JP7385117B2 - Glass fiber for resin reinforcement and glass fiber reinforced resin molded products - Google Patents

Description

The present invention relates to resin-reinforced glass fibers and glass fiber-reinforced resin molded products using the same.

In recent years, fiber-reinforced resin materials have attracted attention as an alternative material to metals. However, since the heat resistance of resin is inferior to that of metal, there is a problem that metals have not been replaced by fiber-reinforced resin materials in applications that require high heat resistance.

In order to solve the above problem, polyetherimide resin (PEI) and polyether ether ketone resin (polyether ether ketone resin), which have a heat deformation temperature of 300°C or higher, are used as fiber-reinforced resin materials that can be used in applications that require high heat resistance. Fiber-reinforced resin molded products containing highly heat-resistant resins such as PEEK) are being considered (see, for example, Patent Documents 1 and 2).

Usually, in the reinforcing fibers used in fiber-reinforced resin molded products, organic matter is attached to the surface of the reinforcing fibers in order to improve the adhesion between the reinforcing fibers and the resin and improve the strength of the fiber-reinforced resin molded products. things are being done. However, the molding temperature of highly heat-resistant resins is high, and most of the organic substances are thermally decomposed. Therefore, in the inventions described in Patent Documents 1 and 2, it is proposed to attach a high heat resistant resin itself to the surface of reinforcing fibers for reinforcing the high heat resistant resin.

International Publication No. 2018/079700 Special table 2017-505843 publication

However, in order to attach the highly heat resistant resin to the surface of the reinforcing fibers, it is necessary to melt the highly heat resistant resin at a high temperature, which is disadvantageous in that productivity is reduced.

The present invention solves such disadvantages, has excellent productivity, and is capable of improving the mechanical strength of a fiber-reinforced resin molded product containing a highly heat-resistant resin with a deflection temperature under load of 120°C or higher. The purpose of the present invention is to provide glass fibers for use in glass fibers and glass fiber reinforced resin molded products using the glass fibers.

In order to achieve this object, the resin-reinforcing glass fiber of the present invention is made of a group consisting of thermoplastic polyimide, polyaryletherketone, polyarylene sulfide, liquid crystal polyester, polyether sulfone, semi-aromatic nylon, and syndiotactic polystyrene. A resin-reinforcing glass fiber selected from The acid has an average number of hydrogen atoms at the alpha carbon position of the group of 0.5 or more, and is characterized in that the amount of the acid attached is in the range of 42 to 400 ppm based on the total amount of the resin-reinforcing glass fiber.

By having the above structure, the resin-reinforced glass fiber of the present invention can be made into a fiber-reinforced resin molded product without adhering a highly heat-resistant resin to the surface of the resin-reinforced glass fiber. Since the adhesion between the glass fiber and the resin can be improved, the productivity of the fiber-reinforced resin molded product is excellent, and the strength of the fiber-reinforced resin molded product can be improved.

In the resin-reinforcing glass fiber of the present invention, when the amount of the acid attached is less than 42 ppm based on the total amount of the resin-reinforcing glass fiber, the adhesion between the resin-reinforcing glass fiber and the resin can be improved. I can't. On the other hand, even if the amount of the acid attached exceeds 400 ppm based on the total amount of the resin-reinforcing glass fibers, it is not possible to further improve the adhesion between the resin-reinforcing glass fibers and the resin.

In the resin-reinforcing glass fiber of the present invention, the acid has an average hydrogen number of preferably 1.2 or more, more preferably 2.0 or more at the α carbon position of the carboxyl group. In the glass fiber for resin reinforcement of the present invention, for example, acetic acid can be used as the acid.

Further, in the resin-reinforcing glass fiber of the present invention, the amount of the acid attached is preferably in the range of 90 to 200 ppm based on the total amount of the resin-reinforcing glass fiber.

Moreover, in the glass fiber for resin reinforcement of the present invention, it is preferable that the silane coupling agent is an amine-containing silane coupling agent.

The present invention also resides in a glass fiber-reinforced resin molded product containing the resin-reinforcing glass fiber of the present invention and a resin having a deflection temperature under load of 120° C. or higher.

Next, embodiments of the present invention will be described in more detail.

