CN108996922B - Glass fiber impregnating compound for reinforcing structure type SMC (sheet molding compound) and application of glass fiber impregnating compound in production of twistless roving - Google Patents
Glass fiber impregnating compound for reinforcing structure type SMC (sheet molding compound) and application of glass fiber impregnating compound in production of twistless roving Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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Abstract
The invention discloses a glass fiber impregnating compound for a reinforced structure type SMC and application thereof in producing twistless roving. The impregnating compound comprises the following components: the water-based paint comprises a coupling agent, a film-forming agent, a lubricant, a pH value regulator and water, wherein the coupling agent is a silane coupling agent, and the film-forming agent is a mixture of non-crosslinking bisphenol A type polyester emulsion, crosslinking unsaturated polyester emulsion and bisphenol A type epoxy emulsion with medium and high molecular weight. The invention provides the application of the impregnating compound in producing the untwisted glass fiber roving for the reinforced structure type SMC sheet, the untwisted glass fiber roving produced by using the impregnating compound has the advantages of less hairiness, high penetration speed, good short cutting property, good production smoothness and good compatibility with reinforced resin, the mechanical strength of a glass fiber reinforced composite material product can be greatly improved, and the impregnating compound is suitable for an SMC forming process.
Description
(I) technical field
The invention relates to a glass fiber impregnating compound and an application thereof in producing untwisted roving, in particular to a glass fiber impregnating compound and an application thereof in producing untwisted glass fiber roving for an enhanced structure type SMC sheet.
(II) background of the invention
Sheet Molding Compound (SMC) is a sheet molding compound prepared by impregnating chopped fibers or mats with unsaturated polyester resin and thickening, and can be divided into a structural type and an A-level surface type, wherein the structural type emphasizes the strength of a product; the class A surface is used for emphasizing the surface effect of the product, and particularly the appearance of the product is required to achieve the same effect and level as the appearance of the spray paint. The method is widely applied to the fields of transportation, buildings, instruments and meters and other industries at present. The most commonly used matrix resins for SMC are unsaturated polyester resins. In the SMC forming process, the crosslinking degree of the glass fiber impregnating compound is very important and is an important factor influencing the SMC forming, if the crosslinking degree is too small, the glass fibers are dissolved into monofilaments too early, the penetration speed of resin is slow, the glass fibers cannot be effectively dispersed in the resin, the content of the glass fibers is uneven, and the strength and the surface performance of an SMC product are reduced; if the crosslinking degree is too high, the compatibility of the glass fiber and the matrix resin is influenced, and the strength of the product is influenced. The film forming agent of the prior SMC glass fiber impregnating compound is mainly formed by mixing general polyvinyl acetate emulsion, polyester emulsion, epoxy emulsion, polyurethane emulsion and acrylic emulsion, the styrene dissolving speed of the glass fiber impregnating compound can be adjusted by adjusting the content of cross-linked polyvinyl acetate, the impregnating speed is improved, and various problems can occur due to different types of polyvinyl acetate and matrix resin and poor compatibility, such as low mechanical strength, large strength fluctuation, low yield and the like of glass fiber reinforced plastic products. Therefore, the use and popularization of the current SMC forming process are not facilitated.
Disclosure of the invention
The invention aims to solve the technical problem of providing the impregnating compound and the application thereof in producing the twistless glass fiber roving for the reinforced structure type SMC sheet.
In order to solve the technical problems, the invention adopts the following technical scheme:
an impregnating compound comprises the following components: the coating comprises a coupling agent, a film-forming agent, a lubricant, a pH value regulator and water, wherein the coupling agent is a silane coupling agent, the film-forming agent is a mixture of non-crosslinking bisphenol A type polyester emulsion, crosslinking unsaturated polyester emulsion and medium and high molecular weight bisphenol A type epoxy emulsion, the epoxy equivalent of bisphenol A type epoxy resin in the medium and high molecular weight bisphenol A type epoxy emulsion is 1200-3600 g/eq, and the solid mass of the crosslinking unsaturated polyester emulsion, the non-crosslinking bisphenol A type polyester emulsion and the medium and high molecular weight bisphenol A type epoxy emulsion accounts for 60-80%, 10-20% and 10-20% of the total solid mass of the film-forming agent respectively; based on the impregnating compound, the content of each component is expressed by mass percent as follows, wherein the content of the film forming agent is calculated by the solid mass of the film forming agent accounting for the mass of the impregnating compound:
(1) silane coupling agent: 0.1-2.0%;
(2) film-forming agent: 5.0-35.0%;
(3) lubricant: 0.03-3.0%;
(4) pH value regulator: 0.01-2.0%;
(5) water: and (4) the balance.
