CN109652981B - Starch-based glass fiber soaking film-forming agent and preparation method thereof - Google Patents
Starch-based glass fiber soaking film-forming agent and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
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Abstract
The invention discloses a starch-based glass fiber soaking film-forming agent and a preparation method thereof, wherein the preparation method comprises the following steps: mixing high amylose starch with water to prepare starch slurry, and adding acid for acidolysis to obtain acidolysis starch slurry; the molecular weight of the starch contained in the acidolysis starch slurry is 20000-80000 g/mol; adjusting pH of the acidolysis starch slurry to 4.0-5.0, filtering, cleaning the filter residue, and mixing with water to obtain starch solution; and curing the starch solution, cooling, adding alkali to adjust the pH value, adding propylene oxide to perform etherification reaction, and drying to obtain the starch-based glass fiber soaking film-forming agent. The preparation method of the starch-based glass fiber infiltration film-forming agent provided by the invention has the advantages of simple process, high reaction speed, no sodium sulfate used in the reaction, good environmental protection, good stability of the prepared starch-based glass fiber infiltration film-forming agent, high strength, good film-forming property on the surface of glass fiber and difficult breakage.
Description
Technical Field
The invention relates to the technical field of glass fiber, in particular to a starch-based glass fiber soaking film-forming agent and a preparation method thereof.
Background
The glass fiber has wide application, and has a large amount of applications in the fields of building materials, petrochemicals, automobiles, printed circuit boards, wind power blades, electronics, electrics, new energy and the like. During the glass fiber drawing process, a special surface treating agent with a multiphase structure mainly comprising organic emulsion or solution is required to be coated on the surface of the glass fiber. The coating not only can effectively lubricate and protect the surface of the glass fiber, but also can integrate hundreds or even thousands of glass fiber monofilaments into a bundle, and can change the surface state of the glass fiber. Therefore, the requirements on the performance of the glass fiber strands in the subsequent processing procedures are met, and the combination of the glass fibers and the reinforced high polymer can be promoted in the composite material. These organic coatings are collectively referred to as glass fiber size (simply referred to as draw size). The impregnating compound is composed of a film forming agent, a coupling agent, a lubricating agent, an antistatic agent and the like, and is generally prepared into a 5-10% aqueous solution. The film-forming agent accounts for 2% -15% of the total amount of the impregnating compound, is a key component of the impregnating compound and determines the performance of the impregnating compound; it not only has the functions of bundling and bonding the protofilaments, but also determines the technological performance of the glass fiber during the forming of the glass fiber reinforced plastic.
Starch has been widely used as a raw material for film-forming agents in sizing agents. The starch type impregnating compound has good protection effect on glass fiber bundling, less broken filaments during unwinding and weaving, nontoxic raw materials, easy thermal cleaning, low decomposition temperature and tidy cloth surface after post-treatment. The starch type impregnating compound belongs to renewable energy sources and is environment-friendly.
In actual production, if ordinary starch is directly used as a film forming agent in the components of the sizing agent, the performance aspect is far from meeting the production requirement. The biggest defect is that the prepared sizing agent can not well form a compact film on the surface of the glass fiber to play roles of protecting and bundling the glass fiber, and the like, so the sizing agent needs to be modified.
When the starch is used for coating the glass fiber by the sizing agent, the starch is high in viscosity and easy to regenerate, and is unevenly spread on the surface of the glass fiber, is not tightly adhered to the surface of the glass fiber and is poorer in sizing effect with the surface of the glass fiber. In the prior art, for reducing the viscosity and retrogradation speed of starch, a hanging chemical group such as hydroxypropyl is generally adopted to modify the starch; however, all modifications are based on modification of starch granules, and the reaction time is long and not environment-friendly.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the starch-based glass fiber soaking film-forming agent and the preparation method thereof, the preparation method has the advantages of simple process, high reaction speed, no sodium sulfate used in the reaction, good environmental protection, good stability and high strength of the prepared starch-based glass fiber soaking film-forming agent, good film-forming property on the surface of glass fiber and difficult breakage.
