CN105174750A - Impregnating agent for winding reinforcement medium-alkali glass fiber direct yarns - Google Patents
Impregnating agent for winding reinforcement medium-alkali glass fiber direct yarns Download PDFInfo
- Publication number
- CN105174750A CN105174750A CN201510556110.0A CN201510556110A CN105174750A CN 105174750 A CN105174750 A CN 105174750A CN 201510556110 A CN201510556110 A CN 201510556110A CN 105174750 A CN105174750 A CN 105174750A
- Authority
- CN
- China
- Prior art keywords
- treating compound
- agent
- emulsion
- lubricant
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
An impregnating agent for winding reinforcement medium-alkali glass fiber direct yarns comprise a coupling agent, a lubricant, a film forming agent, a surfactant, a pH adjusting agent and deionized water, and the impregnating agent comprises 5-14 mass% of a impregnating agent solid, and the balance of water; the coupling agent adopts a silane coupling agent; the lubricant adopts a water-soluble PEG lubricant; the film forming agent is an organo-silicone modified epoxy emulsion, aqueous polyester emulsion A and aqueous polyester emulsion B blend, the molecular weight of polyester in the above aqueous polyester emulsion A is 800-3000, and the molecular weight of polyester in the above aqueous polyester emulsion B is 4000-10000; the surfactant is a cationic surfactant; the pH adjusting agent is an acid; and the pH value of the impregnating agent is 2-10. Direct yarns produced by adopting the impregnating agent have good compatibility with target resin, have good permeability, and make products have good mechanical performances and meet standard requirements.
Description
(1) technical field
The present invention relates to a kind of glass-fiber reinforced thermo-setting resin technology, particularly a kind for the treatment of compound strengthening the direct yarn of winding-type medium-alkali glass fibre.
(2) background technology
Fiber winding forming is a kind of method of quickness and high efficiency.Its technique is wound on core by the continuous fibre of dipped resin adhesive liquid (or strap, prepegged strands) according to certain rule, then through solidification, the demoulding, obtains composite products that is firm, lightweight.Fiber winding forming goods possess the features such as excellent corrosion resistance nature, high-durability, high-strength light and installation and maintenance convenience, fiber winding forming is widely used in the fields such as petroleum transport, sewage disposal, sea water desaltination, aerospace, power transmission, gas-liquid storage, Sport & Casual at present, and typical products and its has oil pressure piping, CNG gas cylinder, pressure vessel for reverse osmosis, reactor, insulation thimble, fiberglass-reinforced glass storage tank, flue gas desulfurization (FGD) unit, golf club etc.
Filamentary material for fiber winding forming has selecting property of plurality of optional, and as alkali free glass fibre, medium-alkali glass fibre, carbon fiber, basalt fibre, HDPE etc., the selection of these materials is design requirementss according to end article, Application Areas is determined.Domestic and international Filament-wound Machine glass fiber reinforced plastics product at present, generally all adopt alkali free glass fibre, especially pipeline and basin are applied to industry-by-industry increasingly extensively, and the feature that medium-alkali glass fibre is lower with its acid-proof, price, raw material is easy to get, day by day draw attention.Because middle alkali glass is low compared with non-alkali glass intensity and crisp, the treating compound that must be coated with outward by fiberglass surfacing makes up the self shortcoming of its glass, improve intensity, most importantly improve the mechanical property of fiberglass products, meet the design requirements of fiberglass products.General property requires following (adopt unsaturated polyester resin, content of glass fiber is 75%, for 2400tex):
● performance index:
| Test event | Tensile strength | Shearing resistance |
| Reference standard | ASTM D2343 | ASTM D2344 |
| Tensile strength | ≥2000MPa | ≥60MPa |
Adopting under the prerequisite that C glass ingredient is constant for this reason, need by developing a kind of novel treating compound: can and target resin possess excellent consistency, the effect of raising interface cohesion, to meet the index request of mechanical property.
