JPS6336378B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a fabric-like glass fiber product that is effective as a base material for molding reinforced plastics, and in particular to a method for manufacturing glass fiber products such as glass fiber mat for reinforcing thermosetting synthetic resins or glass fiber roping cloth. be. Generally, when manufacturing glass fiber, hundreds to thousands of glass fiber filaments are spun out from a spinning furnace, and a binding agent is applied to them while dividing them into a single strand or into several strands and converging them. , is wound on the winding device. In this case, the basic elements required of the sizing agent include lubricity and protection of the filament and strands. That is, the sizing agent has the purpose of protecting the filaments and strands from friction between the filaments and strands during spinning and from various types of friction that occur in subsequent steps. Another factor is the improvement of the physical and chemical properties of glass fibers, which are necessary when molding reinforced plastics from resin and glass fibers. However, conventionally known sizing agents interfere with the bonding of resin and glass fibers, and are even harmful to the molding of reinforced plastics, so they are removed by a method such as heat cleaning before bonding of resin and glass fibers. The glass fibers were treated with a surface treatment agent that increased strength. Later, as a method to improve this, various methods were developed and researched, in which the above-mentioned surface treatment agent was mixed into a sizing agent and treated at once with a sizing agent that had both the functions of a sizing agent and a surface treatment agent. I am getting . However, since it is necessary to bundle a large number of filaments into a strand, all of these types of focusing agents contain components with adhesive strength, such as starch and vinyl synthetic resin emulsion, and the presence of such adhesive components is important for the resin and glass. The results show that it affects the binding strength of fibers and reduces the effectiveness of surface treatment agents. The present invention was developed based on this background, and it applies a sizing agent consisting only of a conventionally known surface treatment agent to the glass fiber filament being spun to improve its bonding strength with the thermosetting resin. The object of the present invention is to obtain fabric-like glass fiber products, particularly glass fiber mats or roving cloth, which are designed to increase It was possible to obtain a reinforced plastic molded product with strong bonding and extremely excellent performance. As the surface treatment agent used in the present invention, the already known organic silane compounds or organic chromium compounds shown in Table 1 are used as a 0.02 to 2% aqueous solution. The selection of agents to be used depends on the type of partner resin to which it is applied. There is no problem in adding a small amount of lubricant or surfactant as needed.

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[Table] Glass fiber filaments coated with such a surface treatment agent solution as a sizing agent are bundled into strands and wound up in a wet state to form a strand package. Next, a method for producing a glass fiber mat, which is one of the glass fiber products of the present invention, from the glass fiber strand package thus wound will be described. Conventionally, glass fiber mats have been manufactured using strand mats, in which glass fiber strands are pulled out of a package cage and deposited in free fall on a moving conveyor, and strand mats, in which the strands are pulled out from a package cage and cut into lengths of about 1 to 10 cm. Chopped strand pine is known as a chopped strand that is deposited on a moving conveyor. However, conventional glass fiber strands are already formed by bonding each filament together using an adhesive component in a sizing agent, but the sizing agent component of the present invention does not contain any such adhesive component. As the strands dry, they easily separate into filaments, increasing friction between the filaments and the strands, causing filament breakage, fuzzing, etc. formation becomes almost impossible. Therefore, the present invention solves the above-mentioned problems by pulling out the wet strands from the still wet package, forming a wet strand mat or chopped strand mat, and then drying this. We were able to obtain the desired glass fiber mat. Since the glass fiber pine obtained by the above method does not have any bonding state between the strands that make up the pine, it is necessary to fix the constituent strands and maintain the shape retention of the pine. For the purpose of improving strength, it is more preferable to needle punch the pine while it is still wet. Although already known needle punching devices can be used as is, glass fibers are susceptible to bending and abrasion, so it is difficult to push the filaments in the thickness direction of the mat without cutting any of the glass fiber filaments that make up the strands. Although it is difficult, when the strand is wet, even if some of the filament is cut, the strand itself will not be cut and will easily move and be pushed into the thickness direction of the mat. can. By changing the density of the needles of the needle punching device, the shape of the needles, the moving speed of the mat, the number of needle punches per unit time, etc., the amount and condition of the strands pushed in the thickness direction of the mat can be controlled. Of course, mats with various performances can be obtained by increasing or decreasing the amount as desired. Next, the roving cloth as a glass fiber product of the present invention is produced by pulling out the strands in a wet state from dozens of package cages that are still in a wet state, pulling them together to form a roving, and using this wet roving as a weft and warp thread. Roving cloth could be easily obtained by weaving it in a wet state and drying it. The roving cloth obtained by the above method retains its shape sufficiently, but in order to further strengthen its shape retention and give it strength in the thickness direction, needle punching is added to the wet roving cloth. There is no difference whatsoever. The glass fiber mat or roving cloth thus obtained, which is an example of the glass fiber product of the present invention, has the surface of the glass fiber coated with only a surface treatment agent that is a binder between the resin and the glass fiber. Since there are no components that inhibit the bonding of glass fibers, when the glass fiber product of the present invention is used as a reinforcing material for thermosetting resin, resin can be easily and quickly bonded not only between glass fiber strands but also between filaments. By impregnating the resin and curing it while firmly bonding the resin and glass fiber, we were able to obtain a glass fiber-reinforced plastic with extremely excellent performance. If the package of strands wound in a wet state becomes dry during storage, the strands are pulled out while applying moisture to the package by spraying or other appropriate methods to form mats or weave roving cloth. Trouble can be prevented by proceeding with work such as configuration. Further, if the concentration of the surface treating agent used in the present invention is less than 0.02%, no effect will be obtained, and if it is more than 2%, the surface treating agent will simply be wasted and is completely meaningless. In order to compare the performance with the glass fiber product of the present invention, the following samples were prepared. (A) Traditionally and widely used. Cationic surfactant 0.2 parts Nonionic lubricant 0.1 part Vinyl acetate emulsion 7.0 parts Water Residual 100 parts of sizing agent is applied to the bundled and wound strands as raw materials, and strand mats, chiyos, etc. Tupdo strand pine,
Each roving cloth was heat-cleaned to once remove the sizing agent, and then treated with (1) a 0.3% aqueous solution of γ-methacryloxypropyltrimethoxysilane and dried to prepare the following samples.