Further, the impregnating compound is prepared from a coupling agent, a film forming agent, a lubricant, a pH value regulator and water.
The impregnating compound disclosed by the invention can be well compatible with unsaturated polyester resin, wherein the molecular structure of the film-forming agent is similar to that of the reinforced resin, so that glass fibers can be quickly dissolved by the reinforced matrix resin.
The film forming agent, which is the most important component in the sizing agent, plays a decisive role in the processing performance of the glass fiber. The film-forming agent is used as the main component of the impregnating compound, plays the roles of protecting glass fibers and improving the compatibility of the glass fibers and basic resin, meets the requirements of quick permeability and smoothness in the subsequent process of the glass fibers, ensures less broken filaments and good dispersibility in the short cutting process of the glass fibers, and can be uniformly mixed with matrix resin. The film forming agent of the conventional reinforcing structure type SMC glass fiber impregnating compound mainly comprises polyester emulsion, epoxy emulsion, polyvinyl acetate emulsion, polyurethane emulsion, acrylic emulsion and the like. The film-forming agent used in the present invention is preferably a combination of a crosslinking type unsaturated polyester emulsion, a non-crosslinking type bisphenol A type polyester emulsion and a medium-high molecular weight bisphenol A type epoxy emulsion. The bisphenol A type epoxy emulsion with medium and high molecular weight has the emulsion particle size of 0.2-3.0 microns, the acetone dissolution rate of 50-95 percent, the Tg of 10-40 ℃, and the epoxy equivalent of 1200-3600 g/eq; preferably, the medium-high molecular weight bisphenol A epoxy emulsion is polyester modified flexible bisphenol A epoxy emulsion with the epoxy equivalent of 1800-3000g/eq, the particle size of the emulsion is 0.3-2.0 microns, the acetone dissolution rate is 60-90%, and the Tg is 15-36 ℃. The non-crosslinked bisphenol A polyester emulsion has the advantages that a dried film can be dissolved in styrene, the Tg is 9-32 ℃, the preferred molecular weight is 4500-7000, the emulsion has the characteristic of fast styrene dissolution, the particle size is 0.2-1.0 micron, and the styrene dissolution rate is 70-100%. The crosslinking type unsaturated polyester emulsion has high crosslinking performance, preferably has the molecular weight of 1400-3400, and is relatively slowly soluble in styrene; the best is the cross-linking m-benzene unsaturated polyester emulsion, the grain diameter is between 0.2 and 1.0 micron, and the dissolution rate of the styrene is less than 20 percent. In the impregnating compound, the total content of the film forming agent is 5.0-35.0%, more preferably 10.0-30.0%, and most preferably 12.0-28.0%.
In the invention, the film forming agent in the impregnating compound is a mixture of crosslinking unsaturated polyester emulsion, non-crosslinking bisphenol A polyester emulsion and medium-high molecular weight bisphenol A epoxy emulsion, and the content ratio of the crosslinking unsaturated polyester emulsion, the non-crosslinking bisphenol A polyester emulsion and the medium-high molecular weight bisphenol A epoxy emulsion determines the penetrating speed of the impregnating compound and the stiffness and short-cut dispersibility of glass fibers, and plays a decisive role in SMC performance. Preferably, the solid mass of the crosslinking type unsaturated polyester emulsion accounts for 60-80% of the total solid mass of the film forming agent, the solid mass of the non-crosslinking type bisphenol A type polyester emulsion accounts for 10-20% of the total solid mass of the film forming agent, and the solid mass of the medium-high molecular weight bisphenol A type epoxy emulsion accounts for 10-20% of the total solid mass of the film forming agent; more preferably, the solid mass of the crosslinking type unsaturated polyester emulsion accounts for 60-71% of the total solid mass of the film forming agent, the solid mass of the non-crosslinking type bisphenol A type polyester emulsion accounts for 10-20% of the total solid mass of the film forming agent, and the solid mass of the medium-high molecular weight bisphenol A type epoxy emulsion accounts for 10-20% of the total solid mass of the film forming agent.
