KR20050094193A - Binder composition for glass fiber and manufacturing method thereof - Google Patents

Abstract

The present invention does not require a separate heat treatment process, and is suitable for directly applying the obtained glass fibers to fiber-reinforced plastics, and when discolored when exposed to ultraviolet rays in preparing a composite material using ultraviolet curing resin as a matrix, The present invention relates to a binder composition for glass fibers and a method for producing the same, which can be rapidly cured by ultraviolet rays sufficiently penetrating without causing peeling or blocking, and 0.1 to 10% by weight of organosilanes as a coupling agent and 0.1 stearic acid as a wetting agent. To 10% by weight, 1 to 10% by weight of an epoxy resin emulsion (solid content of 46 ± 2%) as a softening agent, 1 to 10% by weight of polyvinylacetate emulsion (solid content of 55 ± 1%) as a film forming agent, as an emulsion stabilizer 0.01 to 2% by weight of glacial acetic acid, 0.1 to 3% by weight of dibutyl peroxide (DBP) as a radical initiator, acetone 0.1 to 1% by weight and the balance comprises water.

Description

Binder composition for glass fiber and manufacturing method thereof

The present invention relates to a binder composition for glass fibers and a manufacturing method thereof. More specifically, the present invention does not require a separate heat treatment process, and is suitable for directly applying the obtained glass fibers to fiber-reinforced plastics, and may have been exposed to ultraviolet rays when preparing a composite material using an ultraviolet curable resin as a matrix. At this time, the present invention relates to a binder composition for glass fibers and a method for producing the same, which can sufficiently cure ultraviolet rays and rapidly cure without discoloration or peeling or blocking.

Fiber reinforced plastic (FRP) improves physical properties such as impact resistance by using fibers, especially glass fiber, as a reinforcing material or reinforced material when manufacturing a structure by molding thermoplastic or thermosetting synthetic resin as a raw material. It is a composite material that makes it easy to quantify and quantify the complementary physical properties of resins and reinforcing agents, which are the general characteristics of composite materials, and shows particularly improved physical properties in light weight, corrosion resistance and durability. It has been widely used in various industries such as cars, automobiles or small boats. Not only glass fibers, but also synthetic fibers such as aramid fibers, super tough polyethylene fibers and carbon fibers are used. However, the production of these requires a multi-step process, resulting in higher costs.

On the other hand, glass fibers commonly used in composite materials such as fiber-reinforced plastics are produced by winding glass poured by gravity in platinum nozzles of 100 to 1,600 holes, called bushings. Pulled molten glass from a capillary nozzle with a diameter of about 1.5 mm to produce a yarn shape divided into the diameter (yarn, roving) or the length (chopped fiber mat) of the filament for various purposes. Is a common example. In spinning of fiberglass, a binder is used. This binder is applied at the moment when glass fiber is spun, soaking between glass fiber monofilaments, reducing mutual friction between fibers in the spinning process and preventing the fiber from breaking. It can be considered to function to secure. The binder may contain various components. That is, the addition of a lubricant reduces friction between fibers, prevents trimming during the manufacture of glass strands, and provides moisture to the glass fibers to be produced, thereby making it possible to maintain an amorphous state. In addition to increasing the strength of the filament, it is possible to absolutely reduce the radiant energy of high heat due to moisture and liquid cooling to ensure the safety of the operator and the like. The application of the binder solution to each of the filaments, i.e., coating, involves several methods, such as passing the fiberglass to the surface of the roller applicator on which the binder solution is applied, or impregnating with a spray method. Through this process, the binder liquid is impregnated into the glass fiber strands, wound on the plastic or paper of the winding apparatus, and then transferred to the next process.