The glass fiber for resin reinforcement of this embodiment is selected from the group consisting of thermoplastic polyimide, polyaryletherketone, polyarylene sulfide, liquid crystal polyester, polyether sulfone, semi-aromatic nylon, and syndiotactic polystyrene. A resin-reinforcing glass fiber used for reinforcing resins at a temperature of 120°C or higher, with an acid and a silane coupling agent attached to the surface, and the acid is an average of the α carbon position of the carboxyl group. The acid has a hydrogen number of 0.5 or more, preferably 1.2 or more, more preferably 2.0 or more, and the amount of the acid attached is 42 to 400 ppm, preferably 90 ppm based on the total amount of glass fiber for resin reinforcement. ~200ppm.

The resin reinforced with the resin-reinforcing glass fiber of the present embodiment is a resin having a deflection temperature under load of 120°C or higher, preferably a resin having a deflection temperature under load of 150°C or higher, and more preferably a deflection temperature under load of 150°C or higher. is a resin with a temperature of 180°C or higher. An example of the upper limit of the deflection temperature under load of the resin reinforced with the resin-reinforcing glass fiber of this embodiment is 400°C. Here, the deflection temperature under load of the resin can be measured in accordance with ASTM D648 (1.8 MPa).

Examples of the resin having a deflection temperature under load of 120° C. or higher include resins such as thermoplastic polyimide, polyaryletherketone, polyarylene sulfide, liquid crystal polyester, polyether sulfone, semi-aromatic nylon, and syndiotactic polystyrene. Can be done. The resin reinforced with the glass fiber for resin reinforcement of this embodiment is a thermoplastic polyimide or a polyester resin, since it has better heat resistance and is less likely to deteriorate even when molded at a higher temperature. Aryl ether ketone is preferable, polyether imide or polyether ether ketone is more preferable, and the effect of improving the strength of glass fiber reinforced resin molded products by using the resin reinforcing glass fiber of this embodiment It is more preferable to use polyetherimide because it has a particularly large value.

Examples of the acid include organic acids such as acetic acid, malonic acid, citric acid, maleic acid, propionic acid, succinic acid, and malic acid, but acetic acid is preferred. In the acid, the average number of hydrogens at the α carbon position of the carboxyl group is 0.5 or more means that the average number of hydrogens at the α carbon position of each carboxyl group present in the acid is 0.5 or more. It means something. Here, the chemical structure of the acid can be identified by extracting the acid attached to the surface of the resin-reinforcing glass fiber with an aqueous solvent and analyzing it by ¹ H-NMR or the like.

In addition, examples of the silane coupling agent include aminosilane (γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N' -β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, etc.), chlorosilane (γ-chloropropyltrimethoxysilane, etc.), epoxysilane (γ-glycidoxypropyltrimethoxysilane, etc.) silane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.), mercaptosilane (γ-mercaptotrimethoxysilane, etc.), vinylsilane (vinyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, etc.), acrylic silane (γ-methacryloxypropyltrimethoxysilane, etc.), cationic silane (N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride) , N-phenyl-3-aminopropyltrimethoxysilane hydrochloride, etc.), and amine-containing silane coupling agents are preferred because they are highly effective in improving the strength of glass fiber reinforced resin molded products. More preferred is aminosilane. Here, after extracting the silane coupling agent from the resin-reinforcing glass fiber of this embodiment using an aqueous or organic solvent, the chemical structure of the silane coupling agent is identified by using GC-MS. It can be performed.

In addition to the acid and the silane coupling agent, a surfactant, a resin emulsion, etc. may be attached to the resin-reinforcing glass fiber of this embodiment, but since the adhesiveness with the resin is improved, Preferably, only the acid and the silane coupling agent are attached.

Examples of the form of the glass fiber used for the resin-reinforcing glass fiber of this embodiment include woven fabric (glass cloth), knitted fabric, yarn, chopped strand, roving, chopped strand mat, paper, mesh, braided fabric, and milled fiber. However, woven fabric (glass cloth) is preferable.

When the glass fiber is a woven fabric (glass cloth), the resin-reinforced glass fiber of this embodiment can be manufactured, for example, as follows.

First, glass filaments are obtained by melting and fiberizing a glass batch (glass raw material) that has been adjusted to have a predetermined glass composition.

