JP2009143765A - Glass fiber sizing agent, glass fiber, method for producing the glass fiber and glass fiber reinforced thermoplastic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a glass fiber sizing agent which can suppress the discoloration of a thermoplastic resin caused by heat when the thermoplastic resin is molded and even the discoloration of the thermoplastic resin caused by high-temperature heat treatments over a plurality of times applied on the thermoplastic resin after molding; a glass fiber coated with the glass fiber sizing agent, which is used as a reinforcing material of a thermoplastic resin and provides a resin material having stable mechanical strength; a method for producing the glass fiber; and a glass fiber-reinforced thermoplastic resin using the glass fiber. <P>SOLUTION: The glass fiber sizing agent contains a pyrophosphate and a non-yellowing polyurethane, wherein the content of the non-yellowing polyurethane is ≥50 mass% expressed in terms of solid content. In the glass fiber, the glass fiber sizing agent is applied in a sticking rate of 0.2-0.6 mass%. The method for producing the glass fiber comprises applying the glass fiber sizing agent onto glass filaments drawn out from a bushing, gathering the filaments to make them into a glass strand, and winding the glass strand into a wound article. The glass fiber reinforced thermoplastic resin is reinforced by using the glass fiber. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a glass fiber used to reinforce a thermoplastic resin, a glass fiber sizing agent covering the surface thereof, a method for producing glass fiber using the sizing agent, and the glass fiber. It relates to a glass fiber reinforced thermoplastic resin produced by the manufacturing method.

  Glass fiber mainly used as a structural material is used in many applications, and this glass fiber is generally produced by the following process. First, a glass raw material prepared for glass fiber is heated to a high temperature to obtain molten glass, and this molten glass is continuously drawn out from a number of heat-resistant nozzles formed at the bottom of a platinum bushing. After fiberization, a method of winding the glass fiber bundle (strand) into a glass fiber bundle (strand) by applying a bundling agent to the surface and then bundling is used. Here, the sizing agent applied to the glass fiber is composed of various components such as a film forming agent, a coupling agent, a lubricant, or an antistatic agent. When the glass fiber is used as a reinforcing material for FRTP (Fiberglass-Reinforced Thermoplastic) (also referred to as glass fiber heat-reinforced plastic), the adhesive property to the matrix resin is used as a component of the sizing agent so as to obtain a high strength FRTP. A film-forming agent and a coupling agent selected so as to be good are used. For example, when manufacturing FRTP using this glass fiber, the prepared strand is cut into a predetermined length to obtain a chopped strand, which is then kneaded while being heated with a thermoplastic resin, and then variously shaped. The method of forming into a predetermined shape is adopted.

The thermoplastic resin moldings using glass fibers such as FRTP obtained in this way are used in various applications such as automobiles and OA equipment because they have many excellent performances. Depending on the heating conditions such as kneading during the process, it may be colored brown due to the decomposition reaction of the matrix resin or the reaction of the sizing agent on the surface of the glass fiber, and coloring prevention to prevent such coloring phenomenon Agents are commonly used. However, the use of an anti-coloring agent may reduce the strength of the molded article, and it is not economical to use a large amount of the anti-coloring agent. Therefore, Patent Document 1 discloses an invention in which coloring by heating is suppressed by using 0.05 to 1.5 wt% of hypophosphorous acid or a salt thereof as a coloring inhibitor. Patent Document 2 also discloses an invention in which pyrophosphate is contained in a sizing agent as a means for preventing coloring due to heating.
Japanese Patent Laid-Open No. 2-116648 Japanese Patent Laid-Open No. 9-249434

  However, it has been found that the inventions that have been carried out so far are not satisfactory at all for the use in which glass fibers are used or the specific resin, even if a certain degree of coloring improvement effect can be realized. For example, among various FRTPs, surface mount components manufactured using liquid crystal polymer resins having high heat resistance, polyamide 4,6 resins, aromatic polyamide resins, PPS resins, etc. and used in applications such as electronics industry In some cases, the part is remarkably colored by heating during reflow soldering or discolored to a deep hue. If such coloring occurs, a product with a desired color tone cannot be obtained. This coloring problem is caused by reheating soldering in addition to heating at the time of manufacturing the FRTP, and a desired hue can be obtained in the part after the reflow soldering processing. In addition to the disappearance, there is a problem that the hue variation of each product is large and the hue stability is lacking. That is, the color tone of the obtained product is not stabilized, and the value as an industrial product is lost.

  In the inventions disclosed in Patent Document 1 and Patent Document 2, the effect of suppressing discoloration by primary heating at the time of FRTP molding can be exerted, and if it is not exposed to high temperature heating after that, it can be dealt with as such. It can be done. However, since FRTP has been used in various applications, it became a problem again. The once-molded FRTP is subjected to reheating, so that it is extremely difficult to solve the problem of thermal discoloration for so-called secondary heating. It was a coloring problem. In addition, in the coloring problem related to the secondary heating, if the countermeasure is taken to increase the adhesion amount of hypophosphorous acid or salt thereof of Patent Document 1 or pyrophosphate salt of Patent Document 2 to the glass fiber surface, the hue of FRTP It has also been found that the hue change due to the secondary heating during the reflow soldering process becomes rather noticeable and the hue stability as the final part may be further deteriorated.