Fiber is largely divided into a yarn-based process and a roving-based process, and accordingly, a binder may be selected and used separately from a yarn binder and a roving binder. Yarn binders are binders coated in an applicator to reduce friction between fibers during spinning and to increase the efficiency of the yield point. A post process, that is, a process of removing the binder through heat cleaning is required, and in this process, the components of the binder must be rapidly volatilized and no remaining substances remain. To do this, the resin type is used as little as possible, and the polyester content should be small to prevent discoloration. In addition, water-soluble resins should be used to facilitate pipe transport, and each component should be different. Because this is a different process than roving binders, the yarn binder composition must also be different. Unlike the yarn binder, the roving binder is often impregnated with the ultraviolet curable resin without undergoing a heat treatment process, and thus, often includes a substantial amount of various coupling agents. This is a big difference from the yarn binder.

On the other hand, synthetic resins, ie, most organic materials including polymers, are photooxidized and decomposed when exposed to sunlight or artificial light including ultraviolet rays for a long time. The ultraviolet light source can be roughly classified into sunlight and artificial light. Light is electromagnetic radiation in the wavelength range, including infrared, visible, and X-rays, with only about 5% of the UV emitted from the sun reaching the earth's surface, which is usually longer than 290 nm. It is a light ray having a wavelength. Light generated by fluorescence and similar types of artificial light sources can emit ultraviolet rays, usually having wavelengths shorter than 290 nm. This decomposition usually results in discoloration of the polymer. In addition, due to ultraviolet energy, the polymer coated on the surface of the glass fiber is peeled off, resulting in deterioration of physical properties, adversely affecting adhesion to the resin.

Therefore, in order to solve this problem, in recent years, there are many cases of manufacturing a composite material using a UV curable resin as a matrix (matrix). Herein, the ultraviolet curable resin refers to a resin that is cured when exposed to ultraviolet light, that is, light energy having a wavelength of 290 to 450 nm, unlike a conventional thermosetting resin. When the ultraviolet curable resin is used as the matrix, the adhesion between the matrix and the glass fiber is a matrix that is cured by ultraviolet rays, which can significantly reduce the risk of peeling and the like. However, this is not enough to simply replace the matrix with UV curable resin. That is, the conventional binders used to enhance the adhesion of glass fibers to synthetic resins on the glass fibers rather than UV curing resins in the matrix rather peeling and discoloration, making it difficult to penetrate the ultraviolet rays UV curing is made properly It is not supported.

Therefore, in the case of using the UV curable resin as a matrix, in particular, there is no discoloration, transparency, and the development of a binder that does not cause peeling on the glass fiber surface or blocking of the polymer constituting the binder even in the energy of ultraviolet rays. The need for it still exists.

An object of the present invention does not require a separate heat treatment process, and is suitable for applying the obtained glass fibers directly to fiber-reinforced plastics, when exposed to ultraviolet rays in the production of a composite material using an ultraviolet curing resin as a matrix, The present invention provides a binder composition for glass fibers and a method for producing the same, which can sufficiently cure ultraviolet rays and rapidly cure without discoloration or peeling or blocking.

The binder composition for glass fibers according to the present invention comprises 0.1 to 10% by weight of organosilanes as a coupling agent, 0.1 to 10% by weight of stearic acid as a wetting agent, and 1 to 10% by weight of an epoxy resin emulsion (solid content of 46 ± 2%) as a softening agent. , 1 to 10% by weight of polyvinylacetate emulsion (solid content 55 ± 1%) as a film forming agent, 0.01 to 2% by weight glacial acetic acid as an emulsion stabilizer, 0.1 to 3% by weight of dibutyl peroxide (DBP) as a radical initiator %, Acetone 0.1 to 1% by weight and the balance comprises water.

The organosilanes are preferably gamma-methacryloxy propyl trimethoxy silane, gamma-glycidoxy propyl trimethoxy silane, gamma-amino Propyltriethoxysilane (γ-amino propyl triethoxy silane) or a mixture of two or more thereof may be used.

