A high-temperature starch-type wetting agent and its preparation method and application

Abstract

The present invention relates to a high-temperature starch-type wetting agent and a preparation method and application thereof, wherein the wetting agent comprises an active ingredient and water, wherein the mass ratio of the active ingredient to the water is (0.05-0.15): 1, and the active ingredient comprises the following raw materials in parts by weight: 45-65 parts of a starch-based film-forming agent, 5-10 parts of a plasticizer, 15-20 parts of a lubricant, 1-2.5 parts of an emulsifier, 4-6 parts of a coupling agent, 0.5-1.5 parts of a preservative, and 0.02-0.05 parts of a defoaming agent; wherein the plasticizer is cardanol acetate, tributyl citrate, and mannitol in a mass ratio of 1:1:(1.5-2); and the starch-based film-forming agent is at least one of acetylated distarch adipate, oxidized starch, and hydroxypropyl starch. The glass fiber yarn products produced with the wetting agent have significantly reduced scattered silk defects on the cloth surface, and the amount of powder falling during the weaving process is also greatly reduced, which meets the high standard requirements for the production of printed circuit boards.

Description

Technical Field

[0001] The invention relates to the technical field of glass fiber surface treatment agents, and in particular to a high-temperature starch-type sizing agent and a preparation method and application thereof. Background Art

[0002] Electronic-grade glass fiber is the core material for the manufacture of printed circuit boards. The drawing, twisting and weaving links in its production process must be strictly controlled. In order to optimize the textile processing characteristics of electronic-grade glass fiber yarn, a wetting agent is usually coated on its surface. Currently, starch-based wetting agents are widely used in this coating process. Starch-based wetting agents can effectively enhance the bundling and protection properties of yarns, significantly reduce the phenomenon of lint during the desizing and weaving process, and its composition is easy to heat desizing and has a low decomposition temperature. The yarn after post-treatment is white in color, without black-brown stripes, and has low ash residue, ensuring the excellent electrical insulation properties of the final product.

[0003] According to the different cooking temperatures and methods of starch during the production process, starch-based wetting agents can be divided into two types: high-temperature and low-temperature. High-temperature starch-based wetting agents use a continuous high-temperature and high-pressure cooking process, which significantly improves production efficiency; while low-temperature starch-based wetting agents are prepared by normal pressure cooking, making the production process easier to control.

[0004] Although high-temperature starch-based sizing agents have certain advantages in glass fiber production, they also have some disadvantages, which are mainly reflected in the following aspects:

[0005] High-temperature starch-based wetting agents generally have the problem of poor textile performance in practical applications, especially the phenomenon of loose fibers is prone to occur during the weaving process, resulting in reduced production efficiency. When using high-temperature starch-based wetting agents, the operating rate of glass fiber production and the utilization rate of the wetting agent are often not high, which directly affects production efficiency and cost. Due to the film-forming properties of the starch-based wetting agent, the stiffness of the coated yarn is relatively high, which may cause the yarn to be insufficiently flexible in subsequent processing, affecting weaving performance. Traditional high-temperature starch-based wetting agents may still produce more hairiness and powdering during the production process due to their poor wear resistance, affecting product quality. Summary of the invention

[0006] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a high-temperature starch-type wetting agent and a preparation method and application thereof. The glass fiber yarn products produced with the wetting agent have significantly reduced loose fiber defects on the surface, and the amount of powder falling during the weaving process is also greatly reduced, which meets the high standard requirements for the production of printed circuit boards.

[0007] To achieve the above object, the technical solution adopted by the present invention is:

[0008] In a first aspect, the present invention provides a high-temperature starch-based wetting agent, the wetting agent comprising an active ingredient and water, the mass ratio of the active ingredient to water being (0.05-0.15): 1, the active ingredient comprising the following raw materials in parts by weight: 45-65 parts of a starch-based film-forming agent, 5-10 parts of a plasticizer, 15-20 parts of a lubricant, 1-2.5 parts of an emulsifier, 4-6 parts of a coupling agent, 0.5-1.5 parts of a preservative, and 0.02-0.05 parts of a defoaming agent;

[0009] The plasticizer is cardanol acetate, tributyl citrate and mannitol in a mass ratio of 1:1:(1.5-2); the starch-based film-forming agent is at least one of acetylated distarch adipate, oxidized starch and hydroxypropyl starch.