The predetermined glass composition includes the most general-purpose E glass composition (SiO ₂ in the range of 52.0 to 56.0% by mass in terms of oxides, and 12.0 to 16% by mass based on the total amount of glass fibers). Al ₂ O ₃ in the range of .0 mass %, MgO and CaO in the range of 20.0 to 25.0 mass % in total, and B ₂ O ₃ in the range of 5.0 to 10.0 mass %. composition), high strength and high modulus glass composition (SiO ₂ in the range of 64.0 to 66.0 mass % and Al ₂ O ₃ in the range of 24.0 to 26.0 mass % based on the total amount of glass fibers) and MgO in the range of 9.0 to 11.0 mass %), high elastic modulus easily manufacturable glass composition (SiO in the range of 57.0 to 60.0 mass % based on the total amount of glass fiber) ₂ , Al ₂ O ₃ in the range of 17.5 to 20.0 mass %, MgO in the range of 8.5 to 12.0 mass %, and CaO in the range of 10.0 to 13.0 mass %. , B ₂ O ₃ in the range of 0.5 to 1.5 mass %, and the total amount of SiO ₂ , Al ₂ O ₃ , MgO and CaO is 98.0 mass % or more), and , low dielectric constant and low dielectric loss tangent glass composition (SiO ₂ in the range of 48.0 to 62.0 mass % and B ₂ O ₃ in the range of 17.0 to 26.0 mass % with respect to the total amount of glass fibers, Al ₂ O ₃ in the range of 9.0 to 18.0 mass %, CaO in the range of 0.1 to 9.0 mass %, MgO in the range of 0 to 6.0 mass %, and a total of 0.05 Na ₂ O, K ₂ O and Li ₂ O in the range of ~0.5% by mass, TiO ₂ in the range of 0 to 5.0% by mass, SrO in the range of 0 to 6.0% by mass, the total compositions containing F ₂ and Cl ₂ in the range from 0 to 3.0% by weight and P ₂ O ₅ in the range from 0 to 6.0% by weight).

The filament diameter of the glass filament is not particularly limited, but is preferably, for example, 30 μm or less, more preferably in the range of 3 to 25 μm, and particularly preferably in the range of 6 to 20 μm.

The glass filaments, for example, in a number ranging from 25 to 5000, preferably from 200 to 800, more preferably from 300 to 600, are bundled by a method known per se to form a glass fiber thread. Note that spinning is a process in which a glass batch is melted and made into fibers to obtain glass filaments, and then a plurality of these glass filaments are bundled to obtain a glass fiber thread.

The count of the glass fiber yarn is, for example, 0.5 to 2500 tex, preferably 30 to 1500 tex, more preferably 40 to 500 tex, even more preferably 50 to 250 tex, and even more preferably 60 to 135 tex. It is particularly preferable that Note that the count (tex) of the glass fiber yarn corresponds to the mass (g) of the glass fiber per 1000 m. Here, the count of the glass fiber yarn can be measured in accordance with JIS R 3420:2013.

The glass fiber thread may be twisted 0 to 2 times/25 mm. Here, the number of twists of the glass fiber yarn can be measured in accordance with JIS R 3420:2013.

The glass fiber threads can be used, for example, by bundling 2 to 5 glass fiber threads without twisting them together, or by twisting 2 to 5 glass fiber threads together. The number of twists when twisting a plurality of glass fiber threads is 0 to 5 times/25 mm.

Next, a woven fabric (glass cloth) is obtained by weaving the glass fiber yarn as warp or weft. The weaving method is not particularly limited, and examples thereof include plain weave, satin weave, twill weave, ribbed weave, and diagonal weave, and plain weave is preferred. The weaving density of the warp and weft of the glass fiber yarn during the weaving is not particularly limited, but can be, for example, 10 to 150 yarns/25 mm, preferably 15 to 65 yarns/25 mm, and 20 to 65 yarns/25 mm. It is more preferable that the number is 45 lines/25 mm. Here, the weave density can be measured in accordance with JIS R 3420:2013.

During the weaving, a sizing agent is used to bundle the glass filaments and warp the warp threads. Examples of the sizing agent include sizing agents whose film-forming agent component is starch-based or PVA (polyvinyl alcohol)-based. The sizing agent may include an oil agent, a softener, or the like.