The coupling agent adopted by the invention is a compound of a cationic styrylamine functional silane coupling agent and a methacryloxy silane coupling agent. The total content of the coupling agent is 0.1-2.0%, preferably 0.3-1.5%, and most preferably 0.5-0.6%; wherein the content ratio of the cationic styrylamine-functional silane coupling agent to the methacryloxy silane coupling agent is 1:5 to 5: 1.
In the invention, the lubricant is one or a combination of more of cationic polyolefin amine, surfactant alkyl imidazoline derivative and nonionic methyl phenyl silicone oil. The content of the lubricant is 0.03 to 3.0%, preferably 0.03 to 2.0%, and most preferably 0.03 to 1.2%.
In the present invention, the pH adjuster is selected from one of the following: acetic acid, citric acid, formic acid, ammonia water and organic amine. The content of the pH value regulator is 0.01-2.0%, preferably 0.04-1.5%.
Preferably, based on the impregnating compound, the content of each component is expressed by mass percent as follows:
(1) silane coupling agent: 0.3 to 1.5 percent
(2) Film-forming agent: 10.0 to 30.0 percent
(3) Lubricant: 0.03 to 2.0 percent
(4) pH value regulator: 0.04 to 1.5 percent
(5) Water: and (4) the balance.
More preferably, the impregnating compound comprises the following components: the impregnating compound comprises a coupling agent, a film forming agent, a lubricant, a pH value regulator and water, wherein the content of each component is expressed by mass percent based on the impregnating compound as follows:
(1) silane coupling agent: 0.3 to 1.5 percent
(2) Film-forming agent: 10.0 to 30.0 percent
(3) Lubricant: 0.03 to 2.0 percent
(4) pH value regulator: 0.04 to 1.5 percent
(5) Water: balance of
The film forming agent is a mixture of non-crosslinking bisphenol A type polyester emulsion, crosslinking unsaturated polyester emulsion and medium-high molecular weight bisphenol A type epoxy emulsion, wherein the solid mass of the crosslinking unsaturated polyester emulsion, the non-crosslinking bisphenol A type polyester emulsion and the medium-high molecular weight bisphenol A type epoxy emulsion accounts for the total solid mass of the film forming agent, and the proportions of the solid mass of the crosslinking unsaturated polyester emulsion, the non-crosslinking bisphenol A type polyester emulsion and the medium-high molecular weight bisphenol A type epoxy emulsion in the total solid mass of the film forming agent are respectively as follows: 60-71%, 10-20% and 10-20%. (ii) a The epoxy equivalent of the bisphenol A type epoxy emulsion with medium and high molecular weight is 1200-3600 g/eq; the molecular weight of the non-crosslinked bisphenol A polyester emulsion is 4500-7000; the crosslinking type unsaturated polyester emulsion is crosslinking type m-benzene type unsaturated polyester emulsion, and the molecular weight is 1400-3400;
the coupling agent is a compound of a cationic styrylamine-functional silane coupling agent and a methacryloxy silane coupling agent, wherein the content ratio of the cationic styrylamine-functional silane coupling agent to the methacryloxy silane coupling agent is 1: 5-5: 1;
the lubricant is one or a combination of more of cationic polyolefin amine, surfactant alkyl imidazoline derivatives and nonionic methyl phenyl silicone oil;
the pH value regulator is selected from one of the following: acetic acid, citric acid, formic acid, ammonia water and organic amine.
Still more preferably, the impregnating compound comprises the following components: the impregnating compound comprises a coupling agent, a film forming agent, a lubricant, a pH value regulator and water, wherein the content of each component is expressed by mass percent based on the impregnating compound as follows:
(1) silane coupling agent: 0.5 to 0.6 percent
(2) Film-forming agent: 12.0 to 28.0 percent
(3) Lubricant: 0.03 to 1.2 percent
(4) pH value regulator: 0.04 to 1.5 percent
(5) Water: and (4) the balance.