Further, in the method for producing a binder composition for glass fibers according to the present invention, in the preparation of the binder composition for glass fibers, (1) about 70% of the amount of water prescribed by the remaining amount excluding the remaining components is filled in a tank, A first mixing step of adding 0.01 to 2% by weight of glacial acetic acid as an emulsion stabilizer and stirring for 1 to 10 minutes at a temperature of 20 to 40 ° C; (2) a second mixing step of adding 0.1 to 10% by weight of organosilanes as a coupling agent to the mixture obtained in the first mixing step and stirring for 5 to 20 minutes at a temperature of 20 to 40 ° C; (3) 3 to 10 wt% of a polyvinylacetate emulsion (solid content 55 ± 1%) as a film-forming agent is added to the mixture obtained in the second mixing step and stirred at 40 to 50 ° C. for 10 to 30 minutes. Mixing process; (4) 0.1 to 3% by weight of dibutyl peroxide (DBP; dibutylperoxide) and 4 to 5% by weight of the remaining water are added to the mixture obtained in the third mixing step as a radical initiator, and 20 to 40 ° C. A fourth mixing step of stirring for 5 to 20 minutes; (5) 1 to 10% by weight of an epoxy resin emulsion (solid content of 46 ± 2%) and 0.1 to 1% by weight of acetone are mixed with 0.1 to 2% by weight of a 10% solution of polyvinyl alcohol (PVA; polyvinylalcohol) in a homomixer as a softening agent. And a fifth mixing step of adding the mixture obtained in the fourth mixing step to a tank containing the mixture and stirring the mixture at 40 to 50 ° C. for 5 to 20 minutes; And (6) simultaneously adding 0.1 to 10% by weight of stearic acid and 4 to 6% by weight of water in the residual amount as a humectant to the mixture obtained in the fifth mixing step, and then adding the remaining amount of water to 100% by weight. It comprises a sixth mixing step of adjusting to 40 to 60 minutes at 40 to 60 ℃ mixing.

Hereinafter, the present invention will be described in detail with reference to specific examples.

The binder composition for glass fibers according to the present invention comprises 0.1 to 10% by weight of organosilanes as a coupling agent, 0.1 to 10% by weight of stearic acid as a wetting agent, and 1 to 10% by weight of an epoxy resin emulsion (solid content of 46 ± 2%) as a softening agent. , 1 to 10% by weight of polyvinylacetate emulsion (solid content 55 ± 1%) as a film forming agent, 0.01 to 2% by weight glacial acetic acid as an emulsion stabilizer, 0.1 to 3% by weight of dibutyl peroxide (DBP) as a radical initiator %, Acetone 0.1 to 1% by weight and the balance comprises water. The basic role of the binder is to focus hundreds or thousands of glass fibers as described above. In other words, the filaments radiated from 100 to 1,600 holes are collected and wound together at the same time, which aims to reduce friction between fibers and to focus well. The present invention relates to a binder that can be used for the preparation of FRP immediately after spinning, unlike a yarn binder involving a heat treatment process, and thus, it is necessary to be able to configure an interface structure without discoloration when impregnated with an ultraviolet curable resin. For this purpose, that is, organosilanes are used as the coupling agent in order to impart excellent impregnation with the ultraviolet curable resin. The organosilanes are preferably gamma-methacryloxy propyl trimethoxy silane, gamma-glycidoxy propyl trimethoxy silane, gamma-amino Propyltriethoxysilane (γ-amino propyl triethoxy silane) or a mixture of two or more thereof may be used. These organosilanes are generally well soluble in water and have low reactivity with many matrix resins at low temperatures. When the content of the organosilanes as the coupling agent is included in less than 0.1% by weight, there may be a problem that the adhesion between the ultraviolet curable resin and the glass fiber is not enough, the adhesive strength is lowered, on the contrary, if the content of the organosilanes exceeds 10% by weight, It can act as a problem that leads to under-content of other main ingredients. Stearic acid is used as a wetting agent, which functions to allow the binder to penetrate well enough between the filaments. If the stearic acid is included in less than 0.1% by weight, there may be a problem that this enhancement effect is not enough to penetrate between the filaments, on the contrary, more than 10% by weight is less than the content of the other major components It can work as a problem. As the wetting agent, amines may be used in addition to the stearic acid described above. Epoxy resin emulsions function as softeners, which also increase the wet penetration effect between glass fibers. When the epoxy resin emulsion is contained in less than 1% by weight, there may be a problem that the above-mentioned wet permeation effect is insignificant and the binder does not sufficiently penetrate between the filaments, on the contrary, more than 10% by weight is less than the content of other main components. Can act as a problem. Polyvinylacetate emulsions function as film formers, which serve to improve the stability of the binder overall composition. If the polyvinylacetate emulsion is included in less than 1% by weight, there may be a problem that the stability of the binder is lowered, on the contrary, exceeding 10% by weight may act as a problem that the content of the other major components is less than. In addition, glacial acetic acid is used as an emulsion stabilizer for stabilizing these emulsions. If glacial acetic acid is used at less than 0.01% by weight, the emulsion will not stabilize, which may eventually cause deterioration of the stability of the binder as a whole. It can work as a problem. In addition, a radical initiator is used to form a film by a film forming agent, and dibutyl peroxide is used as this radical initiator. When the dibutyl peroxide is included in less than 0.1% by weight, there may be a problem that the film formation is not sufficient, on the contrary, more than 3% by weight may act as a problem that brings the content of the other major components less than . If acetone is included in less than 0.1% by weight, there may be a problem that the manufacturing cost is increased, the precipitation occurs, more than 1% by weight is bad smell, wrong viscosity, uneven surface wettability, precipitation It may occur, and may act as a problem that causes the content of other main ingredients to fall short. In addition, the water serves to form a binder composition by serving as a carrier to accommodate the other active ingredients as described above, and the water increases the strength by rapidly cooling the filament during the spinning of the glass fiber to have an amorphous structure To function.