The invention provides a preparation method of a starch-based glass fiber soakage film-forming agent, which comprises the following steps:
s1, mixing high amylose starch with water to prepare starch slurry, and adding acid into the starch slurry for acidolysis to obtain acidolysis starch slurry; wherein the molecular weight of the starch contained in the acidolysis starch slurry is 20000-80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 4.0-5.0, filtering, cleaning filter residues, and mixing with water to obtain a starch solution; and curing the starch solution, cooling, adding alkali to adjust the pH value, adding propylene oxide to perform etherification reaction, and drying after the reaction is finished to obtain the starch-based glass fiber soaking film-forming agent.
Preferably, in S1, the high amylose starch has an amylose content of 50wt% to 60 wt%; in the starch slurry, the mass content of the high amylose is 35-45 wt%.
Preferably, the mass content of high amylose starch in the starch slurry is 40 wt%.
Preferably, in S1, the acid is one or more of sulfuric acid, hydrochloric acid, and acetic acid.
Preferably, in S1, using phenolphthalein as an indicator, acid is added until 50ml of the sample is titrated with 56-60 ml of 0.1mol/L sodium hydroxide solution to discolor phenolphthalein.
Preferably, in S1, heating the starch slurry to 50-60 ℃, and then adding acid for acidolysis; the acidolysis time is 8-24 h.
Preferably, the time for the acid hydrolysis is 16 h.
Preferably, in S2, the starch solution has a solid content of 35-45 wt%.
Preferably, the starch solution has a solid content of 40 wt%.
Preferably, in S2, the temperature of curing is 115-125 ℃.
Preferably, the temperature of the aging is 120 ℃.
Preferably, in S2, phenolphthalein is used as an indicator, and base is added until 50mL of sample is titrated with 61-65mL of 0.1mol/L hydrochloric acid to discolor phenolphthalein.
Preferably, in S2, the temperature of the etherification reaction is 45-50 ℃ and the time is 2.5-3.5 h.
Preferably, the temperature of the etherification reaction is 48 ℃ and the time is 3 hours.
The invention also provides a starch-based glass fiber soaking film-forming agent, which is prepared by adopting the preparation method of the starch-based glass fiber soaking film-forming agent.
The invention also provides application of the starch-based glass fiber impregnating film-forming agent in a glass fiber impregnating agent.
The invention also provides an application method of the starch-based glass fiber impregnating film-forming agent in the glass fiber impregnating compound, which comprises the following steps: mixing 40 parts of starch-based glass fiber soaking film-forming agent and deionized water according to the parts by weight to obtain a solution with the mass percentage of 5%, and adjusting the temperature to 70-80 ℃ to obtain starch paste for later use; dissolving 0.25-0.65 parts of GW-18 in water, and adjusting the temperature to be more than 75 ℃ to obtain a solution A; dissolving 0.7-1.2 parts of NBL-70 in hot water at 78-82 ℃ to obtain solution B; adding auxiliary agents NBL-e-2010.8-1.5 parts, Sofbon GF-10.50-0.85 part, L-440.05-0.15 part, Newlon GF-1010.02-0.08 part and Newlon GF-1000.05-0.15 part into an emulsification container, heating to 75-85 ℃, adding the solution A at the stirring speed of 5000r/min, stirring to paste, adding hot water with the temperature of more than 85 ℃ to obtain a stable oil-in-water emulsion, stirring at the stirring speed of 5000r/min for 3-8min, then adding the solution B into starch paste, and quantifying to 1000 parts by using water with the temperature of 68-75 ℃ to obtain the glass fiber impregnating compound.