More preferably, the medium-high molecular weight bisphenol A epoxy emulsion is a polyester modified flexible bisphenol A epoxy emulsion with the epoxy equivalent of 1800-3000 g/eq.
Still more preferably, the impregnating compound is prepared from a coupling agent, a film forming agent, a lubricant, a pH value regulator and water.
The impregnating compound can be prepared by the following method:
1. predispersing cationic styrylamine-functional silane coupling agent: firstly, adding deionized water with the weight of 1/4 of the cationic styrylamine functional group silane coupling agent into a clean coupling agent disperser, adding a pH value regulator, stirring for 4-5 minutes, then slowly adding the cationic styrylamine functional group silane coupling agent under the stirring state, and stirring for 25-30 minutes until the mixture is transparent;
2. dispersing cationic styrylamine-functional silane coupling agent: firstly, adding deionized water with the weight about 10 times of that of the pre-dispersed cationic styrene amine functional group silane coupling agent into a clean coupling agent disperser, then adding a pH value regulator, controlling the pH value to be 3.5-5.0, slowly adding the pre-dispersed cationic styrene amine functional group silane coupling agent under the stirring state, and stirring until the mixture is clear;
3. dispersed methacryloxy silane coupling agent: firstly, adding deionized water with the weight about 50 times that of a methacryloxy silane coupling agent into a clean coupling agent disperser, then adding a pH value regulator, controlling the pH value to be 3.5-4.0, slowly adding the methacryloxy silane coupling agent in a stirring state, and stirring until the mixture is clear;
4. pre-dissolving and diluting the lubricant: dissolving and diluting the lubricant into an unsaturated solution by using deionized water with the weight of 10-15 times of the lubricant and the temperature of about 80 ℃;
5. dissolving and diluting other raw materials by using deionized water of which the volume is about 2-3 times that of the raw materials;
the feeding sequence is as follows: the deionized water of 1/3 weight of the prepared size → the silane coupling agent dispersion liquid → the film forming agent → the lubricant solution → the rest of the deionized water is added into the preparation kettle. And (3) continuously stirring for 20-25 minutes after the materials are added, and simultaneously, controlling the pH value of the impregnating compound solution by adding a pH value regulator in the preparation process.
The amount of each component in the above preparation process needs to satisfy the proportional relationship of the present invention, and those skilled in the art can adaptively adjust the above preparation method according to actual conditions.
The invention also provides an application of the impregnating compound in producing the untwisted glass fiber roving for the reinforced structure type SMC sheet.
In the invention, the LOI (combustible content) of the glass fiber yarn is generally controlled to be 0.70-1.80%, the specific dosage is determined according to the performance of the raw materials and the performance index and experimental test result which need to be achieved by the product, and the LOI of 1.00-1.60% can meet the requirements of the production process.
The roving of the untwisted glass fiber is generally drawn by a 400-3200-hole platinum bushing, each final precursor is formed by stranding 200-400 monofilaments, the optimum is synthesized by 200 monofilaments, the diameter of each monofilament is controlled to be 12-16 microns, the drying process can adopt microwave and hot air drying, the optimum drying mode adopts hot air drying, the drying time is 10-16 hours, and the specific drying process can be determined according to the drying film forming condition and the migration condition. The number of the final product precursor is 2400-4800 tex, and the product can be produced according to the requirements of customers. The glass fiber yarn produced by using the impregnating compound has the characteristics of good short cutting property, accelerated glass fiber penetration, capability of improving the mechanical strength of glass fiber reinforced unsaturated polyester and the like.
The invention further provides an SMC sheet with the structure reinforced by the untwisted glass fiber roving, wherein the untwisted glass fiber roving is prepared by adopting the impregnating compound.
In the invention, the preparation of the twistless glass fiber roving reinforced structural SMC sheet adopts a conventional process.