[0010] Both cardanol acetate and tributyl citrate contain ester groups, which can form hydrogen bond interactions with hydroxyl groups (OH-) in starch molecules, thereby destroying the hydrogen bond network between starch molecules and making starch molecular chains more flexible and mobile, which helps to reduce the stiffness of yarns treated with starch-based impregnation agents and increase their softness and plasticity. The benzene ring in cardanol acetate provides good thermal and chemical stability, allowing the impregnation agent to maintain hydrophobic properties even at high temperatures. Tributyl citrate also has a long butyl side chain, which can act as a steric hindrance to prevent excessive aggregation of starch molecular chains, thereby increasing the activity space of starch molecular chains, reducing the stiffness of the yarn and making it softer. Mannitol, as a plasticizer, can significantly improve the flexibility of starch films. The multiple hydroxyl groups in its molecular structure can form hydrogen bonds with starch molecules, thereby reducing the interaction between starch molecules and increasing the flexibility of the film. Mannitol can also act as a lubricant, helping to reduce friction and wear. Cardanol acetate, tributyl citrate and mannitol can significantly reduce the yarn stiffness of starch-based sizings through the action of their functional groups. These plasticizers can improve the flexibility and processing properties of the yarn by weakening the interaction between starch molecules and increasing the flexibility of the molecular chain. These three plasticizers work synergistically to form a stable network structure in the starch-based sizing, which helps to enhance the overall strength and durability of the sizing, thereby improving wear resistance.

[0011] Preferably, the lubricant is paraffin and / or ethylene bisoleamide.

[0012] Preferably, the preservative is sodium methyl paraben.

[0013] Preferably, the emulsifier is polyoxyethylene fatty acid ester.

[0014] Preferably, the defoaming agent is a phosphate defoaming agent.

[0015] Preferably, the starch-based film-forming agent is a composition of acetylated distarch adipate, oxidized starch and hydroxypropyl starch in a mass ratio of (0.5-1):1:(1-1.2). The low gelatinization temperature of acetylated distarch adipate and oxidized starch can quickly form a preliminary film structure, while the high gelatinization temperature of hydroxypropyl starch can further enhance the strength and toughness of the film in subsequent high-temperature treatment. Acetylated distarch adipate, oxidized starch and hydroxypropyl starch will complement each other in function, improve the film-forming effect of starch, make the starch film less prone to friction and damage, and significantly improve the wear resistance and damage resistance of the film.

[0016] Preferably, the coupling agent is a silane coupling agent.

[0017] In a second aspect, the present invention provides a method for preparing the high temperature starch-type wetting agent in the first aspect, comprising the following steps:

[0018] S1, mixing the starch-based film-forming agent in a formula amount with water, stirring evenly, heating and keeping warm, and cooling to obtain a film-forming agent solution;

[0019] S2, mixing the formulated amount of plasticizer, lubricant, emulsifier, coupling agent, preservative and defoamer, stirring evenly to obtain an additive solution;

[0020] S3, mixing the film-forming agent solution and the auxiliary agent solution, stirring until an emulsion is formed, and obtaining the starch-based wetting agent.

[0021] Preferably, in step S1, the stirring speed is 200-300 rpm, the stirring time is 10-20 min, the insulation temperature is 90-100° C., and the insulation time is 20-40 min.

[0022] Preferably, in step S1, the step of mixing the starch-based film-forming agent with water is carried out in a high-temperature and high-pressure cooker.

[0023] Preferably, the stirring temperature in step S2 and step S3 is 60-70° C., the stirring speed is 300-500 rpm, and the stirring time is 20-40 min.