According to the preparation method of the starch-based glass fiber infiltration film-forming agent, specific high amylose starch is selected as a raw material, a starch amorphous region is cut when acid is used for starch solid phase, the size distribution of starch molecules is specifically controlled to be 20000-80000g/mol, then the starch is dissolved in water to become a starch dispersion phase through high-temperature curing, and then propylene oxide is used for etherification reaction to graft hydroxypropyl and starch molecules, so that the starch-based glass fiber infiltration film-forming agent is obtained; compared with the prior art, the method has the following advantages: 1. compared with the existing solid-phase hydroxypropyl grafting method, the hydroxypropyl is more uniformly distributed on starch molecules, the obtained film forming agent is more stable and better in strength, and is not easy to regenerate, and the formed film is not easy to break; 2. starch molecules are dissolved in water by adopting a high-temperature curing mode, and then etherification reaction is carried out, so that sodium sulfate is not used, and the environmental pollution is reduced; 3. the time of etherification reaction is shortened from more than ten hours to 2.5-3.5h, and the reaction speed is high.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The invention provides a preparation method of a starch-based glass fiber soakage film-forming agent, which comprises the following steps:
s1, weighing 500g of high amylose with 50% of amylose content, adding 750 g of water to prepare starch slurry with 40wt% of solid content, heating to 55 ℃, then adding sulfuric acid and sampling, titrating by taking phenolphthalein as an indicator, stopping adding acid when 50mL of sample is titrated by 56mL of 0.1mol/L sodium hydroxide solution to discolor phenolphthalein, and carrying out acidolysis for 16h to obtain acidolysis starch slurry; measuring the molecular weight of starch in the acidolysis starch slurry to be 20000-80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 4.0, filtering, cleaning filter residues to remove redundant salt, adding water to form a starch solution with the solid content of 40wt%, curing the starch solution at 120 ℃, cooling to 48 ℃, adding alkali to adjust the pH value, sampling, titrating, taking phenolphthalein as an indicator, stopping adding alkali when 50mL of sample is titrated with 61mL and 0.1mol/L hydrochloric acid to change the color of the phenolphthalein, adding 27.5 g of propylene oxide, reacting for 3 hours at 48 ℃, cleaning and drying to obtain the starch-based glass fiber infiltration film forming agent.
The invention also provides a starch-based glass fiber soaking film-forming agent, which is prepared by adopting the preparation method of the starch-based glass fiber soaking film-forming agent.
Comparative example 1
A preparation method of a starch-based glass fiber soakage film-forming agent comprises the following steps:
s1, weighing 500g of high amylose with 50% of amylose content, adding 750 g of water to prepare starch slurry with 40wt% of solid content, heating to 55 ℃, and adding sulfuric acid for acidolysis to obtain acidolysis starch slurry; determining the molecular weight of starch in the acidolysis starch slurry to be more than 80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 4.0, filtering, cleaning filter residues to remove redundant salt, adding water to form a starch solution with the solid content of 40wt%, curing the starch solution at 120 ℃, cooling to 48 ℃, adding alkali to adjust the pH value, sampling, titrating, taking phenolphthalein as an indicator, stopping adding alkali when 50mL of sample is titrated with 61mL and 0.1mol/L hydrochloric acid to change the color of the phenolphthalein, adding 27.5 g of propylene oxide, reacting for 3 hours at 48 ℃, cleaning and drying to obtain the starch-based glass fiber infiltration film forming agent.
Comparative example 2
A preparation method of a starch-based glass fiber soakage film-forming agent comprises the following steps:
s1, weighing 500g of high amylose with 50% of amylose content, adding 750 g of water to prepare starch slurry with 40wt% of solid content, heating to 55 ℃, and adding sulfuric acid for acidolysis to obtain acidolysis starch slurry; determining the molecular weight of starch in the acidolysis starch slurry to be less than 20000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 4.0, filtering, cleaning filter residues to remove redundant salt, adding water to form a starch solution with the solid content of 40wt%, curing the starch solution at 120 ℃, cooling to 48 ℃, adding alkali to adjust the pH value, sampling, titrating, taking phenolphthalein as an indicator, stopping adding alkali when 50mL of sample is titrated with 61mL and 0.1mol/L hydrochloric acid to change the color of the phenolphthalein, adding 27.5 g of propylene oxide, reacting for 3 hours at 48 ℃, cleaning and drying to obtain the starch-based glass fiber infiltration film forming agent.