Compared with the prior art, the invention has the beneficial effects that:
a) the film forming agent in the existing impregnating compound selects a mixture of conventional polyester and PVAc emulsion, while the mixture of crosslinking unsaturated polyester emulsion, non-crosslinking bisphenol A polyester emulsion and medium-high molecular weight bisphenol A epoxy emulsion is selected as the film forming agent in the invention, so that the dissolving speed of styrene of the glass fiber impregnating compound can be controlled, the impregnating speed in the production process of SMC sheets is improved, and the production efficiency is improved; in addition, the use of the epoxy resin emulsion of the medium-high molecular bisphenol A type can improve the bundling property of the glass fiber, reduce hairiness and improve the production smoothness.
b) The conventional silane coupling agent is used in the formula of the traditional sizing agent, and the compound of the cationic styrene amine functional group silane coupling agent and the gamma-methacryloxy trimethoxy silane is preferably used as the coupling agent in the method, so that the short cutting property of the glass fiber can be greatly improved, the interface bonding property between the glass fiber and matrix resin can be improved, and the mechanical strength of a composite material product can be improved.
(IV) detailed description of the preferred embodiments
The technical solution of the present invention is further described below by using specific examples, but the scope of the present invention is not limited thereto:
raw material use description:
the crosslinking unsaturated polyester emulsion (marked as emulsion film forming agent A) adopts TX-120 produced by a megalithic plant;
the non-crosslinking bisphenol A polyester emulsion (marked as emulsion film former B) is produced by the DSM company as Neoxil 2105;
the high-molecular-weight bisphenol A type epoxy emulsion (marked as emulsion film former C) is EPI-REZresin3540 produced by HEXION company;
the proportion of the solid mass of the emulsion film-forming agent A, B, C to the total solid mass of the film-forming agent is generally as follows:
a accounts for 60-80%; b accounts for 10-20%; c accounts for 10-20%. Thus, the bundling property of the impregnating compound can be ensured, and the permeation speed can be improved.
The lubricant adopts cation alkyl imidazoline derivative Cationic SoftenerConc.Flakes produced by EVONIK company in Germany;
acetic acid is used as pH value regulator;
silane coupling agents used were A-174 (designated as coupling agent A) from Meiji corporation, USA, and EVONIKIDynasylan 1178 (designated as coupling agent B) from Germany.
The final pH value of the impregnating compound is controlled to be 4.0-7.0, and the LOI value is controlled to be 1.0-1.8%.
Table 1 shows some examples of formulations (where the values are weight percent of the sizing and the weight percent of the film former is based on the solid mass of the sizing as a percentage of the mass of the sizing):
| components | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| Coupling agent A | 0.1 | 0.2 | 0.4 | 0.5 | 0.3 | 0.3 | 0.4 | 0.5 |
| Coupling agent B | 0.45 | 0.3 | 0.2 | 0.1 | 0.3 | 0.3 | 0.2 | 0.2 |
| Lubricant agent | 0.03 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.8 |
| Film forming agent A | 15.5 | 13 | 12 | 12.2 | 12 | 11 | 9.5 | 8.5 |
| Film-forming agent B | 4.5 | 4 | 3 | 2.5 | 3 | 2.5 | 2.2 | 2 |
| Film-forming agent C | 4 | 3.5 | 3.5 | 3.4 | 2 | 2.5 | 2.5 | 1.5 |
| pH value regulator | 0.1 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 2 |
| Deionized water | Balance of | Balance of | Balance of | Balance of | Balance of | Balance of | Balance of | Balance of |
| LOI(％) | 1.80 | 1.60 | 1.40 | 1.35 | 1.25 | 1.20 | 1.10 | 1.00 |
The drawing process adopted in the experiment is that a platinum bushing with 2400 holes is drawn by three branches to form four-beam drawing, each final precursor is formed by stranding 200 monofilaments, the diameter of each monofilament is controlled to be 14 micrometers, the drying process is hot air drying, and the drying time is 12 hours. A 4800Tex ply laid zero twist roving was produced.