  That is, the present invention is a glass fiber sizing agent that can reliably suppress not only the heating during the molding of the thermoplastic resin but also the coloration caused by the multiple times of high-temperature heat treatment that the molded thermoplastic resin undergoes. A glass fiber capable of obtaining a resin material having a stable mechanical strength as a thermoplastic resin reinforcing material by applying the glass fiber sizing agent, a method for producing the same, and a glass reinforced by the glass fiber An object is to provide a fiber-reinforced thermoplastic resin.

  The inventors of the present invention are for reinforcing a thermoplastic resin that is difficult to be colored by heating, that is, has high heat discoloration, has good adhesion to a matrix resin, and can increase the mechanical strength of the composite molded body. The present invention has been reached through intensive research on glass fibers. That is, by using a finely adjusted compounding amount of a specific component as a sizing agent component applied to the glass fiber surface, it is possible to improve the adhesion with the matrix resin and increase the mechanical strength of FRTP. In addition to the primary heating at the time of molding the glass fiber, the discoloration during the post-heating process with secondary heating such as reflow soldering is also possible due to the good convergence and the fiber bundles are not easily loosened in the transport process. Finally, after many trials and errors, it was found that it was possible to efficiently suppress the noise. And glass fiber sizing agent capable of realizing both high mechanical strength and heat discoloration, glass fiber coated with this glass fiber sizing agent, glass fiber production method, and glass using this glass fiber A fiber reinforced thermoplastic resin is presented here.

  The sizing agent for glass fiber of the present invention is a sizing agent applied to the surface of glass fiber, and contains a non-yellowing polyurethane and a pyrophosphate, and the content of the non-yellowing polyurethane in terms of solid content It is 50 mass% or more.

  Here, the sizing agent applied to the surface of the glass fiber, which contains non-yellowing polyurethane and pyrophosphate, and the content of the non-yellowing polyurethane is 50% by mass or more in terms of solid content Is a non-yellowing type polyurethane which is a polyurethane containing a non-yellowing type polyisocyanate as a component of a glass fiber sizing agent applied so as to cover the surface of the glass fiber used for reinforcing the thermoplastic resin made of an inorganic glass material It means that the polyurethane and pyrophosphate are contained, and the content of the non-yellowing polyurethane is 50% by mass or more in terms of solid content.

  Non-yellowing polyurethane includes aliphatic, alicyclic diisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, or derivatives thereof. As the pyrophosphate, an anhydride or hydrate such as sodium pyrophosphate, potassium pyrophosphate, calcium pyrophosphate, or copper pyrophosphate is used.

  The glass fiber sizing agent of the present invention exhibits the effect of suppressing discoloration at the initial stage of heating, that is, at the time of primary heating when the content ratio of the non-yellowing polyurethane contained is less than 50% by mass in terms of solid content. When a heating operation such as secondary heating is required several times or when the heating temperature is extremely high, it is difficult to obtain a sufficient coloring suppression effect, and dark coloring is recognized. Non-yellowing polyurethane has been used in glass fiber bundling materials until now, but it has been used at a content of less than 50% by mass in terms of solid content, so it exerts a great coloring suppression effect. It was something that could not be done. On the other hand, if the content ratio of the non-yellowing polyurethane is too large, the content of pyrophosphate is relatively lowered, and in that case, the heat discoloration may be impaired. Therefore, there is an upper limit to the content ratio of the non-yellowing polyurethane contained, and the content ratio of the non-yellowing polyurethane is preferably 90% by mass or less. In order to obtain a more stable glass fiber sizing agent with respect to heat discoloration, the content is preferably 88% by mass or less, and more preferably 85% or less.

  The sizing agent for glass fibers of the present invention may contain various components as long as the components other than the non-yellowing polyurethane and pyrophosphate exhibit desired performance. For example, an appropriate amount of a coupling agent such as a silane or titanate, a known antistatic agent, a surfactant, a polymerization initiator, a polymerization inhibitor, an antioxidant, or a lubricant can be added. If necessary, water reducing agents, fluidizers, thickeners, waterproofing agents, rust preventives, curing accelerators, curing retarders, slag, fly ash, silica fume, colorants or quick setting agents are mixed in. Also good.

  Especially about a coupling agent, if a silane coupling agent is used, you may use it in combination with various existing silane coupling agents. For example, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -N′-β- (aminoethyl) -γ-aminopropyltri Aminosilanes such as methoxysilane and γ-anilinopropyltrimethoxysilane; epoxysilanes such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Chlorosilanes such as chloropropyltrimethoxysilane, mercaptosilanes such as γ-mercaptotrimethoxysilane, vinylmethoxysilane, or N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane. Vinyl silanes, or γ-methacryloxypropyl It may be used depending on the application of the acrylic silanes such as trimethoxysilane and the like.