Further, in the method for producing a binder composition for glass fibers according to the present invention, in the preparation of the binder composition for glass fibers, (1) about 70% of the amount of water prescribed by the remaining amount excluding the remaining components is filled in a tank, A first mixing step of adding 0.01 to 2% by weight of glacial acetic acid as an emulsion stabilizer and stirring for 1 to 10 minutes at a temperature of 20 to 40 ° C; (2) a second mixing step of adding 0.1 to 10% by weight of organosilanes as a coupling agent to the mixture obtained in the first mixing step and stirring for 5 to 20 minutes at a temperature of 20 to 40 ° C; (3) 3 to 10 wt% of a polyvinylacetate emulsion (solid content 55 ± 1%) as a film-forming agent is added to the mixture obtained in the second mixing step and stirred at 40 to 50 ° C. for 10 to 30 minutes. Mixing process; (4) 0.1 to 3% by weight of dibutyl peroxide (DBP; dibutylperoxide) and 4 to 5% by weight of the remaining water are added to the mixture obtained in the third mixing step as a radical initiator, and 20 to 40 ° C. A fourth mixing step of stirring for 5 to 20 minutes; (5) 1 to 10% by weight of an epoxy resin emulsion (solid content of 46 ± 2%) and 0.1 to 1% by weight of acetone are mixed with 0.1 to 2% by weight of a 10% solution of polyvinyl alcohol (PVA; polyvinylalcohol) in a homomixer as a softening agent. And a fifth mixing step of adding the mixture obtained in the fourth mixing step to a tank containing the mixture and stirring the mixture at 40 to 50 ° C. for 5 to 20 minutes; And (6) simultaneously adding 0.1 to 10% by weight of stearic acid and 4 to 6% by weight of water in the residual amount as a humectant to the mixture obtained in the fifth mixing step, and then adding the remaining amount of water to 100% by weight. It is characterized by consisting of; sixth mixing step of adjusting to 40 to 60 minutes at 40 to 60 ℃ mixed. In the present invention, in the preparation of the binder composition, glacial acetic acid is first added to the water as an emulsion stabilizer, and then mixed with water, followed by organosilanes as a coupling agent and polyvinylacetate emulsion as a film forming agent (solid content of 55 ± 1%). ), Dibutyl peroxide as a radical initiator, and then an epoxy resin emulsion, acetone, and polyvinyl alcohol as a homomixer were added separately. Finally, stearic acid and water were added simultaneously as a wetting agent, and then the remaining amount of water was added. Consisting of adding and mixing. This order can be particularly affected by the stability of the binder composition, characterized in that the film-forming agent is added first, followed by sequentially adding a radical initiator, a softening agent and a wetting agent. In the first mixing step of (1), it is made of mixing glacial acetic acid with water, where the mixing temperature is less than 20 ℃, there is a problem that can not be homogeneous mixing is not easy mixing, contrary 40 If it exceeds the ℃ it may be a problem that the volatilization occurs easily, which is also undesirable for mixing. Mixing time is in the appropriate range of 1 to 10 minutes, less than 1 minute, there may be a problem that the sufficient mixing is not made, exceeding 10 minutes may take a lot of time to manufacture may act as a problem that lowers the productivity have. In the second mixing step of (2), 0.1 to 10% by weight of organosilanes are added to the mixture obtained in the first mixing step as a coupling agent and stirred, and 5 to 20 at a temperature of 20 to 40 ° C. It is preferable to stir for a minute, and if it is out of this range, there may be a problem that homogeneous mixing becomes difficult. The third mixing step of (3) consists of adding 1 to 10% by weight of a polyvinylacetate emulsion (solid content of 55 ± 1%) as a film forming agent and stirring the mixture obtained in the second mixing step, It is preferable to stir for 10 to 30 minutes at 40 to 50 ℃, if outside this range there may be a problem that homogeneous mixing becomes difficult. In the fourth mixing step (4), 0.1 to 3% by weight of dibutyl peroxide (DBP; dibutylperoxide) and 4 to 5% by weight of the residual water are added to the mixture obtained in the third mixing step as a radical initiator. It consists of the addition, stirring, it is preferable to stir at 20 to 40 ℃ for 5 to 20 minutes, if out of this range there may be a problem that homogeneous mixing becomes difficult. The fifth mixing process of (5) is a 10% solution of polyvinyl alcohol (PVA; polyvinylalcohol) in a homomixer with 1-10% by weight of an epoxy resin emulsion (solid content of 46 ± 2%) and 0.1-1% by weight of acetone. It is mixed with 0.1 to 2% by weight and then added to the tank containing the mixture obtained in the fourth mixing process and stirred, preferably stirring for 5 to 20 minutes at 40 to 50 ℃, if outside this range There may be a problem that homogeneous mixing becomes difficult. In the sixth mixing step of (6), 0.1 to 10% by weight of stearic acid and 4 to 6% by weight of water in the remaining amount of water are simultaneously added to the mixture obtained in the fifth mixing step as a humectant, followed by remaining amount. After adjusting to 100% by weight of water to be mixed for 20 to 40 minutes at 40 to 60 ℃, if out of this range there may be a problem that homogeneous mixing becomes difficult.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