Comparative example: 0.50% of coupling agent Dynasylan MEMO, 9.0% of film former D (unsaturated polyester emulsion DSM Nexil966), 8% of film former E (polyvinyl acetate emulsion Vinamul8852), 1.5% of film former F (polyurethane emulsion DIC 1980), 0.2% of antistatic agent Nexil AO83634, 0.2% of lubricant DSM LC 88710: 0.25 percent of deionized water and the balance.
The glass fiber plied twistless roving reinforced structural SMC sheet process produced using these formulation examples and comparative examples, using rich-rhomb FL-9508 unsaturated polyester, has the following test results:
| testing performance | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example |
| Acetone dissolution (%) | 65 | 55 | 51 | 62 | 61 | 59 | 65 | 72 | 60 |
| Short cutting Property (g/min) | 1510 | 1190 | 1470 | 1390 | 1350 | 1280 | 1257 | 1380 | 1051 |
| Speed of penetration (S) | 121 | 145 | 133 | 152 | 124 | 137 | 143 | 141 | 178 |
| Amount of feather (mg) | 0.07 | 0.12 | 0.14 | 0.12 | 0.06 | 0.33 | 0.71 | 0.34 | 0.64 |
| Tensile Strength (Mpsi) | 11.9 | 11.1 | 11.9 | 11.4 | 11.2 | 11.3 | 11.9 | 11.4 | 10.3 |
| Flexural strength (Mpsi) | 28.2 | 27.1 | 27.5 | 27.6 | 28.3 | 27.5 | 27.3 | 27.8 | 26.7 |
| Glass fiber content (%) | 26.96 | 27.02 | 26.99 | 27.04 | 27.11 | 26.94 | 27.16 | 26.96 | 26.83 |
The above test data were measured according to the general glass fiber product test method, wherein the tensile strength was measured according to ASTM D638 and the flexural strength was measured according to ASTM D790. From the above formulation test examples, we can see that examples 1 and 5 best meet the design requirements, the strength of the product is higher than the conventional one, the short-cut property is better than the conventional one, and the other basically can meet the general requirements, but the above proportions still have the space for optimizing.
According to the technical characteristics of the SMC production process, the embodiment of the invention produces the structural glass fiber product for SMC, which meets the requirements of high-end customers, by selecting the raw materials of the impregnating compound, optimizing the formula and adopting a proper and mature glass fiber production process.
Claims (9)
1. A sizing agent for producing untwisted glass fiber roving for a reinforced structure type SMC sheet comprises the following components: the adhesive comprises a coupling agent, a film forming agent, a lubricant, a pH value regulator and water, wherein the coupling agent is a compound of a cationic styrylamine functional silane coupling agent and a methacryloxy silane coupling agent, and the content ratio of the cationic styrylamine functional silane coupling agent to the methacryloxy silane coupling agent is 1: 5-5: 1; the film forming agent is a mixture of non-crosslinking bisphenol A type polyester emulsion, crosslinking unsaturated polyester emulsion and medium and high molecular weight bisphenol A type epoxy emulsion, the epoxy equivalent of bisphenol A type epoxy resin in the medium and high molecular weight bisphenol A type epoxy emulsion is 1200-3600 g/eq, and the solid mass of the crosslinking unsaturated polyester emulsion, the non-crosslinking bisphenol A type polyester emulsion and the medium and high molecular weight bisphenol A type epoxy emulsion accounts for 60-80%, 10-20% and 10-20% of the total solid mass of the film forming agent respectively; based on the impregnating compound, the content of each component is expressed by mass percent as follows, wherein the content of the film forming agent is calculated by the solid mass of the film forming agent accounting for the mass percent of the impregnating compound:
(1) coupling agent: 0.1-2.0%;
(2) film-forming agent: 5.0-35.0%;
(3) lubricant: 0.03-3.0%;
(4) pH value regulator: 0.01-2.0%;
(5) water: and (4) the balance.
2. An impregnating compound as defined in claim 1, wherein: the impregnating compound is prepared from a coupling agent, a film forming agent, a lubricant, a pH value regulator and water.
3. An impregnating compound according to claim 1 or 2, wherein: the content of each component is expressed by mass percent as follows:
(1) coupling agent: 0.3 to 1.5 percent
(2) Film-forming agent: 10.0 to 30.0 percent
(3) Lubricant: 0.03 to 2.0 percent
(4) pH value regulator: 0.04 to 1.5 percent
(5) Water: and (4) the balance.