  In addition to the above, the glass fiber sizing agent of the present invention has a mass reduction rate according to JIS K7120 (1987) of a non-yellowing polyurethane while the temperature is increased from 200 ° C. to 300 ° C. at a temperature increase rate of 25 ° C./min. If it is 2% or less, since it will exhibit high heat-resistant discoloration property, it is preferable.

  Here, the mass reduction rate according to JIS K7120 (1987) of the non-yellowing polyurethane is 2% or less during the temperature increase from 200 ° C. to 300 ° C. at a temperature increase rate of 25 ° C./min. In accordance with JIS K7120 “Thermogravimetric method for measuring plastics”, a Japanese industrial standard issued in 1987, the temperature increase rate from a room temperature (25 ° C.) is 25 ° C./min. The change in mass over time obtained by heating at a heating rate of 2 is obtained as a TG (thermogravimetry) curve plotted with the vertical axis representing the mass value and the horizontal axis representing the temperature, and the mass at 200 ° C. is obtained from this TG curve. When the mass reduction rate when the temperature is raised to 300 ° C. is calculated based on the above, it means that the value is 2% or less.

  The sample used for the measurement is a sample kept in a constant temperature and humidity chamber maintained at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% for 24 hours.

  The non-yellowing polyurethane can reach such a temperature by reducing the mass reduction rate according to JIS K7120 (1987) to 2% or less at a temperature increase from 200 ° C. to 300 ° C. of 25 ° C./min. When heated, the composition of the components is maintained without damage, and therefore, a phenomenon in which a part of the components are chemically changed by heating, for example, brown or ocher is suppressed.

  In addition to the above, the glass fiber sizing agent of the present invention has an adhesiveness to a matrix resin as long as the mass content ratio in terms of solid content of pyrophosphate to non-yellowing polyurethane is in the range of 10% to 75%. Is preferable because the mechanical strength of FRTP can be increased.

  Here, the mass content ratio in terms of solid content of pyrophosphate with respect to non-yellowing polyurethane is within the range of 10% to 75%. The solid content of pyrophosphate contained in the sizing agent for glass fibers of the present invention. The mass-converted mass value is divided by the solid-value-converted mass value of the non-yellowing polyurethane contained in the glass fiber sizing agent of the present invention. % Is in the range of%.

  When the mass content ratio in terms of solid content of pyrophosphate to non-yellowing polyurethane is less than 10%, the content of pyrophosphate is too small, and it is not preferable because it tends to discolor when heated, whereas non-yellowing polyurethane When the mass content ratio in terms of solid content of pyrophosphate with respect to 75% exceeds 75%, as a result of the content of non-yellowing polyurethane being too small, the flexible and tough film does not cover the glass fiber surface, Since the strength of FRTP using the glass fiber coated with the glass fiber sizing agent may not be sufficiently obtained, it is not preferable. That is, when the mass content ratio in terms of solid content of pyrophosphate to non-yellowing polyurethane is in an appropriate range of 10 to 75%, the glass fiber coated with this sizing agent is transported on a transport line. When loosening occurs, it becomes a cotton-like product, and when it enters the extruder, a mechanical shearing force stronger than usual is applied to the glass fiber during heating and kneading with the thermoplastic resin, and heat generation due to the shearing force becomes more prominent. Thus, it is possible to avoid a situation in which the molten resin temperature rises and causes the FRTP discoloration.

  Further, in order to obtain a sizing agent capable of exhibiting more stable performance from such a viewpoint, the mass content ratio in terms of solid content of pyrophosphate to non-yellowing polyurethane is in the range of 10.1% to 73%. More preferably, the mass content ratio in terms of solid content of pyrophosphate to non-yellowing polyurethane is in the range of 10.3% to 71.5%.

  In addition to the above, the glass fiber sizing agent of the present invention has a heat-resistant discoloration that is stable over a long period of time as long as the pyrophosphate content falls within the range of 1% to 40% by mass in terms of solid content. Since it can be set as the glass fiber sizing agent which exhibits property, it is preferable.

  When the content of pyrophosphate is less than 1% by mass in terms of solid content, when the sizing agent of the present invention is used as a sizing agent for glass fibers used in FRTP applications, after the heat treatment of FRTP This is not preferable because the effect of suppressing discoloration is reduced. On the other hand, when the pyrophosphate content exceeds 40% by mass in terms of solid content, the pyrophosphate content is too high, and the mechanical strength of FRTP may be lowered, which is not preferable.

  Regarding the method for obtaining the value in terms of solid content, if it is a liquid substance, quantitative analysis such as liquid chromatographic method of the constituent components of various glass fiber sizing agents is performed, or if it is attached to glass fiber, glass fiber What is necessary is just to calculate solid content by the method of eluting from the surface.

  In the glass fiber of the present invention, the adhesion rate of the glass fiber sizing agent of the present invention is in the range of 0.2 mass% to 0.6 mass%, so that a glass strand having high sizing properties can be obtained.