[0024] In a third aspect, the present invention provides the use of the high temperature starch-type wetting agent in the first aspect in the preparation of glass fiber textile spun yarn.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The high-temperature starch wetting agent of the present invention adds cardanol acetate, tributyl citrate and mannitol as plasticizers, and the three have a synergistic effect, increase the flexibility of starch molecular chains, significantly reduce yarn stiffness, improve softness and plasticity, and also weaken the intermolecular forces of starch, enhance the flexibility of molecular chains, form a stable network structure, enhance the strength and durability of the wetting agent, and improve the wear resistance of starch film. The glass fiber yarn products produced with the wetting agent have significantly reduced scattered silk defects on the cloth surface, and the amount of powder falling during weaving is also greatly reduced, which meets the high standard requirements for the production of printed circuit boards. DETAILED DESCRIPTION

[0027] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0028] The sources of the raw materials used in the following examples and comparative examples are as follows:

[0029] Cardanol acetate: the manufacturer is Fuyong (Shandong) Biotechnology Co., Ltd., the model is Cardanol acetate grade A product;

[0030] Tributyl citrate: manufacturer is Guangdong Wengjiang Chemical Reagent Co., Ltd., model number is PB06267;

[0031] Mannitol: manufacturer is Guangdong Wengjiang Chemical Reagent Co., Ltd., model number is DA00385;

[0032] Acetylated distarch adipate: the manufacturer is Hangzhou Prostar Starch Co., Ltd.;

[0033] Oxidized starch: the manufacturer is Foshan Nanhai Huahao Huafeng Starch Co., Ltd.

[0034] Hydroxypropyl starch: the manufacturer is Hangzhou Prostar Starch Co., Ltd.

[0035] Paraffin: manufacturer is Guangdong Wengjiang Chemical Reagent Co., Ltd., model number is DB00867;

[0036] Ethylene bisoleamide: manufacturer is Guangdong Wengjiang Chemical Reagent Co., Ltd., model number is PA12872;

[0037] Fatty acid polyoxyethylene ester: manufacturer is Jiangsu Hai'an Petrochemical Plant, model SG-9;

[0038] Silane coupling agent: γ-aminopropyltriethoxysilane, manufactured by Wuhan Xinyang Ruihe Chemical Technology Co., Ltd., model KH-550;

[0039] Preservative: sodium methyl paraben, manufacturer is Guangdong Wengjiang Chemical Reagent Co., Ltd., brand name PA59051;

[0040] Defoamer: Phosphate defoamer, manufacturer: Guangzhou Oupeng Chemical Co., Ltd., model: MOUSSEX ® 941PL;

[0041] Unless otherwise specified, other materials, reagents, etc. used in the examples can be obtained from commercial sources.

[0042] Example 1

[0043] A high-temperature starch-based wetting agent, the wetting agent comprising an active ingredient and water, the mass ratio of the active ingredient to water being 0.1:1, the active ingredient comprising the following raw materials in parts by weight: 45-65 parts of a starch-based film-forming agent, 7 parts of a plasticizer, 16 parts of a lubricant, 2 parts of an emulsifier, 5 parts of a coupling agent, 1 part of a preservative, and 0.03 parts of a defoaming agent;

[0044] Among them, the plasticizer is cardanol acetate, tributyl citrate and mannitol in a mass ratio of 1:1:1.8; the starch-based film-forming agent is a composition of acetylated distarch adipate, oxidized starch and hydroxypropyl starch in a mass ratio of 0.6:1:1.1; the lubricant is paraffin and ethylenebisoleamide in a mass ratio of 1:1, the emulsifier is fatty acid polyoxyethylene ester, the silane coupling agent is γ-aminopropyl triethoxysilane, the preservative is sodium methyl parahydroxybenzoate, and the defoaming agent is a phosphate defoaming agent.

[0045] The preparation method of the high temperature starch type wetting agent comprises the following steps:

[0046] S1. Mix the starch-based film-forming agent in the formula amount with water, stir at 250 rpm for 150 min, heat to 95° C. and keep warm for 25 min, and cool to obtain a film-forming agent solution;

[0047] S2, mixing the formulated amount of plasticizer, lubricant, emulsifier, coupling agent, preservative and defoamer, stirring at a temperature of 65° C. and a rotation speed of 400 rpm for 30 min to obtain an additive solution;

[0048] S3, mixing the film-forming agent solution and the auxiliary agent solution, stirring at 65° C. and 400 rpm for 30 min to form an emulsion, and obtaining the starch-based wetting agent.