(3) summary of the invention
Technical problem to be solved by this invention is to provide a kind for the treatment of compound strengthening the direct yarn of winding-type medium-alkali glass fibre, adopt the direct yarn that this treating compound is produced, not only good with target resin compatible, soak into, and the mechanical property of goods can be made high, meet the requirement of standard.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
The invention discloses a kind for the treatment of compound strengthening the direct yarn of winding-type medium-alkali glass fibre, described treating compound comprises coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value regulator and deionized water, the solid masses (namely drying the quality of rear remainder) of described treating compound accounts for 5 ~ 14% for the treatment of compound total mass, and surplus is water (water comprising raw material its own band adds the deionized water that preparation treating compound adds); Described coupling agent adopts silane coupling agent; Described lubricant adopts water miscible PEG series lubricant agent; Described membrane-forming agent is the blend of organic siloxane modified epoxy emulsion, waterborne polyester latex A and waterborne polyester emulsion B, molecular weight of polyesters in described waterborne polyester latex A is 800 ~ 3000, and the molecular weight of polyesters in described waterborne polyester emulsion B is 4000 ~ 10000; Described tensio-active agent is cats product; Described pH adjusting agent is acid; The percentage that in described treating compound, each component concentration accounts for treating compound solid masses with its consumption is expressed as follows, if component adds with dispersion, then its consumption is in its solid masses:
Further, the preferred described treating compound of the present invention is made up of coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value regulator and deionized water.
Further, in the preferred described treating compound of the present invention, each component concentration is as follows:
Further, in the preferred described treating compound of the present invention, each component concentration is as follows:
Again further, in the preferred described treating compound of the present invention, each component concentration is as follows:
The pH value for the treatment of compound of the present invention is 2 ~ 10, and preferable ph is 3 ~ 7.
Coupling agent of the present invention generally adopts the silane based coupling agents of band epoxy group(ing), acryloxy, vinyl or amino, and the available product grade of the silane coupling agent that the present invention is suitable for has A-172, A-174, A-1100, A-187 etc.The use of coupling agent; fiber can be protected to avoid in drawing process impaired; and " bridge joint " effect played between glass fibre and matrix resin; therefore be the key affecting glass fiber strength and glass fiber reinforced plastics product intensity; suitable coupling agent is selected, and the product produced can be made to have better mechanical property.The present invention preferably adopts the silane based coupling agents of band acryloxy, most preferably uses methacryloxypropyl trimethoxy silane coupling agent.In the present invention, the content of silane coupling agent is 4 ~ 18%, preferably 6 ~ 16%, more preferably 7 ~ 14%, further preferably 9 ~ 12%.
The lubricant that the present invention uses can adopt water miscible organic compound, and particularly PEG series lubricant agent, as PEG400, PEG600, PEG1000, PEG3000 etc.The use of lubricant is mainly and meets the lubricant effect of glass fibre in wire drawing, aftertreatment, use procedure, but too much lubricant can affect the convergency of glass fiber yarn, and the mechanical property of final glass fiber reinforced plastics product can be affected, therefore the content of lubricant described in the present invention is 4 ~ 18%, preferably 5 ~ 15%, more preferably 6 ~ 12%, further preferably 7 ~ 9%.
The tensio-active agent that the present invention uses is cats product, adopts the one in Fixanol, quaternary ammonium salt, amine salt, preferred quaternary cationic surfactant.The content of preferred cationic tensio-active agent of the present invention is 0.1 ~ 10%, preferably 1 ~ 8%, more preferably 2 ~ 6%, further preferably 3 ~ 5%.