  The adhesion ratio of the glass fiber sizing agent of the present invention is in the range of 0.2 mass% to 0.6 mass% is a sizing agent applied to the surface of the glass fiber, which is a non-yellowing polyurethane and pyrroline. A glass fiber sizing agent containing an acid salt and having a non-yellowing polyurethane content of 50% by mass or more in terms of solid content is applied to the surface of the glass fiber, and the surface adhesion rate of the sizing agent is When the mass of the glass fiber after application | coating is set to 100, it represents that it exists in the range of 0.2 mass% to 0.6 mass%.

  When the adhesion rate of the glass fiber sizing agent of the present invention on the surface of the glass fiber is less than 0.2% by mass, sufficient sizing property may not be realized, and fluff is likely to occur during the production of the glass fiber. Even when FRTP is used, high strength cannot be obtained. On the other hand, when the adhesion rate of the glass fiber sizing agent of the present invention on the surface of the glass fiber exceeds 0.6% by mass, it is possible to improve the sizing property and the mechanical strength even though the sizing agent is applied as much. It is difficult to obtain a large contribution and it is not preferable because it is economically expensive.

  The glass fiber of the present invention may use various materials with respect to the material of the glass fiber. For example, E glass (non-alkali glass composition), AR glass (alkali resistant glass composition), C glass (acid-resistant alkali lime-containing glass composition), D glass (composition realizing low dielectric constant), S glass (high strength, To achieve high performance, T glass (composition realizing high strength and high modulus) and H glass (composition realizing high dielectric constant) can be used. It may be composed of a new glass composition developed in

  Moreover, the glass fiber of this invention is not specifically limited about the fiber diameter and fiber cross-sectional shape of the monofilament which comprises a strand. That is, a monofilament glass fiber having a diameter of several μm to several tens of μm can be used, and a true circle, a substantially ellipse, a flat circle, a hollow circle, a substantially rectangular shape, and the like can be appropriately employed for the cross-sectional shape. .

  Moreover, if the glass fiber of this invention is used for reinforcement | strengthening of a thermoplastic resin, the reinforcement which makes it possible to fully exhibit the mechanical performance suitable for a use by applying to various thermoplastic resins. Can be used as a material.

  Moreover, it is suitable for the glass fiber of this invention that the form of glass fiber is a short fiber in addition to the above-mentioned.

  Here, the form of the glass fiber is a short fiber, including, for example, a cut fiber so as to be a short fiber adjusted to a predetermined length, such as a glass chopped strand. It may be processed so as to have an arbitrary short dimension by a molding method such as. However, in order to achieve a predetermined performance and achieve a stable strength, it is more preferable to use a glass chopped strand.

  In the case of a glass chopped strand, the diameter of the glass fiber is preferably 3 μm to 40 μm as described above, and the longitudinal dimension thereof is preferably in the range of 1 mm to 20 mm.

  As a method of processing into a glass chopped strand, a specific method is not particularly recommended, and any method may be adopted as long as a desired processing dimension can be realized. As the processing method, cutting is suitable, but other methods may be used. Further, as a cutting method, there is no problem as long as the glass fiber bundle can be efficiently cut by using a device such as a drum cutter having an inner peripheral blade, a roll cutter having an outer peripheral blade cutter, and a hammer mill.

  Also, the aggregated form of chopped strands is not particularly limited. That is, glass fibers cut to an appropriate length can be laminated in a non-directional manner on a flat surface and molded with a specific binder, or can be three-dimensionally accumulated in a non-directional direction. In a one-dimensional direction, that is, parallel to a specific axial direction and solidified with a predetermined agent, that is, a resin or the like (also referred to as a glass master batch (GMB) pellet, resin columnar body, LFTP, etc.) There may be.

  Here, being used for the reinforcement of a thermoplastic resin means that it is used to improve the mechanical strength of a resin material that softens when heated and exhibits plasticity and solidifies when cooled. Yes.

  Examples of the thermoplastic resin include polyester resins such as PET resin and PBT resin, polyamide resins, olefin resins such as polyethylene and polypropylene, styrene resins such as AS resin and ABS resin, polycarbonate resins, polyacetal resins and polyphenylene sulfide (PPS). ) A thermoplastic resin such as a resin or a liquid crystal polymer (LCP) resin or a polymer alloy thereof is used, and is preferably an aromatic polyamide or semi-aromatic polyamide, PA46, PPS, or LCP used for reflow treatment. .

  When a polyamide resin is used as the thermoplastic resin, polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, Polyamide 6/6, Polyamide MXD (m-xylylenediamine), 6, Polyamide 6, T, Polyamide 6, I, Polyamide 6/6, T, Polyamide 6/6, I, Polyamide 6, 6/6 T, polyamide 6,6 / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12/6, T, polyamide 6,6 / 12 / 6, T, polyamide 6/12/6, I, or polyamide 6, 6/12/6, I, polyamide 9, T, etc., and a polymer obtained by copolymerizing a plurality of polyamides with an extruder or the like. Amides may also be used.