[0049] Example 2

[0050] A high-temperature starch-based wetting agent, the wetting agent comprising an active ingredient and water, the mass ratio of the active ingredient to water being 0.05:1, the active ingredient comprising the following raw materials in parts by weight: 65 parts of a starch-based film-forming agent, 10 parts of a plasticizer, 20 parts of a lubricant, 2.5 parts of an emulsifier, 6 parts of a coupling agent, 1.5 parts of a preservative, and 0.05 parts of a defoaming agent;

[0051] Among them, the plasticizer is cardanol acetate, tributyl citrate and mannitol in a mass ratio of 1:1:2; the starch-based film-forming agent is a composition of acetylated distarch adipate, oxidized starch and hydroxypropyl starch in a mass ratio of 1:1:1.2, the lubricant is paraffin, the emulsifier is fatty acid polyoxyethylene ester, the silane coupling agent is γ-aminopropyl triethoxysilane, the preservative is sodium methyl parahydroxybenzoate, and the defoamer is a phosphate defoamer.

[0052] The preparation method of the high temperature starch type wetting agent comprises the following steps:

[0053] S1. Mix the starch-based film-forming agent in the formula amount with water, stir at 300 rpm for 20 min, heat to 100° C. and keep warm for 20 min, and cool to obtain a film-forming agent solution;

[0054] S2, mixing the formulated amount of plasticizer, lubricant, emulsifier, coupling agent, preservative and defoamer, stirring at a temperature of 70° C. and a rotation speed of 500 rpm for 20 min to obtain an additive solution;

[0055] S3, mixing the film-forming agent solution with the auxiliary agent solution, stirring at 70° C. and 500 rpm for 20-40 min to form an emulsion, and obtaining the starch-based wetting agent.

[0056] Example 3

[0057] A high-temperature starch-based wetting agent, the wetting agent comprising an active ingredient and water, the mass ratio of the active ingredient to water being 0.15:1, the active ingredient comprising the following raw materials in parts by weight: 45 parts of a starch-based film-forming agent, 5 parts of a plasticizer, 15 parts of a lubricant, 1 part of an emulsifier, 4 parts of a coupling agent, 0.5 parts of a preservative, and 0.02 parts of a defoaming agent;

[0058] Among them, the plasticizer is cardanol acetate, tributyl citrate and mannitol in a mass ratio of 1:1:1.5; the starch-based film-forming agent is a composition of acetylated distarch adipate, oxidized starch and hydroxypropyl starch in a mass ratio of 0.5:1:1, the lubricant is ethylene bisoleamide, the emulsifier is fatty acid polyoxyethylene ester, the silane coupling agent is γ-aminopropyl triethoxysilane, the preservative is sodium methyl parahydroxybenzoate, and the defoaming agent is a phosphate defoaming agent.

[0059] The preparation method of the high temperature starch type wetting agent comprises the following steps:

[0060] S1. Mix the starch-based film-forming agent in the formula amount with water, stir at 200 rpm for 20 min, heat to 90° C. and keep warm for 40 min, and cool to obtain a film-forming agent solution;

[0061] S2, mixing the formulated amounts of plasticizer, lubricant, emulsifier, coupling agent, preservative and defoamer, stirring at a temperature of 60° C. and a rotation speed of 300 rpm for 40 min to obtain an additive solution;

[0062] S3, mixing the film-forming agent solution and the auxiliary agent solution, stirring at 60° C. and 300 rpm for 40 min to form an emulsion, and obtaining the starch-based wetting agent.

[0063] Example 4

[0064] The difference between Example 4 and Example 1 is that the amount of starch-based film-forming agent added remains unchanged, acetylated distarch adipate is not added, and oxidized starch and hydroxypropyl starch in a mass ratio of 1:1.1 are used to make up for the missing amount.