Membrane-forming agent plays as the main component for the treatment of compound the effect protecting fiber, and meet the continuous seepage of fiber, and play conclusive impact to the physical strength of glass fibre end article, therefore, the selection of membrane-forming agent is emphasis of the present invention.The membrane-forming agent that the present invention uses is the combination of organic siloxane modified epoxy emulsion, polyester emulsion A and polyester emulsion B.The present invention adopts the collocation of dissimilar emulsion to use, and except taking into account the convergency of glass fiber yarn, yarn matter, also will meet the feasibility of fiber production, avoid the situations such as lousiness to produce, especially meet the production of the direct yarn of alkali in more than 1200tex large size number.Also to consider the consistency with resin simultaneously, thus improve the physical strength of glass fiber reinforced plastics product.The content summation of membrane-forming agent of the present invention is 60 ~ 80%, preferably 62 ~ 76%, and be more preferably 65 ~ 73%, be further preferably 68 ~ 72%.
The present invention use organic siloxane modified epoxy emulsion be by organo-siloxane monomer modified can be water-soluble modified epoxy resin emulsion, the molecular weight of organic siloxane modified epoxy resin is 800 ~ 2500, be preferably the scope of 1200 ~ 2000, particle diameter of dispersing phase 0.2 ~ 2.0 μm.The present invention is the dual modified aqueous epoxy emulsion of KH570 and KH550 particularly preferably, its preparation method can reference [Guo Wenlu, Lu Hanqing, Zhou Hongchun. the research (J) of the dual modified aqueous epoxy emulsion of organo-siloxane. coatings industry, 2011 years 09 phases].The content of described organic siloxane modified epoxy emulsion is 15 ~ 40%, preferably 18 ~ 35%, more preferably 22 ~ 32%, further preferably 25 ~ 30%.
The waterborne polyester latex A that the present invention uses, wherein molecular weight of polyesters is 800 ~ 3000, is preferably the scope of 1500 ~ 2500, particle diameter of dispersing phase 0.2 ~ 2.0 μm.In the present invention, waterborne polyester latex A can be prepared voluntarily according to existing document or use commercial goods.The content of described waterborne polyester latex A is 15 ~ 40%, preferably 10 ~ 38%, more preferably 20 ~ 35%, further preferably 25 ~ 32%.
The waterborne polyester emulsion B that the present invention uses, wherein molecular weight of polyesters is 4000 ~ 10000, is preferably the scope of 5000 ~ 8000, particle diameter of dispersing phase 0.2 ~ 2.0 μm.In the present invention, waterborne polyester emulsion B can prepare voluntarily according to existing document or use commercial goods.The content of described waterborne polyester emulsion B is 10 ~ 25%, preferably 12 ~ 22%, more preferably 15 ~ 21%, further preferably 16 ~ 20%.
PH adjusting agent of the present invention adopts acid, and organic acid or mineral acid, as used citric acid, acetic acid, formic acid, acetic acid etc.The effect of pH adjusting agent is mainly used for ancillary coupling agent dispersion and regulate the pH value preparing treating compound, and the pH value for the treatment of compound of the present invention is 2 ~ 10, and preferable ph is 3 ~ 7.
A kind of compound method strengthening the treating compound of the direct yarn of winding-type medium-alkali glass fibre of the present invention comprises the following steps: the deionized water adding 40% ~ 50% of total amount in a clean container, and then the pH adjusting agent added in treating compound composition, abundant stirring is after 3 ~ 5 minutes, slowly add the silane coupling agent in treating compound composition again, Keep agitation 40 ~ 50 minutes; Lubricant in treating compound composition, tensio-active agent add container after abundant agitation and dilution at 5 times in the warm deionized water (40 ~ 50 DEG C) of its amount; In treating compound composition, membrane-forming agent adds container after adopting the water of 2 times of film forming dosage to dilute, if treating compound pH value can not reach optimum range, adds appropriate pH adjusting agent and carries out adjusting and stirring, until pH value reaches optimum range.
Combustible content (namely treating compound coating amount on the glass fibers accounts for the ratio of the glass fiber quality) general control of glass fibre of the present invention is 0.4 ~ 1.2%, concrete value needs to determine according to the performance of raw material itself, the performance index reached from product needed and experimental results, the product that combustible content is produced 0.6 ~ 0.9%, physical strength can meet the demands.