Example

About 70% of the prescribed amount of water, excluding the remaining ingredients, was charged to the tank, to which 0.05 wt% glacial acetic acid was added as an emulsion stabilizer and stirred for 5 minutes at a temperature of 30 ° C. As organosilanes used herein as coupling agents, 0.3 wt% each of trade names A-174 and A-187 from Union Carbide, USA, were added and stirred. Again, 3% by weight of polyvinylacetate emulsion (solid content: 55 ± 1%) was added and stirred, followed by addition of 0.1% by weight of DBP and 4.5% by weight of water, followed by stirring. Separately, water-soluble epoxy resin emulsion (solid content of 46 ± 2%) and 0.3% by weight of acetone were mixed with 0.5% by weight of polyvinyl alcohol (10% solution) in a homomixer, and then added to the tank and stirred. 0.15% by weight of stearic acid and 5% by weight of water were added to the tank at the same time, and the remaining amount of water was added to adjust the amount to 100% by weight, followed by stirring at 50 ° C for 30 minutes to obtain a binder composition according to the present invention. After applying to the filament during the spinning of the glass fiber using the obtained glass fiber filament was cut to a length of 1 inch to produce a FRP (450g / ㎡) as a matrix of ultraviolet curing resin according to the known FRP manufacturing method as it is. , And tested for the loss of ignition, the presence or absence of discoloration, tensile strength, and impact strength after irradiation of the prepared FRP is shown in Table 1 below.