The performance parameters of the starch-based fiberglass sizing film formers prepared in example 1, comparative example 1, and comparative example 2 were determined and the results are shown in the following table:
the starch-based glass fiber soaking film-forming agent prepared in the example 1 and the comparative examples 1 and 2 is used for preparing a soaking agent according to the application method of the invention, the prepared soaking agent is used for glass fiber drawing, and the related performance is detected, wherein the detection results are shown in the following table:
example 2
The invention provides a preparation method of a starch-based glass fiber soakage film-forming agent, which comprises the following steps:
s1, weighing 500g of high amylose with 60% of amylose content, adding 928g of water to prepare starch slurry with 35 wt% of solid content, heating to 50 ℃, then adding hydrochloric acid and sampling, titrating by taking phenolphthalein as an indicator, stopping adding acid when 50mL of sample is titrated by 60mL of 0.1mol/L sodium hydroxide solution to discolor phenolphthalein, and carrying out acidolysis for 8h to obtain acidolysis starch slurry; measuring the molecular weight of starch in the acidolysis starch slurry to be 20000-80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 5.0, filtering, cleaning filter residues to remove redundant salt, adding water to form a starch solution with the solid content of 40wt%, curing the starch solution at 115 ℃, cooling to 48 ℃, adding alkali to adjust the pH value, sampling, titrating, taking phenolphthalein as an indicator, stopping adding alkali when 50mL of sample is titrated by 65mL and 0.1mol/L hydrochloric acid to change the color of the phenolphthalein, adding 27.5 g of propylene oxide, reacting for 2.5 hours at 50 ℃, cleaning and drying to obtain the starch-based glass fiber infiltration film forming agent.
Example 3
The invention provides a preparation method of a starch-based glass fiber soakage film-forming agent, which comprises the following steps:
s1, weighing 500g of high amylose with 55% of amylose content, adding 611g of water to prepare starch slurry with 45wt% of solid content, heating to 60 ℃, adding acetic acid, sampling, titrating by taking phenolphthalein as an indicator, stopping adding acid when 50mL of sample is titrated by 57mL of 0.1mol/L sodium hydroxide solution to discolor phenolphthalein, and performing acidolysis for 24 hours to obtain acidolysis starch slurry; measuring the molecular weight of starch in the acidolysis starch slurry to be 20000-80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 4.5, filtering, cleaning filter residues to remove redundant salt, adding water to form a starch solution with the solid content of 45wt%, curing the starch solution at 125 ℃, cooling to 48 ℃, adding alkali to adjust the pH value, sampling, titrating, taking phenolphthalein as an indicator, stopping adding alkali when 50mL of sample is titrated by 65mL and 0.1mol/L hydrochloric acid to change the color of the phenolphthalein, adding 27.5 g of propylene oxide, reacting for 3.5 hours at 45 ℃, cleaning and drying to obtain the starch-based glass fiber infiltration film forming agent.
Example 4
The invention provides a preparation method of a starch-based glass fiber soakage film-forming agent, which comprises the following steps:
s1, mixing high amylose starch with water to prepare starch slurry, and adding acid into the starch slurry for acidolysis to obtain acidolysis starch slurry; wherein the molecular weight of the starch contained in the acidolysis starch slurry is 20000-80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 5.0, filtering, cleaning filter residues, and mixing with water to obtain a starch solution; and curing the starch solution, cooling, adding alkali to adjust the pH value, adding propylene oxide to perform etherification reaction, and drying after the reaction is finished to obtain the starch-based glass fiber soaking film-forming agent.
Example 5
The invention provides a preparation method of a starch-based glass fiber soakage film-forming agent, which comprises the following steps:
s1, mixing high amylose starch with water to prepare starch slurry, and adding acid into the starch slurry for acidolysis to obtain acidolysis starch slurry; wherein the molecular weight of the starch contained in the acidolysis starch slurry is 20000-80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 4.0, filtering, cleaning filter residues, and mixing with water to obtain a starch solution; and curing the starch solution, cooling, adding alkali to adjust the pH value, adding propylene oxide to perform etherification reaction, and drying after the reaction is finished to obtain the starch-based glass fiber soaking film-forming agent.
