prepolymer mass percent 19%, react 3 hours at 85 DEG C, obtain Silante terminated polyurethane prepolymer.
Embodiment two
A kind of high strong water resistant mildew-resistant glass cement, described glass cement is made up of following component with parts by weight: end base polyurethane prepolymer for use as 64 parts, dibutyl phthalate 9 parts, talcum powder 20 parts, diatomite in powder 15 parts, lithium bentonite 8 parts, 8 parts, bamboo charcoal particle powder ,-200 order cerium oxide powders 4 parts, Irganox 1,010 1.4, Tinuvin 327 0.8 parts, aerosil 0.4 part, benzimidazole carbamate 1 part, benzyl trimethyl ammonium chloride 2 parts, 3-aminopropyl trimethoxysilane 2.5 parts, dibutyl tin laurate 0.4 part, the preparation method of wherein said silane end capped polyurethane performed polymer is: the polytetrahydrofuran diol of molecular mass between 6500-7500 and the polyoxytrimethylene triol of molecular mass between 8500-10000 are mixed, the ratio of the two is 1: 3, at the temperature of 120 DEG C, to be less than under the vacuum of 0.1MPa dry 1.5 hours, then be cooled to 75 DEG C to add again and account for 1 of said mixture mass percent 19%, 6-hexamethylene diisocyanate and the dibutyl tin laurate accounting for said mixture mass percent 0.1%, react 4 hours, obtained polyurethane prepolymer, in above-mentioned obtained polyurethane prepolymer, add the 3-mercaptopropyl trimethoxysilane accounting for above-mentioned polyurethane prepolymer mass percent 17%, react 2.5 hours at 90 DEG C, obtain Silante terminated polyurethane prepolymer.
Embodiment three
A kind of high strong water resistant mildew-resistant glass cement, described glass cement is made up of following component with parts by weight: silane end capped polyurethane performed polymer 62 parts, dioctyl phthalate (DOP) 7 parts, talcum powder 19 parts, diatomite in powder 20 parts, lithium bentonite 6 parts, 9 parts, bamboo charcoal particle powder ,-200 order cerium oxide powders 3 parts, Irganox 1,076 1.2, Tinuvin 327 1.2 parts, hydrogenated castor oil 0.2 part, benzimidazole carbamate 2 parts, benzyl trimethyl ammonium chloride 1 part, N-(β-aminoethyl-3-aminopropyl trimethoxysilane 3.5 parts, dibutyltin diacetate 0.2 part; The preparation method of wherein said silane end capped polyurethane performed polymer is: the polytetrahydrofuran diol of molecular mass between 6500-7500 and the polyoxytrimethylene triol of molecular mass between 8500-10000 are mixed, the ratio of the two is 1: 2.5, at the temperature of 130 DEG C, under the vacuum that is less than 0.1MPa dry 1 hour, then be cooled to 80 DEG C and add the '-diphenylmethane diisocyanate accounting for said mixture mass percent 17% and the dibutyl tin laurate accounting for said mixture mass percent 0.3% again, react 3 hours, obtained polyurethane prepolymer; In above-mentioned obtained polyurethane prepolymer, add the N-cyclohexyl-3-aminopropyltriethoxy dimethoxysilane accounting for above-mentioned polyurethane prepolymer mass percent 19%, react 3 hours at 85 DEG C, obtain Silante terminated polyurethane prepolymer.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (8)