  Moreover, it is preferable that the mixing ratio of the glass fiber used when reinforcing the thermoplastic resin is 2 to 80% by mass of the glass fiber.

  In the method for producing glass fiber of the present invention, the glass fiber sizing agent of the present invention is applied to the glass filament drawn from the bushing, and then the filament is gathered to form a glass strand, and the glass strand is wound around a wound body. It is characterized by producing the glass fiber of the present invention by taking.

  Here, the glass fiber sizing agent of the present invention is applied to the glass filament drawn from the bushing, and then the filament is gathered to form a glass strand, and the glass strand is wound around a wound body to thereby form the glass fiber of the present invention. When manufacturing various glass raw materials so as to have a desired composition, and after homogeneously mixing, the raw materials are melted in a glass melting furnace made of a ceramic or refractory metal refractory substrate, The obtained molten glass is drawn out from a bushing made of a platinum heating and melting apparatus having thousands to tens of thousands of nozzles, and while cooling, the glass fiber bundling of the present invention containing non-yellowing polyurethane and pyrophosphate on the surface thereof Applying the agent, the filaments to which the sizing agent is applied are focused into glass strands. A glass fiber bundle called a strand, which means to form a cake-like structure by winding the holder surface of the tubular.

  And the glass fiber bundle of this cake-like structure can be utilized by reprocessing as various forms, such as roving, roving cloth, chopped strand, chopped strand mat, middle fiber, as needed.

  The glass fiber reinforced thermoplastic resin of the present invention is obtained by reinforcing a thermoplastic resin with the glass fiber of the present invention.

  Here, reinforced thermoplastic resin with the glass fiber of the present invention means that the glass fiber sizing agent of the present invention is applied so that the adhesion rate is in the range of 0.2 mass% to 0.6 mass%. This means that the glass fiber is obtained by compounding with a thermoplastic resin.

  In the present invention, the amount of glass fiber used for constituting the glass fiber reinforced thermoplastic resin is such that the mass of the glass fiber is 2% to 80% with respect to the total amount of the glass fiber thermoplastic resin. It is preferable. The glass fiber to be used may have any form, but it is more preferable to use the glass chopped strand in a dried state.

  The glass fiber reinforced thermoplastic resin of the present invention does not prevent the combined use of a reinforcing material other than the glass fiber of the present invention, and various other reinforcing materials may be used in appropriate amounts, for example, glass beads, mechanical pulverization Glass particles, ceramic particles other than glass, such as silica and alumina, natural minerals such as talc, various organic fibers, organic fillers, and carbon fibers.

  In addition to the above, the glass fiber reinforced thermoplastic resin of the present invention can obtain a homogeneous resin molding with low thermal expansion if the thermoplastic resin is a liquid crystal polymer resin. It can be used as a high-performance component used in the above.

  The glass fiber reinforced thermoplastic resin of the present invention can be used in various applications. In particular, printed circuit boards, case members for optical components related to optical fibers, electronic circuit boards used for highly integrated circuits, micro-circuits, etc. High performance as a micro member such as a motor, a compressor member and a shock absorber member for in-vehicle use, an internal structural member in various mechatronics devices such as a personal computer and a copying machine, a shaft member that requires rotating operation, and a fuel cell member It is possible to demonstrate.

  (1) As described above, the glass fiber sizing agent of the present invention is a sizing agent applied to the surface of glass fiber, and contains a non-yellowing polyurethane and a pyrophosphate, and the non-yellowing polyurethane When the content of the glass fiber is 50% by mass or more in terms of solid content and used on the surface of the glass fiber shared for the purpose of reinforcing the thermoplastic resin, it is added several times in addition to the molding of the thermoplastic resin. Even in applications where heat treatment is performed over a wide range, it exhibits high heat discoloration and exhibits excellent performance without impairing the mechanical strength of the thermoplastic resin.

  (2) Moreover, the sizing agent for glass fibers of the present invention has a mass reduction rate according to JIS K7120 (1987) of a non-yellowing polyurethane while the temperature is increased from 200 ° C. to 300 ° C. at a temperature increase rate of 25 ° C./min. If it is 2% or less, even when the glass fiber sizing agent is exposed to a high temperature state, the non-yellowing polyurethane contained in the glass fiber sizing agent is unlikely to deteriorate, resulting in high film system performance. Thus, it is possible to obtain a thermoplastic resin having stable mechanical strength.

  (3) Further, the glass fiber sizing agent of the present invention has the effect of adding non-yellowing polyurethane as long as the mass content ratio in terms of solid content of pyrophosphate to non-yellowing polyurethane is within the range of 10% to 75%. Thus, it is possible to obtain a glass fiber reinforced thermoplastic resin having excellent performance in both heat discoloration and mechanical strength.

  (4) Further, the glass fiber of the present invention has an adhesion rate of the glass fiber sizing agent of the present invention in the range of 0.2% to 0.6% by mass. It is possible to impart sufficient performance to the glass fiber without excess or deficiency, and to produce a stable glass fiber.