The amount of the sizing agent adhered to the textile (glass cloth) is preferably 0.1 to 3 parts by mass, and preferably 0.5 to 1 part by mass relative to 100 parts by mass of the glass fiber yarn. More preferably, the amount is .5 parts by mass. Note that the range of the amount of the sizing agent attached and the amount of the sizing agent attached unless otherwise specified represent the average amount of the sizing agent attached to the warp or weft.

The woven fabric (glass cloth) has, for example, a weight in the range of 50 to 1500 g/m ² , preferably a weight in the range of 110 to 800 g/m ² , more preferably 150 to 400 g/m 2 It has a mass in the range of ² . Here, the mass of the fabric can be measured in accordance with JIS R 3420:2013.
Next, the woven fabric (glass cloth) may be subjected to a fiber opening treatment. Examples of the fiber-spreading treatment include fiber-spreading using water pressure, fiber-spreading using high-frequency vibration using a liquid as a medium, fiber-spreading using the pressure of a fluid having a surface pressure, fiber-spreading using roll pressure, and the like. Can be done. Among the above-mentioned opening treatments, using opening using water pressure or opening using high-frequency vibration using liquid as a medium reduces the variation in yarn width after opening for each of the warp and weft. It is preferable because Further, the fiber opening treatment may be performed using a plurality of treatment methods in combination.

Next, the woven fabric (glass cloth) is subjected to oil removal treatment. The deoiling treatment is performed, for example, by placing the glass cloth in a heating furnace at an ambient temperature of 350° C. to 450° C. for 40 to 80 hours, and removing the spinning sizing agent and weaving sizing agent attached to the glass cloth. This can be done by thermally decomposing.

Next, the woven fabric (glass cloth) subjected to the oil removal treatment is immersed in a surface treatment agent solution containing the silane coupling agent and the acid. Next, after squeezing out excess water from the fabric (glass cloth) to which the surface treatment agent solution has been applied, it is heated at a temperature in the range of 80 to 180°C for 1 to 30 minutes, for example at 110°C for 5 minutes. By heating and drying, a surface-treated glass cloth as the resin-reinforced glass fiber of this embodiment is obtained. In addition, in the surface-treated glass cloth to which the surface treatment agent solution has been applied, a part of the acid adhering to the surface evaporates when the surface-treated glass cloth is heated and dried.

Examples of the solvent for the surface treatment agent solution include water, ethylene glycol, and ethanol. Further, after the oil removal treatment, the surface-treated glass cloth can be subjected to a second opening treatment.

The thickness of the surface-treated glass cloth obtained is, for example, in the range of 50 to 1500 μm, preferably in the range of 110 to 700 μm, more preferably in the range of 140 to 400 μm, and even more preferably in the range of 160 μm. ~250 μm. Here, the thickness of the surface-treated glass cloth can be measured in accordance with JIS R 3420:2013.

In the glass fiber for resin reinforcement of the present embodiment, the amount of the silane coupling agent attached is, for example, 400 to 2000 ppm, preferably 500 to 1200 ppm, more preferably 600 to 1000 ppm, based on the total amount of the glass fiber for resin reinforcement. is within the range of

The amount of the silane coupling agent attached can be measured as follows.

[Measurement of silane coupling agent adhesion amount]
The surface-treated glass cloth is cut into pieces approximately 1 cm x 3 cm in size, weighed, and then a solvent is placed in a screw tube and heated to a predetermined temperature on a hot plate to extract the silane coupling agent. Specifically, after washing by heating at 45°C in a methylene chloride solvent, insoluble matter is filtered off, and extracted twice with methanol at 70°C and water at 80°C.

Each concentrated extract is subjected to ¹ H-NMR measurement, and the amount of silane coupling agent in each extract is determined from the integral value using the internal standard method (internal standard: 1,4-pyrazine). From the sum of the amount of silane coupling agent in the methanol extract and the silane coupling agent in the water extract and the weight of the surface-treated glass cloth, the silane cup of the surface-treated glass cloth obtained in this example was determined. Calculate the amount of ring agent attached.

Further, in the resin-reinforcing glass fiber of the present embodiment, the ignition loss is, for example, 500 to 5000 ppm, preferably 600 to 4800 ppm, more preferably 700 to 4500 ppm, and even more preferably ranges from 750 to 3000 ppm, particularly preferably from 800 to 2000 ppm, most preferably from 850 to 1500 ppm. The ignition loss can be measured in accordance with JIS R 3420:2013.