Compared with prior art, treating compound of the present invention can, good penetrability good with resin compatible, and the mechanical property of goods can be made high, thus meets market and application demand.
(4) embodiment
By the following examples the present invention is specifically described, but content of the present invention is not by any restriction of following examples.
The each component for the treatment of compound that the embodiment of the present invention uses is as follows:
Described coupling agent uses methacryloxypropyl trimethoxy silane coupling agent, and product grade is A-174;
Described lubricant uses PEG1000;
Described membrane-forming agent modified epoxy resin emulsion is self-control, adopt organo-siloxane KH570 and KH550 (KH570 and KH550 content accounts for the massfraction of epoxy resin than being 5:1) dual modified aqueous epoxy emulsion (reference: Guo Wenlu, Lu's sweat is clear, Zhou Hongchun. the research (J) of the dual modified aqueous epoxy emulsion of organo-siloxane. coatings industry, 09 phase in 2011);
Described membrane-forming agent polyester emulsion A, product grade is DSMNeoxil958 (manufacturer: Dutch DSM N. V., relative molecular mass 1800);
Described membrane-forming agent polyester emulsion B, product grade is DSMNeoxil954 (manufacturer: Dutch DSM N. V., relative molecular mass 6000);
Described cats product adopts organic quaternary ammonium salt 1831;
Described pH value regulator adopts acetic acid.
Following table is concrete formulation examples and the concrete test result of the direct yarn of 2400Tex produced according to certain glass fibre production technique.In the embodiment of the present invention, the content of water accounts for 92% for the treatment of compound total mass, and numerical value is wherein each component accounts for treating compound solid masses per-cent in its solid content.
From above formula test case, we can therefrom find out, by the design to component and component concentration, we can obtain the treating compound meeted the requirements, wherein especially better with example 3,4 effect.Below be only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
The embodiment of the present invention is according to the technical characterstic of winding shaping process and the direct yarn of medium-alkali glass fibre, by the selection for the treatment of compound raw material, the optimization of formula, adopts suitable glass fibre production technique, produces the direct yarn product of the medium-alkali glass fibre meeting this domain requirement.
Claims (10)
1. one kind strengthens the treating compound of the direct yarn of winding-type medium-alkali glass fibre, described treating compound comprises coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value regulator and deionized water, the solid masses of described treating compound accounts for 5 ~ 14% for the treatment of compound total mass, and surplus is water; Described coupling agent adopts silane coupling agent; Described lubricant adopts water miscible PEG series lubricant agent; Described membrane-forming agent is the blend of organic siloxane modified epoxy emulsion, waterborne polyester latex A and waterborne polyester emulsion B, molecular weight of polyesters in described waterborne polyester latex A is 800 ~ 3000, and the molecular weight of polyesters in described waterborne polyester emulsion B is 4000 ~ 10000; Described tensio-active agent is cats product; Described pH adjusting agent is acid; The pH value of described treating compound is 2 ~ 10; The percentage that in described treating compound, each component concentration accounts for treating compound solid masses with its consumption is expressed as follows, if component adds with dispersion, then its consumption is in its solid masses:
2. treating compound as claimed in claim 1, is characterized in that: in described treating compound, each component concentration is as follows:
3. treating compound as claimed in claim 2, is characterized in that: in described treating compound, each component concentration is as follows:
4. treating compound as claimed in claim 3, is characterized in that: in described treating compound, each component concentration is as follows:
5. the treating compound as described in one of Claims 1 to 4, is characterized in that: described treating compound is made up of coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value regulator and deionized water.
6. the treating compound as described in one of Claims 1 to 5, is characterized in that: described organic siloxane modified epoxy emulsion is the dual modified aqueous epoxy emulsion of KH570 and KH550.
7. treating compound as claimed in claim 6, it is characterized in that: in described organic siloxane modified epoxy emulsion, the molecular weight of organic siloxane modified epoxy resin is 800 ~ 2500.