[0065] Example 5

[0066] The difference between Example 5 and Example 1 is that the amount of starch-based film-forming agent added remains unchanged, oxidized starch is not added, and acetylated distarch adipate and hydroxypropyl starch in a mass ratio of 0.6:1.1 are used to make up for the missing amount.

[0067] Example 6

[0068] The difference between Example 6 and Example 1 is that the amount of starch-based film-forming agent added remains unchanged, hydroxypropyl starch is not added, and acetylated distarch adipate and oxidized starch in a mass ratio of 0.6:1 are used to make up for the missing amount.

[0069] Comparative Example 1

[0070] The difference between Comparative Example 1 and Example 1 is that the total amount of plasticizer added remains unchanged, cardanol acetate is not added, and tributyl citrate and mannitol in a mass ratio of 1:1.8 are used to make up for the missing amount.

[0071] Comparative Example 2

[0072] The difference between Comparative Example 2 and Example 1 is that the total amount of plasticizer added remains unchanged, tributyl citrate is not added, and cardanol acetate and mannitol in a mass ratio of 1:1.8 are used to make up for the missing amount.

[0073] Comparative Example 3

[0074] The difference between Comparative Example 3 and Example 1 is that the total amount of plasticizer added remains unchanged, mannitol is not added, and cardanol acetate and tributyl citrate in a mass ratio of 1:1 are used to make up for the missing amount.

[0075] Comparative Example 4

[0076] The difference between Comparative Example 4 and Example 1 is that the total amount of plasticizer added remains unchanged, and the mass ratio of cardanol acetate, tributyl citrate and mannitol is 1:1.8:1.

[0077] Comparative Example 5

[0078] The difference between Comparative Example 5 and Example 1 is that the total amount of plasticizer added remains unchanged, and the mass ratio of cardanol acetate, tributyl citrate and mannitol is 1.8:1:1.

[0079] Performance Testing

[0080] Stiffness, hairiness, powder loss, surface loose fibers and the flexibility of fiber monofilaments are important performance indicators for evaluating glass fiber products. They directly affect the processing performance, use effect and final quality of the products. Specifically: Stiffness is a measure of the deformation resistance of glass fiber when subjected to bending load. The greater the stiffness, the less likely the glass fiber is to bend and deform during processing and use, and it shows higher rigidity. Hairiness refers to the number of fine fiber bundles formed on the surface of glass fiber due to fiber breakage or looseness. The fewer the hairiness, the better the surface quality of the glass fiber, the lower the possibility of fiber breakage during processing, and the higher the performance and appearance quality of the product. Powder loss refers to the amount of powder that falls off the surface of glass fiber during processing or use. The lower the powder loss, the better the wear resistance and stability of the fiber, and the less dust pollution generated during processing. Surface loose fibers refer to the number of loose fibers formed on the surface of glass fiber cloth due to fiber breakage or looseness during weaving. The fewer the surface loose fibers, the better the winding performance and weaving stability of the fiber, and the better the appearance quality and use performance of the product. The flexibility of fiber monofilament refers to the ratio of the critical diameter A of the glass fiber monofilament to the diameter d of the fiber filament after infiltration (the diameter of the fiber filament of each group of samples after infiltration is the same), which reflects the flexibility of the fiber monofilament. The smaller the flexibility value, the better the flexibility of the fiber monofilament.

[0081] The sizing agents of Examples 1-6 and Comparative Examples 1-5 were respectively applied to electronic grade glass fiber products with a single fiber diameter of 9 μm, the oil coating line speed was 18-20 m / min, the oil content of the bobbin was controlled at 1.2±0.20%, and the weaving speed was 700 rpm. The performance of the products after production was tested, and the test results are shown in Table 1.