1. a high strong water resistant mildew-resistant glass cement, it is characterized in that, described glass cement is made up of following component with parts by weight: silane end capped polyurethane performed polymer 60-64 part, softening agent 7-9 part, talcum powder 18-20 part, diatomite in powder 15-25 part, lithium bentonite 4-8 part, bamboo charcoal particle powder 8-10 part,-200 order cerium oxide powder 2-4 parts, oxidation inhibitor 1.2-1.4, uv-absorbing agent 0.8-1.2 part, thixotropic agent 0.2-0.4 part, benzimidazole carbamate 1-2 part, benzyl trimethyl ammonium chloride 1-2 part, adhesive accelerant 2.5-3.5 part, catalyzer 0.2-0.4 part, the preparation method of wherein said silane end capped polyurethane performed polymer is: the polytetrahydrofuran diol of molecular mass between 6500-7500 and the polyoxytrimethylene triol of molecular mass between 8500-10000 are mixed, the ratio of the two is 1: 2.5-3, at the temperature of 120 DEG C-130 DEG C, dry 1-1.5 hour under being less than the vacuum of 0.1MPa, then be cooled to 75 DEG C-80 DEG C and add the isocyanic ester accounting for said mixture mass percent 17-19% and the dibutyl tin laurate accounting for said mixture mass percent 0.1-0.3% again, reaction 3-4 hour, obtained polyurethane prepolymer, in above-mentioned obtained polyurethane prepolymer, add the terminated silane coupling agent accounting for above-mentioned polyurethane prepolymer mass percent 17-19%, at 85 DEG C-90 DEG C, react 2.5-3 hour, obtain Silante terminated polyurethane prepolymer.
2. a kind of high strong water resistant mildew-resistant glass cement as claimed in claim 1, it is characterized in that, described isocyanic ester is any one in two-(4-isocyanic ester butylcyclohexyl) methane, '-diphenylmethane diisocyanate, tolylene diisocyanate or 1,6-hexamethylene diisocyanate.
3. a kind of high strong water resistant mildew-resistant glass cement as described in claim 1-2, it is characterized in that, described terminated silane coupling agent is that one or more in 3-mercaptopropyl trimethoxysilane, N-cyclohexyl-3-aminopropyltriethoxy dimethoxysilane, N-cyclohexyl-3-aminopropyl trimethoxysilane, N-butyl-3-aminopropyl trimethoxysilane, 3-isocyanic ester propyl trimethoxy silicane, N-ethyl-3-methoxyl group silicon-2-methyl-propyl amine are used in combination with any ratio.
4. a kind of high strong water resistant mildew-resistant glass cement as described in claim 1-3, it is characterized in that, described softening agent is: any one in dibutyl phthalate (DBP), dioctyl phthalate (DOP) (DOP), Di Iso Decyl Phthalate (DIDP) or chlorinated paraffinic oil.
5. a kind of high strong water resistant mildew-resistant glass cement as described in claim 1-4, it is characterized in that, described oxidation inhibitor is any one in Irganox1010, Irganox1076, Irganox1098 or Irgafos168; Described uv-absorbing agent is that any one or more in Tinuvin531, Tinuvin327, Tinuvin622 or Tinuvin770 is used in combination with any ratio.
6. a kind of high strong water resistant mildew-resistant glass cement as described in claim 1-5, is characterized in that, described thixotropic agent is any one in hydrogenated castor oil or aerosil.
7. a kind of high strong water resistant mildew-resistant glass cement as described in claim 1-6, it is characterized in that, described adhesive accelerant is 3-aminopropyl trimethoxysilane, the N-(any one in β-aminoethyl-3-aminopropyl trimethoxysilane or 3-mercaptopropyl trimethoxysilane.
8. a kind of high strong water resistant mildew-resistant glass cement as described in claim 1-7, is characterized in that, described catalyzer is that one or more in dibutyl tin laurate, dibutyltin diacetate, stannous octoate or amino dodecane are used in combination with any ratio.
CN201510287510.6A 2015-05-29 2015-05-29 High-strength water-resistant and mildew-proof glass cement Pending CN104910850A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106589286A (en) * 2016-11-21 2017-04-26 万华化学集团股份有限公司 Silane modified polyurethane resin and preparation method thereof
CN106698675A (en) * 2016-12-08 2017-05-24 苏州赛斯德工程设备有限公司 High-performance water purification material for removing heavy metal ions in water
CN107556958A (en) * 2017-09-29 2018-01-09 东莞市科惠工业材料有限公司 A kind of mould proof beauty glue
CN107603555A (en) * 2017-10-17 2018-01-19 高俊 A kind of preparation method of mould proof clean type glass cement
CN107987772A (en) * 2017-11-30 2018-05-04 安徽坤大化学锚固有限公司 A kind of high tear type cloud stone glue and its processing technology
CN108084942A (en) * 2017-12-27 2018-05-29 天长市墨缘玻璃建材有限公司 A kind of water-fast weather-resistant pu glass cement
CN108250449A (en) * 2017-12-19 2018-07-06 广东省石油与精细化工研究院 A kind of line style end-silicane-group block polyether and its preparation method and application
CN108276946A (en) * 2017-12-27 2018-07-13 天长市墨缘玻璃建材有限公司 A kind of water resistance polyurethane glass glue
CN108300398A (en) * 2017-12-27 2018-07-20 天长市墨缘玻璃建材有限公司 A kind of water-fast weather-resistant pu glass cement of antibacterial

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CN101402845A (en) * 2008-11-11 2009-04-08 北京市化学工业研究院 Process for producing flame-proof fluid sealant for construction
CN101434825A (en) * 2008-12-12 2009-05-20 河南永丽化工有限公司 Bicomponent terminal mercapto polyurethane mildewproof sealant and preparation thereof
CN104194318A (en) * 2014-09-22 2014-12-10 东莞市雄林新材料科技股份有限公司 TPU (thermoplastic polyurethane) film for shoe material printing and preparation method of TPU film

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CN101402845A (en) * 2008-11-11 2009-04-08 北京市化学工业研究院 Process for producing flame-proof fluid sealant for construction
CN101434825A (en) * 2008-12-12 2009-05-20 河南永丽化工有限公司 Bicomponent terminal mercapto polyurethane mildewproof sealant and preparation thereof
CN104194318A (en) * 2014-09-22 2014-12-10 东莞市雄林新材料科技股份有限公司 TPU (thermoplastic polyurethane) film for shoe material printing and preparation method of TPU film

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106589286A (en) * 2016-11-21 2017-04-26 万华化学集团股份有限公司 Silane modified polyurethane resin and preparation method thereof
CN106698675A (en) * 2016-12-08 2017-05-24 苏州赛斯德工程设备有限公司 High-performance water purification material for removing heavy metal ions in water
CN107556958A (en) * 2017-09-29 2018-01-09 东莞市科惠工业材料有限公司 A kind of mould proof beauty glue
CN107603555A (en) * 2017-10-17 2018-01-19 高俊 A kind of preparation method of mould proof clean type glass cement
CN107987772A (en) * 2017-11-30 2018-05-04 安徽坤大化学锚固有限公司 A kind of high tear type cloud stone glue and its processing technology
CN108250449A (en) * 2017-12-19 2018-07-06 广东省石油与精细化工研究院 A kind of line style end-silicane-group block polyether and its preparation method and application
CN108084942A (en) * 2017-12-27 2018-05-29 天长市墨缘玻璃建材有限公司 A kind of water-fast weather-resistant pu glass cement
CN108276946A (en) * 2017-12-27 2018-07-13 天长市墨缘玻璃建材有限公司 A kind of water resistance polyurethane glass glue
CN108300398A (en) * 2017-12-27 2018-07-20 天长市墨缘玻璃建材有限公司 A kind of water-fast weather-resistant pu glass cement of antibacterial

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Application publication date: 20150916