Example 6
The invention provides a preparation method of a starch-based glass fiber soakage film-forming agent, which comprises the following steps:
s1, mixing high amylose starch with water to prepare starch slurry, heating the starch slurry to 58 ℃, and then adding acid for acidolysis to obtain acidolysis starch slurry; wherein the molecular weight of the starch contained in the acidolysis starch slurry is 20000-80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 4.5, filtering, cleaning filter residues, and mixing with water to obtain a starch solution; curing the starch solution, cooling, adding alkali to adjust the pH value, adding propylene oxide to perform etherification reaction, and drying after the reaction is finished to obtain the starch-based glass fiber soaking film-forming agent;
wherein in S1, the high amylose starch has an amylose content of 60 wt%; in the starch slurry, the mass content of the high amylose starch is 35 wt%;
in S1, the acid is sulfuric acid;
in S1, using phenolphthalein as an indicator, adding acid until 50ml of sample is titrated with 56ml of 0.1mol/L sodium hydroxide solution to discolor phenolphthalein;
in S1, the acidolysis time is 24 h;
in S2, the starch solution has a solid content of 45 wt%;
in S2, the curing temperature is 125 ℃;
in S2, taking phenolphthalein as an indicator, adding alkali until 50mL of sample is titrated by 65mL of hydrochloric acid with 0.1mol/L to discolor the phenolphthalein;
in S2, the temperature of the etherification reaction is 45 ℃ and the time is 3.5 h.
Example 7
The invention provides a preparation method of a starch-based glass fiber soakage film-forming agent, which comprises the following steps:
s1, mixing high amylose starch with water to prepare starch slurry, heating the starch slurry to 52 ℃, and then adding acid for acidolysis to obtain acidolysis starch slurry; wherein the molecular weight of the starch contained in the acidolysis starch slurry is 20000-80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 5.0, filtering, cleaning filter residues, and mixing with water to obtain a starch solution; curing the starch solution, cooling, adding alkali to adjust the pH value, adding propylene oxide to perform etherification reaction, and drying after the reaction is finished to obtain the starch-based glass fiber soaking film-forming agent;
wherein in S1, the high amylose starch has an amylose content of 50 wt%; in the starch slurry, the mass content of the high amylose is 45 wt%;
in S1, the acid is hydrochloric acid;
in S1, using phenolphthalein as an indicator, adding acid until 50ml of sample is titrated with 60ml of 0.1mol/L sodium hydroxide solution to discolor phenolphthalein;
in S1, the acidolysis time is 8 h;
in S2, the starch solution has a solid content of 35 wt%;
in S2, the curing temperature is 115 ℃;
in S2, taking phenolphthalein as an indicator, adding alkali until 50mL of sample is titrated by 61mL of hydrochloric acid with 0.1mol/L to discolor the phenolphthalein;
in S2, the temperature of the etherification reaction is 50 ℃ and the time is 2.5 h.
Example 8
The invention provides a preparation method of a starch-based glass fiber soakage film-forming agent, which comprises the following steps:
s1, mixing high amylose starch with water to prepare starch slurry, heating the starch slurry to 55 ℃, and then adding acid for acidolysis to obtain acidolysis starch slurry; wherein the molecular weight of the starch contained in the acidolysis starch slurry is 20000-80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 4.0, filtering, cleaning filter residues, and mixing with water to obtain a starch solution; curing the starch solution, cooling, adding alkali to adjust the pH value, adding propylene oxide to perform etherification reaction, and drying after the reaction is finished to obtain the starch-based glass fiber soaking film-forming agent;
wherein in S1, the high amylose starch has an amylose content of 55 wt%; in the starch slurry, the mass content of the high amylose is 40 wt%;
in S1, the acid is a mixture of sulfuric acid, hydrochloric acid, acetic acid;
in S1, using phenolphthalein as an indicator, adding acid until 50ml of sample is titrated with 59 ml of 0.1mol/L sodium hydroxide solution to discolor phenolphthalein;
in S1, the acidolysis time is 16 h;
in S2, the starch solution has a solids content of 40 wt%;
in S2, the curing temperature is 120 ℃;
in S2, taking phenolphthalein as an indicator, adding alkali until 50mL of sample is titrated by 63mL of hydrochloric acid with 0.1mol/L to discolor the phenolphthalein;
in S2, the temperature of the etherification reaction is 48 ℃ and the time is 3 h.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of a starch-based glass fiber soakage film-forming agent is characterized by comprising the following steps:
s1, mixing high amylose starch with water to prepare starch slurry, and adding acid into the starch slurry for acidolysis to obtain acidolysis starch slurry; wherein the molecular weight of the starch contained in the acidolysis starch slurry is 20000-80000 g/mol;
s2, adjusting the pH value of the acidolysis starch slurry to 4.0-5.0, filtering, cleaning filter residues, and mixing with water to obtain a starch solution; curing the starch solution, cooling, adding alkali to adjust the pH value, adding propylene oxide to perform etherification reaction, and drying after the reaction is finished to obtain the starch-based glass fiber soaking film-forming agent;
in S2, the curing temperature is 115-125 ℃;
in S1, the high amylose starch has an amylose content of 50wt% to 60 wt%; in the starch slurry, the mass content of the high amylose is 35-45 wt%.