8. the treating compound as described in one of claim 1 ~ 7, is characterized in that: in described waterborne polyester latex A, and molecular weight of polyesters is 1500 ~ 2500; In described waterborne polyester emulsion B, molecular weight of polyesters is 5000 ~ 8000.
9. the treating compound as described in one of claim 1 ~ 8, is characterized in that: described coupling agent adopts the silane based coupling agents of band epoxy group(ing), acryloxy, vinyl or amino.
10. the treating compound as described in one of claim 1 ~ 9, is characterized in that: described cats product adopts quaternary cationic surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510556110.0A CN105174750B (en) | 2015-09-02 | 2015-09-02 | A kind of size for strengthening the direct yarn of winding-type medium-alkali glass fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510556110.0A CN105174750B (en) | 2015-09-02 | 2015-09-02 | A kind of size for strengthening the direct yarn of winding-type medium-alkali glass fibre |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105174750A true CN105174750A (en) | 2015-12-23 |
| CN105174750B CN105174750B (en) | 2018-03-02 |
Family
ID=54897285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510556110.0A Active CN105174750B (en) | 2015-09-02 | 2015-09-02 | A kind of size for strengthening the direct yarn of winding-type medium-alkali glass fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105174750B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186730A (en) * | 2016-07-15 | 2016-12-07 | 巨石集团有限公司 | The wetting agent of FFU synthesis wooden sleeper alkali-free glass fibre yarn |
| CN106242318A (en) * | 2016-07-26 | 2016-12-21 | 巨石集团有限公司 | A kind of wetting agent and its production and use |
| CN106242317A (en) * | 2016-07-15 | 2016-12-21 | 巨石集团有限公司 | Strengthen the wetting agent of the polyurethane direct yarn of pultrusion alkali-free glass fibre |
| CN106630683A (en) * | 2016-12-07 | 2017-05-10 | 巨石集团有限公司 | Impregnating compound for alkali-free glass fiber rough yarn for strengthened PP or PBT |
| CN110156346A (en) * | 2019-05-27 | 2019-08-23 | 泰安顺茂新材料技术有限公司 | A kind of Wrapping formed fiberglass surface modifiers and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294200A (en) * | 2001-03-29 | 2002-10-09 | Nitto Boseki Co Ltd | Binder for glass fibers |
| CN102807331A (en) * | 2011-06-01 | 2012-12-05 | 江西大华玻纤集团有限公司 | Alkali-containing glass fiber direct roving sizing agent for spinning |
| CN102976633A (en) * | 2012-11-29 | 2013-03-20 | 山东玻纤复合材料有限公司 | Medium-alkali glass fiber direct roving sizing agent and preparation method thereof |
| CN103435790A (en) * | 2013-07-22 | 2013-12-11 | 南通天和树脂有限公司 | Polyester emulsion film former for medium-alkali direct twistless roving impregnating compound |
| CN103889916A (en) * | 2011-10-20 | 2014-06-25 | 3B玻璃纤维公司 | Sizing composition for glass fibres |
-
2015
- 2015-09-02 CN CN201510556110.0A patent/CN105174750B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294200A (en) * | 2001-03-29 | 2002-10-09 | Nitto Boseki Co Ltd | Binder for glass fibers |
| CN102807331A (en) * | 2011-06-01 | 2012-12-05 | 江西大华玻纤集团有限公司 | Alkali-containing glass fiber direct roving sizing agent for spinning |
| CN103889916A (en) * | 2011-10-20 | 2014-06-25 | 3B玻璃纤维公司 | Sizing composition for glass fibres |
| CN102976633A (en) * | 2012-11-29 | 2013-03-20 | 山东玻纤复合材料有限公司 | Medium-alkali glass fiber direct roving sizing agent and preparation method thereof |
| CN103435790A (en) * | 2013-07-22 | 2013-12-11 | 南通天和树脂有限公司 | Polyester emulsion film former for medium-alkali direct twistless roving impregnating compound |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186730A (en) * | 2016-07-15 | 2016-12-07 | 巨石集团有限公司 | The wetting agent of FFU synthesis wooden sleeper alkali-free glass fibre yarn |