  (5) Furthermore, if the glass fiber of the present invention is used to reinforce a thermoplastic resin, it is possible to obtain a thermoplastic resin having sufficient mechanical strength in addition to high heat discoloration performance. It is possible to further expand the application range of the reinforced thermoplastic resin.

  (6) The method for producing glass fiber of the present invention comprises applying the glass fiber sizing agent of the present invention to a glass filament drawn from a bushing, and then gathering the filament to form a glass strand. Since the glass fiber of the present invention is produced by winding it on a wound body, it is possible to apply various production conditions established so far, and efficiently and efficiently produce high-quality glass fiber. Can be manufactured automatically.

  (7) Since the glass fiber reinforced thermoplastic resin of the present invention is formed by reinforcing the thermoplastic resin with the glass fiber of the present invention, a glass fiber reinforced thermoplastic resin having a function suitable for various uses, In particular, it has an appropriate function as a glass fiber reinforced thermoplastic resin used in applications exposed to high temperature environments.

  (8) The glass fiber reinforced thermoplastic resin of the present invention, if the thermoplastic resin is a liquid crystal polymer resin, in addition to improving the mechanical strength of the liquid crystal polymer resin used as engineering plastics, Even when heat treatment is performed a plurality of times, it has an appearance that is not discolored or colored.

  Hereinafter, based on an Example, the glass fiber sizing agent of this invention, the glass fiber which apply | coated this sizing agent, its manufacturing method, and the glass fiber reinforced thermoplastic resin using the glass fiber of this invention are demonstrated in detail.

  Sample No. which is an example of the present invention. 1 to sample no. 5 is shown in Table 1. Sample No. 101 to sample no. 103 is shown in Table 2, and the evaluation results of the glass fiber sizing agent, glass fiber, and glass fiber reinforced thermoplastic resin molded product are summarized and described in detail below.

  First, the glass fiber sizing agent of the present invention was measured for the amount of non-yellowing polyurethane and pyrophosphate so as to have the mass% shown in Table 1, respectively, and the silane coupling agent and deionized water (ion) After measuring an appropriate amount (also referred to as exchange water), each is mixed at room temperature so as to be in a homogeneous state to obtain a glass fiber sizing agent. By the way, in this example, the non-yellowing polyurethane is TG (thermogravimetric measurement) at 300 ° C. based on the mass value at 200 ° C. when heated at 25 ° C./min according to JIS K7120 (1987). A non-yellowing urethane emulsion having a value of 2% or less is used according to a method calculated from a curve. As for pyrophosphate, other pyrophosphate such as potassium pyrophosphate can be used, but here, sodium pyrophosphate decahydrate is used. Further, the silane coupling agent may be another silane coupling agent, but γ-aminopropyltriethoxysilane was used here.

  Regarding the glass fiber, the glass fiber having the E glass composition homogeneously melted in the glass melting furnace is continuously drawn out from the nozzle of the heat-resistant bushing, and the glass obtained by the above-described preparation procedure on the surface of the obtained glass filament. A fiber sizing agent was applied by an applicator, 4000 glass filaments were converged by a gathering shoe, and wound as a strand onto a paper tube to obtain a wound body. Next, a glass strand was drawn out from the wound body, cut with a glass fiber cutting device to a length of 3 mm using a cutting device, and then dried to obtain a glass chopped strand.

  Next, 30 mass% of this chopped strand and 70 mass% of liquid crystal polymer resin (trade name Vectra, manufactured by Polyplastics) were kneaded while heating to 330 ° C., and FRTP was obtained by injection molding pellets according to a conventional method. .

  The FRTP obtained in this way was processed so that the shape of the test piece had a thickness of 3.2 mm of type I according to ASTM D-638 issued in 1992 for the tensile strength test, and INSTRON (Model No. 4202) manufactured by Instron Corporation. The measurement was performed three times using and the average value was adopted. Regarding the Izod impact test, an Izod test apparatus manufactured by Ueshima Seisakusho was used, a test piece having a test piece size b of 3.2 mm was prepared according to ASTM D256, and an average value of five measurements was adopted. Further, the hue is measured according to JIS Z8722 (2000) “Color Measurement Method—Reflection and Transmission Object Color” according to the condition d according to the reflection object measurement method, and 4 according to the measurement device (model number Sigma 90) manufactured by Nippon Denshoku Industries Co. Measurement was performed once, and an average value of the measurement values b was adopted. The test method adopted to investigate the hue change Δb value due to the heat treatment is to hold the molded FRTP in a 250 ° C. heating oven for 2 minutes and perform the heat treatment to measure the FRTP hue before and after heating. Thus, the difference between the two is calculated. Therefore, the smaller the Δb value, the smaller the change in color tone due to heating, and the higher the heat discoloration.

  Moreover, about the measurement of the adhesion rate of the glass fiber sizing agent to the glass fiber surface, it is measured by the ignition loss according to JIS R3420 (1999).