[0082] Table 1 Performance data of each group of glass fiber products

[0083] Performance / Group Stiffness (mm) Average number of hairs (roots) Powder fall amount (mg / 10,000 meters) Scattered yarn on the fabric (pcs / 10,000 meters) Flexibility of fiber monofilament Example 1 103 0.6 10.0 6.4 29.1 Example 2 105 0.8 10.5 7.0 28.1 Example 3 107 0.8 10.3 6.8 28.1 Example 4 108 1.2 12.2 11.4 35.9 Example 5 106 1.0 12.1 11.2 36.1 Example 6 105 1.1 12.4 11.9 36.5 Comparative Example 1 106 1.8 19.5 20.9 55.4 Comparative Example 2 106 1.6 18.0 20.6 55.1 Comparative Example 3 105 1.8 19.3 20.4 54.6 Comparative Example 4 103 1.6 15.8 16.6 42.3 Comparative Example 5 107 1.5 15.6 16.9 42.6

[0084] As can be seen from Table 1, combined with the data of Example 1 and Examples 4-6, the starch-based film-forming agent of Example 1 is a compound of three starches: acetylated distarch adipate, oxidized starch and hydroxypropyl starch, which can significantly improve the flexibility, wear resistance and quality of glass fiber products.

[0085] Combining the data of Example 1 and Comparative Examples 1-3, it can be seen that the type of plasticizer has a great influence on the wear resistance and flexibility of the fabric. When cardanol acetate, tributyl citrate and mannitol are used in combination, the performance of the glass fiber product is better. When any one of cardanol acetate, tributyl citrate and mannitol is missing, the performance of the glass fiber product decreases.

[0086] Combining the data of Examples 1-3 and Comparative Examples 4-5, it can be seen that when the mass ratio of cardanol acetate, tributyl citrate and mannitol is 1:1:(1.5-2), the flexibility and wear resistance of the glass fiber product reach a better level.

[0087] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A high temperature starch type wetting agent, characterized in that: The wetting agent includes active ingredients and water, and the mass ratio of active ingredients to water is (0.05-0.15):

1. The active ingredients include the following raw materials in parts by weight: 45-65 parts of starch-based film-forming agent, 5-10 parts of plasticizer, 15-20 parts of lubricant, 1-2.5 parts of emulsifier, 4-6 parts of coupling agent, 0.5-1.5 parts of preservative and 0.02-0.05 parts of defoaming agent; The plasticizer is cardanol acetate, tributyl citrate and mannitol in a mass ratio of 1:1:(1.5-2); the starch-based film-forming agent is a composition of acetylated distarch adipate, oxidized starch and hydroxypropyl starch in a mass ratio of (0.5-1):1:(1-1.2).

2. The high temperature starch type wetting agent according to claim 1, characterized in that: The lubricant is paraffin and / or ethylene bisoleamide.

3. The high temperature starch type wetting agent according to claim 1, characterized in that: The preservative is sodium methyl parahydroxybenzoate; and / or the emulsifier is polyoxyethylene fatty acid ester.

4. The high temperature starch type wetting agent according to claim 1, characterized in that: The defoaming agent is a phosphate defoaming agent.

5. The high temperature starch type wetting agent according to claim 1, characterized in that: The coupling agent is a silane coupling agent.

6. The method for preparing the high temperature starch type wetting agent according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1, mixing the starch-based film-forming agent in a formula amount with water, stirring evenly, heating and keeping warm, and cooling to obtain a film-forming agent solution; S2, mixing the formulated amount of plasticizer, lubricant, emulsifier, coupling agent, preservative and defoamer, stirring evenly to obtain an additive solution; S3, mixing the film-forming agent solution and the auxiliary agent solution, stirring until an emulsion is formed, and obtaining the starch-based wetting agent.

7. The method for preparing the high temperature starch type wetting agent according to claim 6, characterized in that: In step S1, the stirring speed is 200-300 rpm, the stirring time is 10-20 min, the insulation temperature is 90-100° C., and the insulation time is 20-40 min.

8. The method for preparing the high temperature starch type wetting agent according to claim 6, characterized in that: The stirring temperature in step S2 and step S3 is 60-70° C., the stirring speed is 300-500 rpm, and the stirring time is 20-40 min.

9. Use of the high-temperature starch-type sizing agent according to any one of claims 1 to 5 in the preparation of glass fiber textile spun yarn.