2. The method of preparing a starch-based fiberglass sizing film-forming agent according to claim 1, wherein in S1, the mass content of high amylose starch in the starch slurry is 40 wt%.
3. The method for preparing the starch-based glass fiber sizing film forming agent according to claim 1 or 2, wherein in S1, the acid is one or a mixture of sulfuric acid, hydrochloric acid and acetic acid.
4. The method for preparing the starch-based glass fiber sizing film forming agent according to claim 1 or 2, wherein in S1, phenolphthalein is used as an indicator, and acid is added until 50ml of sample is titrated by 56-60 ml of 0.1mol/L sodium hydroxide solution to discolor phenolphthalein.
5. The method for preparing the starch-based glass fiber sizing film-forming agent according to claim 1 or 2, wherein in S1, the starch slurry is heated to 50-60 ℃ and then is acidolyzed by adding acid; the acidolysis time is 8-24 h.
6. The method for preparing the starch-based glass fiber sizing film-forming agent according to claim 1 or 2, wherein in S2, the solid content of the starch solution is 35-45 wt%.
7. The method of preparing a starch-based fiberglass sizing film former according to claim 1 or 2, wherein in S2 the curing temperature is 120 ℃.
8. The method for preparing the starch-based glass fiber sizing film forming agent according to claim 1 or 2, wherein in S2, phenolphthalein is used as an indicator, and alkali is added until 50mL of sample is titrated by 61-65mL of hydrochloric acid with 0.1mol/L to change the color of phenolphthalein.
9. The method for preparing the starch-based glass fiber sizing film-forming agent according to claim 1 or 2, wherein the temperature of the etherification reaction is 45 to 50 ℃ and the time is 2.5 to 3.5 hours in S2.
10. A starch-based glass fiber sizing film-forming agent, characterized in that the film-forming agent is prepared by the method for preparing the starch-based glass fiber sizing film-forming agent according to any one of claims 1 to 9.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4197349A (en) * | 1978-09-29 | 1980-04-08 | Ppg Industries, Inc. | Glass fibers having a reduced tendency to give gumming deposits, forming size |
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| JP4094398B2 (en) * | 2002-10-15 | 2008-06-04 | 三菱アルミニウム株式会社 | Fin coating composition, fin, method for producing the same, and heat exchanger |
| CN103012608A (en) * | 2012-11-21 | 2013-04-03 | 西南科技大学 | Method for preparing etherification linear-chain dextrin starch film-forming agent for glass fiber infiltration |
| CN102923970B (en) * | 2012-11-28 | 2015-02-11 | 江西长江玻璃纤维有限公司 | Modified starch textile type impregnating compound and process for preparing same |
| CN105481989B (en) * | 2015-07-15 | 2020-07-03 | 河南恒瑞淀粉科技股份有限公司 | Glass fiber impregnating compound added with modified starch |
| CN106186731B (en) * | 2016-07-20 | 2019-07-19 | 广东志造生物科技有限公司 | A kind of G75 electronic yarn sizing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4197349A (en) * | 1978-09-29 | 1980-04-08 | Ppg Industries, Inc. | Glass fibers having a reduced tendency to give gumming deposits, forming size |
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