  First, Sample No. as an example. 1 is 7.0% by mass of a non-yellowing urethane emulsion (solid content 40% by mass) having a mass reduction rate of 1.2% measured according to JIS K7120, 0.6% by mass of γ-aminopropyltriethoxysilane, pyrophosphoric acid A sizing agent comprising 0.5% by weight of sodium decahydrate and 91.9% by weight of deionized water is prepared. The solid content of the non-yellowing urethane emulsion in the sizing agent is 76.5%, the pyrophosphate content is 13.7%, and the solid content of the non-yellowing urethane emulsion is solid content. The ratio of pyrophosphate content to content was 17.9%. After applying this sizing agent to the surface of a glass fiber having a diameter of 10 μm, 4000 glass fibers are converged and then cut into 3 mm lengths to produce chopped strands. A fiber-reinforced thermoplastic resin is obtained. Incidentally, the adhesion amount of the glass fiber sizing agent to the glass fiber surface was 0.4% when measured by the method described above. This sample No. As a result of evaluation of 1, the tensile strength according to ASTM D-638 showed a sufficiently high value at 194 MPa, and the Izod impact strength according to ASTM D256 was 115 J / m, which was also sufficiently high. As for the color tone, the b value of the hue in the normal state was measured according to JIS Z8722 (2000). The value was 8.2, and no coloration was observed. Further, the color tone was determined by heating after performing the heat treatment according to the above procedure. The value of Δb of hue change was 1.5, indicating no significant change.

  In addition, sample No. 2 is 7.0% by mass of non-yellowing urethane emulsion (solid content 40% by mass) having a mass reduction rate of 0.8% measured according to JIS K7120, 0.6% by mass of γ-aminopropyltriethoxysilane, pyrophosphoric acid Sample No. 5 was used except that a sizing agent consisting of 2.0% by mass of sodium decahydrate and 90.4% by mass of deionized water was used. FRTP was prepared under the same conditions as in 1. Therefore, the solid content conversion ratio of the non-yellowing urethane emulsion in this sizing agent is 54.3%, and the pyrophosphate content is 38.8%, which is the solid conversion of the non-yellowing urethane emulsion. The ratio of the pyrophosphate content to the content of 71.5% was 71.5%. Incidentally, the adhesion amount of the glass fiber sizing agent to the glass fiber surface was 0.5% when measured by the method described above. And this sample No. For sample No. 3, sample no. When the same evaluation as in Example 1 was performed, the tensile strength was 184 MPa, the Izod impact strength was 107 J / m, which was sufficiently high, the b value of the hue in a normal state was 7.7, and the hue change due to heating The value of Δb representing was 1.1, and had excellent heat discoloration performance that did not show a significant change like the samples of the other examples.

  And sample No. of an Example. 3 is 3.0% by mass of a non-yellowing urethane emulsion (solid content 40% by mass) having a mass reduction rate of 0.9% measured according to JIS K7120, 0.6% by mass of γ-aminopropyltriethoxysilane, pyrophosphoric acid FRTP was prepared under the same conditions as in Example 1 except that a sizing agent consisting of 0.5% by weight of sodium decahydrate and 95.9% by weight of deionized water was used. Therefore, the solid content conversion ratio of the non-yellowing urethane emulsion in this sizing agent is 58.3%, the pyrophosphate content is 24.3%, and the solid content conversion of the non-yellowing urethane emulsion is 24.3%. The ratio of the pyrophosphate content to the content of 41.7% was 41.7%. Incidentally, the adhesion amount of the glass fiber sizing agent to the glass fiber surface was 0.2% when measured by the method described above. This sample No. 4 was evaluated in the same manner as the samples of the other examples. The tensile strength was 188 MPa, the Izod impact strength was 102 J / m, which was sufficiently high, and the b value of the hue in the normal state. The value of Δb representing the hue change due to heating was 1.4, and it had stable heat-resistant discoloration performance that did not show a large change as in the samples of other examples.

  Sample No. of Example 4 is 12.0% by mass of a non-yellowing urethane emulsion (solid content 40% by mass) having a mass reduction rate of 1.3% measured according to JIS K7120, 0.6% by mass of γ-aminopropyltriethoxysilane, pyrophosphoric acid FRTP was prepared under the same conditions as in Example 1 except that a sizing agent consisting of 0.5% by weight of sodium decahydrate and 86.9% by weight of deionized water was used. The content of the non-yellowing urethane emulsion in the sizing agent in terms of solid content is 84.8%, the content of pyrophosphate is 8.8%, and the content in terms of solid content of the non-yellowing urethane emulsion is The ratio of the content rate of pyrophosphate to the content rate was 10.38%. Incidentally, the adhesion amount of the glass fiber sizing agent to the glass fiber surface was 0.6% when measured by the method described above. Sample No. 5 was evaluated in the same manner as the samples of the other examples. The tensile strength was 196 MPa, the Izod impact strength was 115 J / m, which was sufficiently high, and the b value of the hue in the normal state. The value of Δb representing the hue change due to heating was 2.0, and it had stable heat discoloration performance that did not show a large change as in the samples of the other examples.