The glass fiber-reinforced resin molded product of this embodiment includes the resin of this embodiment described above whose deflection temperature under load is 120° C. or higher and the resin-reinforcing glass fiber of this embodiment described above.

The glass fiber-reinforced resin molded product of this embodiment is produced by injection molding, injection compression, etc. using the resin with a deflection temperature under load of 120°C or higher of this embodiment described above, and the resin-reinforcing glass fiber of this embodiment described above. Molding method, two-color molding method, blow molding method, foam molding method (including supercritical fluid foam molding method), insert molding method, in-mold coating molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, lamination molding method, press molding method, blow molding method, stamping molding method, infusion method, hand lay-up method, spray-up method, resin transfer molding method, sheet molding compound method, bulk molding compound method, pultrusion method, It can be obtained by molding using a known molding method such as a filament winding method.

Next, examples and comparative examples of the present invention will be shown.

[Example 1]
In this example, first, E glass cloth corresponding to 7628 according to the IPC standard (68 tex E glass fiber yarn in which E glass filaments with a filament diameter of 9 μm are bundled in the warp and weft) is used, and the warp weave density is 44 fibers. /25.4mm, weft density is 31 threads/25.4mm, 200g/ ^m2 , 175μm thick plain weave glass cloth) After weaving, organic matter present on the surface of the glass cloth was removed by heat cleaning. I prepared a glass cloth.

Next, 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903) was added as a silane coupling agent to an aqueous solution prepared so that acetic acid was 83.7 mmol/kg. The glass cloth was immersed in an aqueous treatment solution containing .5% by mass, squeezed with a mangle, and further dried at 110°C for 5 minutes to obtain the resin-reinforcing glass fiber of this example. A surface-treated glass cloth was obtained. The resulting surface-treated glass cloth had an acid adhesion amount of 120 ppm, a silane coupling agent adhesion amount of 830 ppm, and an ignition loss of 0.101%.

Next, 10 sheets of surface-treated glass cloth as glass fibers for resin reinforcement obtained in this example and a polyetherimide film with a thickness of 100 μm (manufactured by Mitsubishi Plastics Co., Ltd., product name: Superio UT E type, deflection under load) were used. In this example, 18 sheets (temperature: 200°C) were stacked and held at 380°C for 10 minutes under contact pressure, then the surface pressure was set to 30kgw/ ^cm2 , held for 5 minutes, and cooled to room temperature. A polyetherimide composite material having a volume content of 40% and a thickness of 2 mm was obtained as a glass fiber reinforced resin molded product.

Regarding the surface-treated glass cloth as resin-reinforced glass fiber obtained in this example, the amount of acid adhesion was calculated as follows. The normal bending strength of the imide composite material was measured as follows, and the rate of increase in strength was calculated. The results are shown in Table 1.

In Table 1, "average number of hydrogens" means the average number of hydrogens at the α carbon position of a carboxyl group, and "aminosilane" means 3-aminopropyltriethoxysilane.

[Amount of acid adhesion]
The surface-treated glass cloth obtained in this example was cut, weighed, added with chloroform, washed in an ultrasonic bath, shaken in a dilute alkaline solution, and subjected to acid extraction in an ultrasonic bath. The extract was centrifuged, and the aqueous layer was used as a sample solution. Next, the sample solution and standard solution were measured using an electrophoresis system (manufactured by Agilent Technologies, product name: 7100 capillary electrophoresis system, buffer solution: organic acid analysis buffer manufactured by Agilent Technologies), and one-point calibration was performed. The amount of acid in the sample solution was determined by the line method. Next, the amount of acid attached to the surface-treated glass cloth was calculated from the mass of the surface-treated glass cloth and the determined mass of the acid.

[Normal bending strength]
Measurement was performed using a precision universal testing machine (manufactured by Shimadzu Corporation, trade name: Autograph AG-5000B) in accordance with JIS K 7017:1999 (Method A/Class III test piece).

[Strength increase rate]
A glass fiber-reinforced resin molded product (glass fiber-reinforced resin molded product to which no acid is attached) obtained in exactly the same manner as in this example except that a surface-treated glass cloth to which no acid is attached was used was as described above. The normal bending strength was measured by the method described above, and calculated by the following formula. In this example, the "glass fiber-reinforced resin molded product to which no acid is attached" corresponds to the glass fiber-reinforced resin molded product obtained in Comparative Example 1 below.