4. An impregnating compound as defined in claim 3, wherein: the content of each component is expressed by mass percent as follows:
(1) coupling agent: 0.5 to 0.6 percent
(2) Film-forming agent: 12.0 to 28.0 percent
(3) Lubricant: 0.03 to 1.2 percent
(4) pH value regulator: 0.04 to 1.5 percent
(5) Water: and (4) the balance.
5. An impregnating agent according to any one of claims 1 to 4, wherein: the film forming agent is a mixture of non-crosslinking bisphenol A type polyester emulsion, crosslinking unsaturated polyester emulsion and medium-high molecular weight bisphenol A type epoxy emulsion, wherein the solid mass of the crosslinking unsaturated polyester emulsion, the non-crosslinking bisphenol A type polyester emulsion and the medium-high molecular weight bisphenol A type epoxy emulsion accounts for the total solid mass of the film forming agent, and the proportions of the solid mass of the crosslinking unsaturated polyester emulsion, the non-crosslinking bisphenol A type polyester emulsion and the medium-high molecular weight bisphenol A type epoxy emulsion in the total solid mass of the film forming agent are respectively as follows: 60-71%, 10-20% and 10-20%.
6. An impregnating agent according to any one of claims 1 to 4, wherein: the molecular weight of the non-crosslinked bisphenol A polyester emulsion is 4500-7000; the crosslinking type unsaturated polyester emulsion is crosslinking type m-benzene type unsaturated polyester emulsion, and the molecular weight is 1400-3400.
7. An impregnating compound as defined in claim 6, wherein: the medium-high molecular weight bisphenol A epoxy emulsion is polyester modified flexible bisphenol A epoxy emulsion with the epoxy equivalent of 1800-3000 g/eq.
8. An impregnating compound as defined in claim 5, wherein: the lubricant is one or a combination of more of cationic polyolefin amine, surfactant alkyl imidazoline derivatives and nonionic methyl phenyl silicone oil; the pH value regulator is selected from one of the following: acetic acid, citric acid, formic acid, ammonia water, organic amines; the molecular weight of the non-crosslinked bisphenol A polyester emulsion is 4500-7000; the crosslinking type unsaturated polyester emulsion is crosslinking type m-benzene type unsaturated polyester emulsion, and the molecular weight is 1400-3400; the medium-high molecular weight bisphenol A epoxy emulsion is polyester modified flexible bisphenol A epoxy emulsion with the epoxy equivalent of 1800-3000 g/eq; the coupling agent is a compound of a cationic styrylamine-functional silane coupling agent and a methacryloxy silane coupling agent, wherein the content ratio of the cationic styrylamine-functional silane coupling agent to the methacryloxy silane coupling agent is 1: 5-5: 1.
9. Use of the sizing of claim 1 in the production of roving of untwisted glass fibers for use in the production of SMC sheets of reinforced structural type.
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| CN112194387A (en) * | 2020-10-21 | 2021-01-08 | 河南神玖天航新材料股份有限公司 | Quartz fiber monofilament dispersion type chopped strand impregnating compound and preparation method thereof |
| CN112456817A (en) * | 2020-11-20 | 2021-03-09 | 巨石集团有限公司 | Enhanced glass fiber impregnating compound and preparation method and application thereof |
| CN113072308A (en) * | 2021-03-25 | 2021-07-06 | 邢台金牛玻纤有限责任公司 | Low-chroma BMC (bulk molding compound) glass fiber impregnating compound |
| CN112830688B (en) * | 2021-04-16 | 2022-08-09 | 巨石集团有限公司 | Impregnating compound for glass fiber and preparation and application thereof |
| CN113666647B (en) * | 2021-07-09 | 2022-11-15 | 山东玻纤集团股份有限公司 | Preparation method of high-performance direct twistless roving |
| CN115124262A (en) * | 2022-08-25 | 2022-09-30 | 淄博卓意玻纤材料有限公司 | Glass fiber impregnating compound for milk bottle |
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