  Subsequently, sample No. which is a comparative example of the present invention. 101, a non-yellowing urethane emulsion having a mass reduction rate of 1.2% measured in accordance with the same JIS K7120 as the sizing agent for glass fibers used in the same procedure as in Example 1 (solid content: 40% by weight) It was prepared by mixing 5.0% by weight, 0.6% by weight of γ-aminopropyltriethoxysilane, 5.0% by weight of sodium pyrophosphate decahydrate, and 89.4% by weight of deionized water. And FRTP was produced on the same conditions as Example 1 except having used this sizing agent. Therefore, the solid content conversion ratio of the non-yellowing urethane emulsion in the sizing agent is 27.1%, and the pyrophosphate content ratio is 67.9%, which is the solid conversion of the non-yellowing urethane emulsion. The ratio of the pyrophosphate content to the content of 250.6% was a value exceeding 75%. Moreover, when the adhesion amount of the glass fiber sizing agent to the glass fiber surface was measured by the method described above, it was 0.4%. This sample No. The component content ratio of the sizing agent 101 has been conventionally practiced. In this regard, when the same evaluation as the sample of the example was performed, the tensile strength was 150 MPa and the Izod impact strength was 80 J / m. The value of Izod impact strength is small, the b value of the hue in the normal state is 7.4, the value of Δb representing the hue change by heating is 3.0, and a significant discoloration is recognized by heating. When the heat treatment was performed twice or more, discoloration was increased.

  Furthermore, sample No. which is a comparative example of the present invention. For No. 102, 7.0% by mass of a non-yellowing urethane emulsion (solid content of 40% by mass) having a mass reduction rate measured according to JIS K7120 of 3.2% and a value exceeding 2% in the same procedure as in the example. , A sizing agent comprising 0.6% by mass of γ-aminopropyltriethoxysilane, 0.5% by weight of sodium pyrophosphate decahydrate, and 91.9% by mass of deionized water is prepared. Therefore, each mixing ratio is the sample No. of an Example. 1 and the non-yellowing urethane emulsion in the sizing agent has a solid content equivalent content of 76.5% and a pyrophosphate content of 13.7%. The ratio of the pyrophosphate content to the solid content of the emulsion was 17.9%. Moreover, when the adhesion amount of the glass fiber sizing agent to the glass fiber surface was measured by the method described above, it was 0.4%. This sample No. When the same evaluation as in the example was performed for 102, the tensile strength was 183 MPa, the Izod impact strength was 100 J / m, the b value of the hue in the normal state was 10.5, and Δb representing the hue change due to heating The value was 3.3, indicating a large hue change compared to the sample of the example.

  Further, Sample No. which is a comparative example of the present invention. For sample No. 103, the sample No. of the example is the same as the example. The same glass fiber sizing agent as in No. 1 was used, but the amount applied to the glass fiber surface was intentionally adjusted so that the glass fiber sizing agent adhered to the glass fiber surface. When the amount was measured by the method described above, it was 0.18% and a value less than 0.2%. And this sample No. When the same evaluation as in the example was performed for No. 103, the tensile strength was 164 MPa, and the Izod impact strength was 95 J / m, which was a lower value than that of the example. The result was left. Further, the b value of the hue in the normal state was 8.6, and the value of Δb representing the hue change by heating was 2.0.

  From the above-described series of evaluation results, the glass fiber sizing agent of the present invention has high heat discoloration by being coated on glass fiber, and does not change to a dark color even by secondary heat treatment. In addition to that, glass fiber that can realize a sufficiently high value for the strength of the thermoplastic resin and is an essential structural material for producing a glass fiber reinforced thermoplastic resin having excellent quality. It became clear that the quality of the can be improved.

Claims (8)

A sizing agent applied to the surface of glass fiber,
A glass fiber sizing agent comprising non-yellowing polyurethane and pyrophosphate, wherein the content of the non-yellowing polyurethane is 50% by mass or more in terms of solid content.   The mass reduction rate according to JIS K7120 (1987) of a non-yellowing polyurethane is 2% or less during a temperature increase from 200 ° C to 300 ° C at a temperature increase rate of 25 ° C / min. The bundling agent for glass fiber as described.   3. The glass fiber sizing agent according to claim 1, wherein a mass content ratio in terms of solid content of pyrophosphate to non-yellowing polyurethane is in the range of 10% to 75%.   A glass fiber, wherein the adhesion rate of the glass fiber sizing agent according to any one of claims 1 to 3 is in the range of 0.2 mass% to 0.6 mass%.   The glass fiber according to claim 4, wherein the glass fiber is used for reinforcement of a thermoplastic resin.   The glass fiber sizing agent of the present invention is applied to the glass filament drawn from the bushing, and then the filament is gathered to form a glass strand, and the glass strand is wound around a wound body. A method for producing glass fiber, comprising producing the glass fiber described in 1.   A glass fiber reinforced thermoplastic resin obtained by reinforcing a thermoplastic resin with the glass fiber according to claim 4.   The glass fiber reinforced thermoplastic resin according to claim 7, wherein the thermoplastic resin is a liquid crystal polymer resin.