Strength increase rate (%) = ((normal bending strength of the glass fiber reinforced resin molded product obtained in this example - normal bending strength of the glass fiber reinforced resin molded product to which no acid is attached)/acid attached Normal bending strength of glass fiber reinforced resin molded product without
[Example 2]
This example was carried out in the same manner as in Example 1, except that the glass cloth was immersed in the aqueous treatment solution, the liquid was squeezed out with a mangle, and then dried at 110°C for 30 minutes. A surface-treated glass cloth was obtained as a reinforcing glass fiber.

Next, a polyetherimide composite material as a glass fiber-reinforced resin molded article of this example was obtained in exactly the same manner as in Example 1 except that the surface-treated glass cloth obtained in this example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the glass fiber for resin reinforcement obtained in this example, while the amount of acid adhesion was calculated for the glass fiber reinforced resin obtained in this example. The normal bending strength of the polyetherimide composite material as a molded article was measured, and the rate of increase in strength was calculated. The results are shown in Table 1. In this example, the "glass fiber-reinforced resin molded product to which no acid is attached" corresponds to the glass fiber-reinforced resin molded product obtained in Comparative Example 1 below.

[Example 3]
In this example, the surface of the glass fiber for resin reinforcement of this example was completely the same as Example 1, except that an aqueous treatment solution prepared so that malonic acid was 83.7 mmol/kg as the acid was used. A treated glass cloth was obtained.

Next, a polyetherimide composite material as a glass fiber-reinforced resin molded article of this example was obtained in exactly the same manner as in Example 1 except that the surface-treated glass cloth obtained in this example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the glass fiber for resin reinforcement obtained in this example, while the amount of acid adhesion was calculated for the glass fiber reinforced resin obtained in this example. The normal bending strength of the polyetherimide composite material as a molded article was measured, and the rate of increase in strength was calculated. The results are shown in Table 1. In this example, the "glass fiber-reinforced resin molded product to which no acid is attached" corresponds to the glass fiber-reinforced resin molded product obtained in Comparative Example 1 below.

[Example 4]
In this example, the surface of the glass fiber for resin reinforcement of this example was completely the same as in Example 1 except that an aqueous treatment solution prepared so that citric acid was 83.7 mmol/kg as the acid was used. A treated glass cloth was obtained.

Next, a polyetherimide composite material as a glass fiber-reinforced resin molded article of this example was obtained in exactly the same manner as in Example 1 except that the surface-treated glass cloth obtained in this example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the glass fiber for resin reinforcement obtained in this example, while the amount of acid adhesion was calculated for the glass fiber reinforced resin obtained in this example. The normal bending strength of the polyetherimide composite material as a molded article was measured, and the rate of increase in strength was calculated. The results are shown in Table 1. In this example, the "glass fiber-reinforced resin molded product to which no acid is attached" corresponds to the glass fiber-reinforced resin molded product obtained in Comparative Example 1 below.

[Example 5]
This example was completely the same as Example 1 except that an aqueous treatment solution containing 83.7 mmol/kg of maleic acid as the acid was used. A treated glass cloth was obtained.

Next, a polyetherimide composite material as a glass fiber-reinforced resin molded article of this example was obtained in exactly the same manner as in Example 1 except that the surface-treated glass cloth obtained in this example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the glass fiber for resin reinforcement obtained in this example, while the amount of acid adhesion was calculated for the glass fiber reinforced resin obtained in this example. The normal bending strength of the polyetherimide composite material as a molded article was measured, and the rate of increase in strength was calculated. The results are shown in Table 1. In this example, the "glass fiber-reinforced resin molded product to which no acid is attached" corresponds to the glass fiber-reinforced resin molded product obtained in Comparative Example 1 below.

[Example 6]
In this example, an aqueous treatment solution was used in which 0.5% by mass of γ-methacryloxypropyltrimethoxysilane (manufactured by Dow Toray Industries, Inc., trade name: XIAMETER OFS6030) was added as a silane coupling agent. Except for this, a surface-treated glass cloth as a resin-reinforcing glass fiber of this example was obtained in exactly the same manner as in Example 1. The amount of acid attached to the obtained surface-treated glass cloth was 120 ppm, the amount of silane coupling agent attached was 1050 ppm, and the loss on ignition was 0.106%.