[Table] (2) The following samples were prepared by treating with a 0.3% aqueous solution of vinyltri(β-methoxyethoxy)silane and drying.

[Table] (3) Methacrylate chromic chloride
The following samples were prepared by treating with a 0.3% aqueous solution and drying.

[Table] (B) Surface treatment agent contained in the sizing agent component Surface treatment agent 0.3 parts Cationic surfactant 0.2 parts Nonionic lubricant 0.1 part Vinyl acetate emulsion 7.0 parts Water Remaining composition From the composition of 100 parts In the strand mat, chopped strand, mat, and roving cloth made from the bundled and wound strands as raw materials, the surface treatment agent is (1) γ. -The following samples were prepared using methacryloxypropyltrimethoxysilane.

[Table] (2) The following samples were prepared using vinyltri(β-methoxyethoxy)silane.

[Table] (3) The following samples were prepared using methacrylate chromic chloride.

[Table] (C) On the other hand, as the glass fiber product of the present invention,
Only a 0.3% aqueous solution of the surface treatment agent is applied as a sizing agent.In the strand mats, chopped strand mats, and roving cloths made from the bundled and wound strands as raw materials, 1 γ is added to the surface treatment agent. -The following samples were prepared using methacryloxypropyltrimethoxysilane.

[Table] 2 The following samples were prepared using vinyltri(β-methoxyethoxy)silane.

[Table] 3 The following samples were prepared using methacrylate chromic chloride.

[Table] The density of needle punching in each of the above samples is 20 punches/cm ² for strand pine and chopped strand pine, and 50 punches/cm ² for roving cloth. All the samples obtained in this way were impregnated with unsaturated polyester resin according to a conventional method, and then hardened and molded using a pressure molding method to obtain a glass fiber reinforced plastic material, which is the most representative material for comparative study of its performance. The bending strength in dry and wet conditions and the degree of whitening were tested, and the results shown in the table below were obtained. The unsaturated polyester resin used was Rigorakku 157 manufactured by Showa Kobunshi Co., Ltd., and the bending strength was measured in accordance with JIS K6911. Wet bending strength was measured after each sample was boiled for 8 hours. Certification of whitening was performed visually on each sample after boiling for 24 hours for samples using organic silane compounds, and after boiling for 8 hours for samples using organic chromium compounds, and was indicated by the following signal. ◎ No whitening 〇 Almost no whitening △ Slight whitening × Whitening Also, when each of these samples is impregnated with resin and hardened and molded, molded products with a higher amount of resin than those without needle punching are obtained; Since it is not possible to compare the test results of the two, in addition to the actual measured values for those that were needle-punched, we calculated the estimated values when the glass fiber content in the resin was made the same as for those that were not needle-punched. They are listed together for convenience of comparison.

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[Table] The results of these tests are summarized as follows: when using the method of the present invention, regardless of the shape of the glass fiber product, regardless of the presence or absence of needle punching,
The actual measured value is not only compared with the conventional method in which a surface treatment agent is mixed into the sizing agent, but also in comparison with the conventional method in which the sizing agent is removed by heat cleaning and then treated again with a surface treatment agent. It can be clearly seen that the performance is comparable in terms of , but much better in terms of estimated values. This not only eliminates the use of sizing agent components that inhibit the bonding of resin and glass fibers, but also eliminates the various processes for heat cleaning and the surface treatment process after heat cleaning. This is because fiber deterioration, cutting, fuzzing, etc. are completely eliminated, which not only reduces the unit consumption of sizing agent, simplifies processes, saves labor and energy, but also greatly contributes to improving quality. is enormous. In the present invention, strand mats, chopped strand mats, and roving cloths have been described as fabric-like glass fiber products, but the invention is not necessarily limited to these as long as the fabric-like glass fiber products are used. In addition to the organic silane compounds and organic chromium compounds mentioned above, any other organic silane compounds and organic chromium compounds that are effective as surface treatment agents can be used, and the same effect can be obtained. It is.

Claims (1)

[Scope of Claims] 1 Glass fiber strands obtained by binding glass fiber filaments during spinning while applying a 0.02 to 2% aqueous solution of an organosilane compound or an organic chromium compound as a binding agent. ,
A method for producing a glass fiber product reinforced with a thermosetting synthetic resin, which comprises forming a fabric-like glass fiber product in a wet state and then drying the product. 2. The method for producing a glass fiber product reinforced with a thermosetting synthetic resin according to claim 1, wherein mat or roving cloth is formed as the fabric-like glass fiber product and needle punching is applied to this in a wet state.