| CN106242317A (en) * | 2016-07-15 | 2016-12-21 | 巨石集团有限公司 | Strengthen the wetting agent of the polyurethane direct yarn of pultrusion alkali-free glass fibre |
| CN106242317B (en) * | 2016-07-15 | 2019-04-19 | 巨石集团有限公司 | Enhance the size of the direct yarn of polyurethane pultrusion alkali-free glass fibre |
| CN106242318A (en) * | 2016-07-26 | 2016-12-21 | 巨石集团有限公司 | A kind of wetting agent and its production and use |
| CN106242318B (en) * | 2016-07-26 | 2019-04-19 | 巨石集团有限公司 | A kind of size and its preparation method and application |
| CN106630683A (en) * | 2016-12-07 | 2017-05-10 | 巨石集团有限公司 | Impregnating compound for alkali-free glass fiber rough yarn for strengthened PP or PBT |
| CN110156346A (en) * | 2019-05-27 | 2019-08-23 | 泰安顺茂新材料技术有限公司 | A kind of Wrapping formed fiberglass surface modifiers and preparation method thereof |
| CN110156346B (en) * | 2019-05-27 | 2022-04-12 | 泰安顺茂新材料技术有限公司 | Winding forming glass fiber surface modifier and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105174750B (en) | 2018-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105174750A (en) | Impregnating agent for winding reinforcement medium-alkali glass fiber direct yarns | |
| CN103771732B (en) | The treating compound of the direct yarn of a kind of epoxy pressure piping alkali free glass fibre | |
| CN103880300B (en) | A kind of size of thermoplastic glass's direct yarn of steel conduit alkali-free glass fibre | |
| CN102219399B (en) | Impregnating compound special for single-filament plastic coated yarn and preparation method thereof | |
| CN101100355B (en) | Soaking agent capable of increasing glass fiber acid resistance | |
| CN100500722C (en) | Phenol formaldehyde-rubber copolymerized emulsion and its preparation method | |
| CN110818284A (en) | Glass fiber strand twistless roving impregnating compound, preparation method, product and application | |
| CN1972881B (en) | Sizing compositions for glass fibers and sized fiber glass products | |
| CN101391866A (en) | High-strength alkali-free glass fibre direct roving sizing agent for optical cable strengthening core | |
| CN103787592A (en) | Direct twistless rough yarn impregnating compound for reinforcing epoxy resin | |
| CN107868616A (en) | One kind spraying rapid hardening rubber asphalt waterproof coating and preparation method thereof | |
| CN105401422A (en) | Impregnating compound and application thereof in production of non-alkali bulked glass fiber yarn | |
| CN101100356A (en) | Direct untwisted roving soaking agent | |
| CN104405963A (en) | Plastic pipe and preparation method thereof | |
| CN105859158A (en) | Glass fiber infiltration agent with low migration rate | |
| CN108752680A (en) | A kind of high resiliency HDPE resin and preparation method thereof | |
| CN105174751B (en) | A kind of size of the chopped folded yarn of epoxy pipeline | |
| CN107804979A (en) | One kind enhancing rubber basalt fibre size and preparation method of being chopped | |
| CN106186730B (en) | The size of FFU synthesis wooden sleeper alkali-free glass fibre yarn | |
| CN101746963B (en) | Impregnating compound resisting ultrahigh voltage for direct roving of alkali-free glass fibers for insulators | |
| CN105384417B (en) | Coating material composition, ductile iron pipe and preparation method thereof | |
| CN104556740A (en) | Formula of impregnating compound for glass fiber twisted yarn for textile use | |
| CN107434362A (en) | One kind enhancing phenolic resin glass fiber infiltration agent | |
| CN102557486A (en) | Quartz glass fiber soakage agent | |
| CN106832524A (en) | A kind of flexible compound liner tubing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |