CN102558501B - Film forming agent for fiberglass roving and preparation method of film forming agent - Google Patents
Film forming agent for fiberglass roving and preparation method of film forming agent Download PDFInfo
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- CN102558501B CN102558501B CN201110433470.3A CN201110433470A CN102558501B CN 102558501 B CN102558501 B CN 102558501B CN 201110433470 A CN201110433470 A CN 201110433470A CN 102558501 B CN102558501 B CN 102558501B
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Abstract
The invention discloses a preparation method of a film forming agent for a fiberglass roving. The preparation method includes that firstly, polyethylene glycol with the molecular weight of 200 to 400 is mixed with a bisphenol-A epoxy resin to obtain an epoxy resin solution, secondary amine is added into the epoxy resin solution to lead to a reaction between active hydrogen on the secondary amine and parts of epoxy groups to generate tertiary amine, and a reaction between a hydroxyl at chain end of the polyethylene glycol and an epoxy group happens under the catalyst action of the obtained tertiary amine to generate a cross-linked structure. Accordingly, on the one hand, the polyethylene glycol is utilized to improve lubrication performance of the obtained film forming agent, on the other hand, the reaction between the active hydrogen on the secondary amine and the epoxy group is used to introduce a hydrophilic group to achieve hydrophilic character of the prepared film forming agent. According to the preparation method of the film forming agent for the fiberglass roving, reaction temperature of the epoxy resin and the secondary amine, adding temperature of glacial acetic acid, and the like are reduced, a prepared aqueous epoxy resin film forming agent is enabled to be light in color while reactions among materials are fully performed, and the fiberglass which uses the aqueous epoxy resin film forming agent is guaranteed to have a good appearance.
Description
Technical field
The present invention relates to glass fibre technical field, more particularly, relate to membrane-forming agent and preparation method thereof for a kind of glass fiber rough yarn.
Background technology
Glass fiber infiltration agent is a kind of surface treatment agent applying for fiberglass surfacing, most important to the manufacture of glass fibre, has determined transaction capabilities and the performance of fiber in matrix material of fiber.Treating compound is to be mixed to form the polycomponent aqueous solution or emulsion by membrane-forming agent, coupling agent and static inhibitor etc., and energy effectively lubricating fiberglass surfacing, makes glass fibre smooth, soft, wear-resisting, and give the performance of later stage matrix material brilliance.The effect for the treatment of compound is mainly manifested in the following aspects: lubrication protection effect, bonding boundling effect, prevent the accumulation of fiberglass surfacing static charge and make glass fibre obtain the consistency good with base material etc.Under the effect for the treatment of compound, fiberglass product has the application performances such as desirable physicals, mechanical property, chemical property, electric property and ageing-resistant performance.
Membrane-forming agent is most important component in glass fiber treating compound, can form on glass surface a kind of film with the continuous uniform of the performances such as certain flexibility, extensibility and rub resistance, to and the use properties in glass later stage have extremely important effect.Owing to having good cementability between epoxy resin and current conventional composite resin matrix, thereby epoxy resin film-forming agent occupies very large ratio in membrane-forming agent system.
Along with the enhancing of social progress and people's environmental consciousness, the Water-borne modification of epoxy resin has become one of study hotspot of current field of polymer technology.The preparation method of aqueous epoxy resins membrane-forming agent mainly comprises three kinds of mechanical process, phase inversion and chemic modified methods, and wherein chemic modified method is the preparation method of at present comparatively conventional aqueous epoxy resins membrane-forming agent.In prior art, reported a kind of preparation method who adopts chemic modified method to prepare aqueous epoxy resins membrane-forming agent, step comprises: the epoxy resin that (1) is 500～700 by epoxy equivalent (weight) is dissolved in lubricant at 100～110 ℃, obtains epoxy resin solution; (2) at 70 ℃～80 ℃, in epoxy resin solution, add reactive amines, be then warming up to 120 ℃～130 ℃; (3) at 100～110 ℃, add Glacial acetic acid to react, obtain quaternary ammonium salt-modified epoxy resin solution, add after water mixes and obtain epoxy resin film-forming agent.
But the preparation method's of above-mentioned report preparation temperature is higher, thereby cause the dark impact of color of the aqueous epoxy resins membrane-forming agent that obtains to use the outward appearance of the glass fibre of this membrane-forming agent.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide membrane-forming agent and preparation method thereof for a kind of glass fiber rough yarn, aqueous epoxy resins membrane-forming agent prepared by the method for light color, is used the glass fibre of aqueous epoxy resins membrane-forming agent to have good outward appearance and tension intensity.
In order to solve above technical problem, the invention provides the preparation method of membrane-forming agent for a kind of glass fiber rough yarn, comprise the following steps:
The polyoxyethylene glycol that step is a) 200～400 by molecular weight mixes with bisphenol A type epoxy resin, and heated and stirred obtains epoxy resin solution, and the mass ratio of described bisphenol A type epoxy resin and described polyoxyethylene glycol is (2.33～19): 1;
Step b) at 65～75 ℃, in described epoxy resin solution, add secondary amine, obtain mixing solutions after reaction, temperature of reaction is 75～85 ℃, and the mass ratio of described bisphenol A type epoxy resin and secondary amine is (1.8～3.6): 1;
Step c) described mixing solutions is cooled to 55～65 ℃, adds Glacial acetic acid, after reaction, add water and stir, obtain glass fiber rough yarn membrane-forming agent.
Preferably, described step heat-up time a) is 30～60min.
Preferably, the joining day of described secondary amine is 30～60min.
Preferably, the temperature of reaction that obtains mixing solutions is 75～85 ℃, and the reaction times is 30～90min.
Preferably, obtaining glass fiber rough yarn is 70～75 ℃ by the temperature of reaction of membrane-forming agent, and the reaction times is 30～40min.
Preferably, the mol ratio of described Glacial acetic acid and described secondary amine is (1～1.3): 1.
Preferably, obtaining glass fiber rough yarn is 60～120min by the churning time of membrane-forming agent, and whipping temp is 68～75 ℃.
Preferably, the epoxy equivalent (weight) of described bisphenol A type epoxy resin is 150～350.
Accordingly, the present invention also provides glass fiber rough yarn membrane-forming agent prepared by a kind of technique scheme.
Preferably, particle diameter is 20～40nm.
The invention provides the preparation method of membrane-forming agent for a kind of glass fiber rough yarn, the polyoxyethylene glycol and the bisphenol A type epoxy resin that by molecular weight, are first 200～400 are mixed to form epoxy resin solution, and polyoxyethylene glycol plays as solvent the effect that dilution disperses; In described epoxy resin solution, add after secondary amine, reactive hydrogen on secondary amine and part epoxy reaction generate tertiary amine, because tertiary amine is the catalyzer of hydroxyl and epoxy reaction, the hydroxyl of the polyoxyethylene glycol end of the chain reacts under the katalysis of the tertiary amine obtaining with epoxy group(ing) and generates crosslinking structure, thereby the present invention has utilized polyoxyethylene glycol to improve the lubricity of the membrane-forming agent obtaining, on the other hand, the present invention utilizes reactive hydrogen on secondary amine to introduce hydrophilic radical with reacting of epoxy group(ing), makes the membrane-forming agent of preparation possess water-wet behavior.Compared with prior art, what the present invention had reduced the temperature of reaction of epoxy resin and secondary amine and Glacial acetic acid adds the conditions such as temperature, aqueous epoxy resins membrane-forming agent of light color that fully makes preparation between each raw material when reaction, has guaranteed to use the glass fibre of aqueous epoxy resins membrane-forming agent to have good outward appearance.Experimental result shows, glass fiber rough yarn prepared by the present invention is more shallow by the color of membrane-forming agent, uses the tension intensity of glass fibre of aqueous epoxy resins membrane-forming agent better, and the wool yarn of weaving cotton cloth is less.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The invention discloses the preparation method of membrane-forming agent for a kind of glass fiber rough yarn, comprise the following steps:
The polyoxyethylene glycol that step is a) 200～400 by molecular weight mixes with bisphenol A type epoxy resin, and heated and stirred obtains epoxy resin solution, and the mass ratio of described bisphenol A type epoxy resin and described polyoxyethylene glycol is (2.33～19): 1;
Step b) at 65～75 ℃, in described epoxy resin solution, add secondary amine, obtain mixing solutions after reaction, temperature of reaction is 75～85 ℃, and the mass ratio of described bisphenol A type epoxy resin and secondary amine is (1.8～3.6): 1;
Step c) described mixing solutions is cooled to 55～65 ℃, adds Glacial acetic acid, after reaction, add water and stir, obtain glass fiber rough yarn membrane-forming agent.
It is that 200～400 polyoxyethylene glycol (PEG) is as solvent that the present invention adopts molecular weight, in the step of mixing with bisphenol A type epoxy resin, play the effect that dilution disperses, in obtaining the step of epoxy resin solution, do not participate in reaction, the molecular weight of described polyoxyethylene glycol is preferably 200～300, and more preferably 200.Described step is preferably 30～60min, more preferably 30～50min, more preferably 40～50min heat-up time a); Heating temperature is preferably 70～80 ℃, more preferably 70～75 ℃.The mass ratio of described bisphenol A type epoxy resin and described polyoxyethylene glycol is preferably (2.33～19): 1, more preferably (5～15): 1, more preferably (7～10): 1.The preferred epoxy equivalent (weight) of the present invention is lower, is liquid epoxy resin, thereby can dissolves each other at a lower temperature with polyoxyethylene glycol under room temperature.The epoxy equivalent (weight) of described bisphenol A type epoxy resin is preferably 150～350, and more preferably 180～300, more preferably 200～300.
Obtain adding secondary amine in the backward described epoxy resin solution of epoxy resin solution, reactive hydrogen on secondary amine and epoxy reaction, the mass ratio of described bisphenol A type epoxy resin and secondary amine is (2～3.6): 1, more preferably (2.5～3.2): 1, reaction formula is as follows:
Wherein, R
1for substituting group, be preferably methyl, ethyl or propyl group.
In above-mentioned steps, in epoxy resin solution, add after secondary amine, the reactive hydrogen on secondary amine and part epoxy reaction generate tertiary amine, because tertiary amine is the catalyzer of hydroxyl and epoxy reaction.Under the katalysis of tertiary amine, the hydroxyl of the polyoxyethylene glycol end of the chain and the epoxy group(ing) generation crosslinking structure that reacts, also can participate in the reactive solvents of reaction thereby polyoxyethylene glycol is the dilution dissemination that can play solvent, and reaction process is as follows:
Wherein, R
2and R
3be respectively substituting group.
Carrying out along with reaction, part polyoxyethylene glycol enters molecular chain by reaction, remaining polyoxyethylene glycol is still the solvent of this reaction and will in later stage glass fibre manufacturing processed, plays the effect of lubricant, has improved to a certain extent the processing characteristics of glass fibre.Therefore, one aspect of the present invention utilizes polyoxyethylene glycol to improve the lubricity of the membrane-forming agent obtaining, and utilizes on the other hand reactive hydrogen on secondary amine to introduce hydrophilic radical with reacting of epoxy group(ing), makes the membrane-forming agent of preparation possess water-wet behavior.
The more important thing is, the inventor find reactive amines and epoxy resin temperature of reaction surpass 90 ℃ or add Glacial acetic acid after quaternary ammoniated temperature surpass 80 ℃ and can make the modified epoxy its colour changed into yellow obtaining, have a strong impact on product appearance.Therefore, the present invention is controlled at proper range by each phase temperature of reaction and has just solved the shortcoming that color of resin is dark, product appearance is poor.Wherein, the temperature that adds of described secondary amine is preferably 68～73 ℃, and more preferably 70 ℃, the joining day of described secondary amine is preferably 30～60min, more preferably 40～50min.In addition, the temperature of reaction that obtains mixing solutions is preferably 75～85 ℃, and more preferably 75～80 ℃, the reaction times is preferably 30～90min, more preferably 45～70min.
Finally, will after mixing solutions cooling, add Glacial acetic acid (HAc) to carry out quaterisation, reaction formula be as follows:
In membrane-forming agent, epoxy equivalent (weight) is very large to the performance impact of later stage glass fibre.Epoxy equivalent (weight) is little, and epoxide group is residual too much, membrane-forming agent poor stability, and later stage fiber glass yarns is many; Epoxy equivalent (weight) is large, and epoxide group is residual very few, and composite property prepared by glass fibre is poor, therefore controls epoxy equivalent (weight) extremely important.The preparation method of conventional membrane-forming agent generally adopts the test of epoxy equivalent (weight) to control and reacts and carries out, yet the method required time is long, and particularly the larger epoxy equivalent (weight) time error of test is large.The span of control of the epoxy equivalent (weight) of prior art report is 2800～3200, but under this epoxy equivalent (weight), still has a large amount of epoxide groups to fail to obtain modification, makes membrane-forming agent poor storage stability, and fiberglass products wool yarn is many.
The present invention preferably controls the reaction times by particle diameter, and the glass fiber rough yarn obtaining is preferably 20～40nm with the particle diameter of membrane-forming agent, more preferably 20～35nm.Wherein, reactive amines and epoxy resin reaction times are shorter, and the epoxy group(ing) being modified is few; Reactive amines and epoxy resin reaction times increase, and the epoxy group(ing) being modified is many.By above-mentioned reaction formula, can find out, the wetting ability of modified epoxy is provided by the epoxide group being modified, thus secondary amine and the epoxide group reaction times shorter, the modified epoxy wetting ability obtaining is poorer, the particle diameter recording will be larger.The present invention obtains glass fiber rough yarn and is preferably 70～75 ℃ by the temperature of reaction of membrane-forming agent, and more preferably 70 ℃, the reaction times is preferably 30～40min, more preferably 30min.The mol ratio of described Glacial acetic acid and described secondary amine is preferably (1～1.3): 1, more preferably (1～1.2): 1.Obtain glass fiber rough yarn and be preferably 60～120min by the churning time of membrane-forming agent, more preferably 80～110min; Whipping temp is preferably 68～75 ℃, more preferably 70～75 ℃.
In preparation process of the present invention, the temperature of reaction of secondary amine and epoxy resin, Glacial acetic acid add temperature control etc. to be key factor of the present invention, have the reason of following several respects: (1) reactive amines and the too high meeting of epoxy resin temperature of reaction cause that product colour is poor, the high even gel of degree of crosslinking; The low meeting of temperature causes epoxide group modification incomplete, and product stability is poor; (2) reactive amines and epoxy resin reaction times longer, glass fiber compound material mechanical property prepared by the later stage will decline; Reactive amines and epoxy resin reaction times are shorter, and fiber glass yarns is more; (3) Glacial acetic acid temperature of reaction is too low, quaternized incomplete, water-soluble bad; Glacial acetic acid temperature of reaction is too high, and product colour is more yellow, appearance poor.Therefore compared with prior art, what the present invention had reduced the temperature of reaction of epoxy resin and secondary amine and Glacial acetic acid adds temperature etc., aqueous epoxy resins membrane-forming agent of light color that fully makes preparation between each raw material when reaction, has guaranteed to use the glass fibre of aqueous epoxy resins membrane-forming agent to have good outward appearance.Experimental result shows, glass fiber rough yarn prepared by the present invention is more shallow by the color of membrane-forming agent, uses the tension intensity of glass fibre of aqueous epoxy resins membrane-forming agent better, and the wool yarn of weaving cotton cloth is less.
In sum, glass fiber rough yarn prepared by the present invention is easily controlled by membrane-forming agent stable production process, and safety non-toxic meets post-production technique, is conducive to improve the over-all properties of glass fiber compound material goods.
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The chemical reagent that the embodiment of the present invention and comparative example adopt is commercial.
Embodiment 1
(1) it is that in 300 bisphenol A type epoxy resin, heated and stirred 30min, obtains epoxy resin solution that the polyoxyethylene glycol that is 200 by 40g molecular weight adds 400g epoxy equivalent (weight);
(2) at 73 ℃, in described epoxy resin solution, add secondary amine 100g, controlling temperature of reaction is 83 ℃, about 25min of joining day;
(3) at 80 ℃ of insulation reaction 40min, obtain the first mixing solutions;
(4) described the first mixing solutions is cooled to 55 ℃, adds Glacial acetic acid 80g, obtain the mixing solutions that contains quaternary ammonium salt-modified epoxy resin after reaction, controlling temperature of reaction is 70 ℃, about 15min of reaction times;
(5) in the described mixing solutions that contains quaternary ammonium salt-modified epoxy resin, add water, at 70 ℃, insulated and stirred 90min, obtains membrane-forming agent.
The outward appearance of membrane-forming agent prepared by the present embodiment is water white transparency, and particle diameter is 24nm.
Embodiment 2
(1) it is that in 300 bisphenol A type epoxy resin, heated and stirred 45min, obtains epoxy resin solution that the polyoxyethylene glycol that is 200 by 45g molecular weight adds 410g epoxy equivalent (weight);
(2) at 68 ℃, in described epoxy resin solution, add secondary amine 153g, controlling temperature of reaction is 80 ℃, about 35min of joining day;
(3) at 80 ℃ of insulation reaction 65min, obtain the first mixing solutions;
(4) described the first mixing solutions is cooled to 58 ℃, adds Glacial acetic acid 84g, obtain the mixing solutions that contains quaternary ammonium salt-modified epoxy resin after reaction, controlling temperature of reaction is 67 ℃, and the reaction times is 22min;
(5) in the described mixing solutions that contains quaternary ammonium salt-modified epoxy resin, add water, at 70 ℃, insulated and stirred 104min, obtains membrane-forming agent.
Membrane-forming agent outward appearance prepared by the present embodiment is water white transparency, and particle diameter is 22nm.
Embodiment 3
(1) it is that in 300 bisphenol A type epoxy resin, heated and stirred 47min, obtains epoxy resin solution that the polyoxyethylene glycol that is 200 by 52g molecular weight adds 440g epoxy equivalent (weight);
(2) at 68 ℃, in described epoxy resin solution, add secondary amine 205g, controlling temperature of reaction is 84 ℃, about 40min of joining day;
(3) at 82 ℃ of insulation reaction 53min, obtain the first mixing solutions;
(4) described the first mixing solutions is cooled to 62 ℃, adds Glacial acetic acid 106g, obtain the mixing solutions that contains quaternary ammonium salt-modified epoxy resin after reaction, controlling temperature of reaction is 75 ℃, and the reaction times is 29min;
(5) in the described mixing solutions that contains quaternary ammonium salt-modified epoxy resin, add water, insulated and stirred 118min at approximately 70 ℃, obtains membrane-forming agent.
The outward appearance of membrane-forming agent prepared by the present embodiment is water white transparency, and particle diameter is 30nm.
Comparative example 1 changes temperature of reaction and is prepared into film
(1) it is that in 600 bisphenol A type epoxy resin, heated and stirred 47min, obtains epoxy resin solution that the polyoxyethylene glycol that is 200 by 52g molecular weight at 110 ℃ adds 440g epoxy equivalent (weight);
(2) at 80 ℃, in described epoxy resin solution, add secondary amine 205g, about 40min of joining day;
(3) be warming up to 120 ℃ of insulation reaction 53min, obtain the first mixing solutions;
(4) described the first mixing solutions is cooled to 110 ℃, adds Glacial acetic acid 106g, obtain the mixing solutions that contains quaternary ammonium salt-modified epoxy resin after reaction, controlling temperature of reaction is 110 ℃, and the reaction times is 29min;
(5) in the described mixing solutions that contains quaternary ammonium salt-modified epoxy resin, add water, insulated and stirred 118min at approximately 80 ℃, obtains membrane-forming agent.
It is yellow that the outward appearance of membrane-forming agent prepared by this comparative example is, and particle diameter is 20nm.
Comparative example 2 changes reaction raw materials and is prepared into film
(1) it is that in 600 bisphenol A type epoxy resin, heated and stirred 47min, obtains epoxy resin solution that the polyoxyethylene glycol that is 600 by 52g molecular weight at 110 ℃ adds 440g epoxy equivalent (weight);
(2) at 80 ℃, in described epoxy resin solution, add secondary amine 205g, about 40min of joining day;
(3) be warming up to 120 ℃ of insulation reaction 53min, obtain the first mixing solutions;
(4) described the first mixing solutions is cooled to 110 ℃, adds Glacial acetic acid 106g, obtain the mixing solutions that contains quaternary ammonium salt-modified epoxy resin after reaction, controlling temperature of reaction is 110 ℃, and the reaction times is 29min;
(5) in the described mixing solutions that contains quaternary ammonium salt-modified epoxy resin, add water, insulated and stirred 118min at approximately 80 ℃, obtains membrane-forming agent.
It is yellow that the outward appearance of membrane-forming agent prepared by this comparative example is, and particle diameter is 20nm.
The membrane-forming agent prepared by the embodiment of the present invention and comparative example of take is respectively raw material, adopts and prepares with the following method treating compound:
Respectively the membrane-forming agent of the 8wt% embodiment of the present invention 1～3 or comparative example 1～2 preparation, 3% acetic acid, 0.2% white oil, 5% gasoline and the water of 84.8wt% are mixed, obtain treating compound.
The treating compound of above-mentioned preparation is coated on to fiberglass surfacing, obtains the glass fibre after treating compound is processed.Performance to the glass fibre of the membrane-forming agent of the above-mentioned use embodiment of the present invention 1～3 and comparative example 1～2 preparation detects, and detected result is as shown in table 1.
The results of property of glass fibre prepared by table 1 the present invention
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (7)
1. the preparation method of membrane-forming agent for glass fiber rough yarn, comprises the following steps:
The polyoxyethylene glycol that step a) is 200～400 by molecular weight mixes with bisphenol A type epoxy resin, and heated and stirred obtains epoxy resin solution, and the mass ratio of described bisphenol A type epoxy resin and described polyoxyethylene glycol is (2.33～19): 1;
Step b) adds secondary amine at 65～75 ℃ in described epoxy resin solution, the joining day of described secondary amine is 30～60min, after reaction, obtain mixing solutions, temperature of reaction is 75～85 ℃, reaction times is 30～90min, and the mass ratio of described bisphenol A type epoxy resin and secondary amine is (1.8～3.6): 1;
Step c) is cooled to 55～65 ℃ by described mixing solutions, adds Glacial acetic acid, adds water and stir after reaction, obtains glass fiber rough yarn membrane-forming agent; Obtaining glass fiber rough yarn is 70～75 ℃ by the temperature of reaction of membrane-forming agent, and the reaction times is 30～40min.
2. preparation method according to claim 1, is characterized in that, be 30～60min the heat-up time of described step a).
3. preparation method according to claim 1, is characterized in that, the mol ratio of described Glacial acetic acid and described secondary amine is (1～1.3): 1.
4. preparation method according to claim 1, is characterized in that, obtaining glass fiber rough yarn is 60～120min by the churning time of membrane-forming agent, and whipping temp is 68～75 ℃.
5. preparation method according to claim 1, is characterized in that, the epoxy equivalent (weight) of described bisphenol A type epoxy resin is 150～350.
6. the glass fiber rough yarn membrane-forming agent that prepared by the method described in claim 1～5 any one.
7. glass fiber rough yarn membrane-forming agent according to claim 6, is characterized in that, the particle diameter of described membrane-forming agent is 20～40nm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090487A (en) * | 1994-12-13 | 2000-07-18 | Vetrotex France | Sizing composition for glass threads, process using this composition and resulting products |
| CN101759859A (en) * | 2009-12-25 | 2010-06-30 | 巨石集团有限公司 | Production method of epoxy resin emulsion film-forming agent for direct-roving treating compound |
| CN101831078A (en) * | 2010-05-25 | 2010-09-15 | 中材科技股份有限公司 | Preparation method of film forming agent and impregnating compound containing film forming agent |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090487A (en) * | 1994-12-13 | 2000-07-18 | Vetrotex France | Sizing composition for glass threads, process using this composition and resulting products |
| CN101759859A (en) * | 2009-12-25 | 2010-06-30 | 巨石集团有限公司 | Production method of epoxy resin emulsion film-forming agent for direct-roving treating compound |
| CN101831078A (en) * | 2010-05-25 | 2010-09-15 | 中材科技股份有限公司 | Preparation method of film forming agent and impregnating compound containing film forming agent |
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