Comparative example

FRP was prepared and tested under the same conditions as in the above example, except that the glass fiber manufactured by using a known binder commercially known by leading manufacturers in Korea, and the results are also shown in Table 1 below. It was.

division Loss on Ignition (LOI) Discoloration Tensile Strength (MPa) Impact strength (J / ㎠) Comparative example 3 Discoloration (yellow) 260 3.5 Example 3 No discoloration (transparent) 260 3.5  Discoloration; Visually observe whether there is discoloration after solar and ultraviolet irradiation

As described above, it was confirmed that the production of FRP which does not cause discoloration in spite of irradiation of sunlight or ultraviolet rays without change in tensile strength or impact strength, that is, without adversely affecting physical properties.

Therefore, according to the present invention, a separate heat treatment process is not required, and the glass fiber obtained is suitable for applying directly to a fiber-reinforced plastic, and when exposed to ultraviolet rays in manufacturing a composite material using an ultraviolet curable resin as a matrix. There is an effect of providing a binder composition for glass fibers and a method for producing the same, which can sufficiently cure ultraviolet rays and penetrate quickly without causing discoloration or peeling or blocking.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

Claims (3)

0.1 to 10% by weight of organosilanes as coupling agent, 0.1 to 10% by weight of stearic acid as wetting agent, 1 to 10% by weight of epoxy resin emulsion (solid content 46 ± 2%) as softener, polyvinylacetate emulsion (solid content) as film former Content 55 ± 1%) 1 to 10% by weight, 0.01 to 2% by weight glacial acetic acid as an emulsion stabilizer, 0.1 to 3% by weight of dibutyl peroxide (DBP; dibutylperoxide) as a radical initiator, 0.1 to 1% by weight of acetone and the balance Binder composition for glass fibers, characterized in that comprises water. The method of claim 1, As the organosilanes, gamma-methacryloxy propyl trimethoxysilane, gamma-glycidoxy propyl trimethoxysilane, and gamma- A binder composition for glass fibers, characterized in that amino-propyl propyl triethoxy silane or a mixture of two or more thereof is used. In the manufacture of the binder composition for glass fibers, (1) Fill the tank with about 70% of the specified amount of water excluding the remaining ingredients in the tank, add 0.01 to 2% by weight of glacial acetic acid as an emulsion stabilizer and stir for 1 to 10 minutes at a temperature of 20 to 40 ° C. A first mixing process; (2) a second mixing step of adding 0.1 to 10% by weight of organosilanes as a coupling agent to the mixture obtained in the first mixing step and stirring for 5 to 20 minutes at a temperature of 20 to 40 ° C; (3) 3 to 10 wt% of a polyvinylacetate emulsion (solid content 55 ± 1%) as a film-forming agent is added to the mixture obtained in the second mixing step and stirred at 40 to 50 ° C. for 10 to 30 minutes. Mixing process; (4) 0.1 to 3% by weight of dibutyl peroxide (DBP; dibutylperoxide) and 4 to 5% by weight of the remaining water are added to the mixture obtained in the third mixing step as a radical initiator, and 20 to 40 ° C. A fourth mixing step of stirring for 5 to 20 minutes; (5) 1 to 10% by weight of an epoxy resin emulsion (solid content of 46 ± 2%) and 0.1 to 1% by weight of acetone are mixed with 0.1 to 2% by weight of a 10% solution of polyvinyl alcohol (PVA; polyvinylalcohol) in a homomixer as a softening agent. And a fifth mixing step of adding the mixture obtained in the fourth mixing step to a tank containing the mixture and stirring the mixture at 40 to 50 ° C. for 5 to 20 minutes; And (6) 0.1 to 10% by weight of stearic acid and 4 to 6% by weight of water in residual water were added simultaneously as a wetting agent to the mixture obtained in the fifth mixing step, and then the remaining amount of water was added to 100% by weight. A sixth mixing step of adjusting and mixing for 20 to 40 minutes at 40 to 60 ° C; Method for producing a binder composition for glass fibers, characterized in that consisting of.