Next, a polyetherimide composite material as a glass fiber-reinforced resin molded article of this example was obtained in exactly the same manner as in Example 1 except that the surface-treated glass cloth obtained in this example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the glass fiber for resin reinforcement obtained in this example, while the amount of acid adhesion was calculated for the glass fiber reinforced resin obtained in this example. The normal bending strength of the polyetherimide composite material as a molded article was measured. The results are shown in Table 1.

In Table 1, "methacrylicsilane" means γ-methacryloxypropyltrimethoxysilane.

[Example 7]
In this example, an aqueous treatment solution containing 0.5% by mass of 3-glycidyloxypropyltriethoxysilane (manufactured by Dow Toray Industries, Inc., trade name: DOWSIL Z-6040) was used. A surface-treated glass cloth as a resin-reinforcing glass fiber of this example was obtained in exactly the same manner as in Example 1. The amount of acid attached to the surface-treated glass cloth obtained was 120 ppm, the amount of silane coupling agent attached was 1030 ppm, and the loss on ignition was 0.090%.

Next, a polyetherimide composite material as a glass fiber-reinforced resin molded article of this example was obtained in exactly the same manner as in Example 1 except that the surface-treated glass cloth obtained in this example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the glass fiber for resin reinforcement obtained in this example, while the amount of acid adhesion was calculated for the glass fiber reinforced resin obtained in this example. The normal bending strength of the polyetherimide composite material as a molded article was measured. The results are shown in Table 1.

In Table 1, "epoxysilane" means 3-glycidyloxypropyltriethoxysilane.

[Example 8]
In this example, a surface-treated glass cloth as a glass fiber for resin reinforcement was obtained in exactly the same manner as in Example 1.

Next, 10 sheets of the surface-treated glass cloth obtained in this example were stacked with 13 sheets of polyetheretherketone film (manufactured by Victrex, trade name: APTIV film 1000, deflection temperature under load of 156°C) with a thickness of 100 μm. After holding at 400°C for 10 minutes under contact pressure, the surface pressure was set to 10 kgw/cm ² and held for 5 minutes, and then cooled to room temperature. A polyetheretherketone composite material having a content of 40% and a thickness of 2 mm was obtained.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the glass fiber for resin reinforcement obtained in this example, while the amount of acid adhesion was calculated for the glass fiber reinforced resin obtained in this example. The normal bending strength of the polyetheretherketone composite material as a molded article was measured, and the rate of increase in strength was calculated. The results are shown in Table 1. In this example, the "glass fiber-reinforced resin molded product to which no acid is attached" corresponds to the glass fiber-reinforced resin molded product obtained in Comparative Example 4 below.

[Comparative example 1]
In this comparative example, a surface-treated glass cloth as a resin-reinforcing glass fiber was obtained in the same manner as in Example 1 except that no acid was used at all.

Next, a polyetherimide composite material as a glass fiber reinforced resin molded article of this comparative example was obtained in exactly the same manner as in Example 1 except that the surface-treated glass cloth obtained in this comparative example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the resin-reinforcing glass fiber obtained in this comparative example. The normal bending strength of the polyetherimide composite material as a molded article was measured. The results are shown in Table 2.

In Table 2, "average number of hydrogens" means the average number of hydrogens at the α carbon position of the carboxyl group, and "aminosilane" means 3-aminopropyltriethoxysilane.

[Comparative example 2]
This comparative example was carried out in exactly the same manner as in Example 1, except that an aqueous treatment solution containing 83.7 mmol/kg of formic acid as the acid was used, and a surface-treated glass cloth was used as the resin-reinforcing glass fiber. Obtained.

Next, a polyetherimide composite material as a glass fiber reinforced resin molded article of this comparative example was obtained in exactly the same manner as in Example 1 except that the surface-treated glass cloth obtained in this comparative example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the resin-reinforcing glass fiber obtained in this comparative example. The normal bending strength of the polyetherimide composite material as a molded article was measured, and the rate of increase in strength was calculated. The results are shown in Table 2. In this comparative example, the "glass fiber reinforced resin molded product to which no acid is attached" corresponds to the glass fiber reinforced resin molded product obtained in Comparative Example 1 above.

[Comparative example 3]
In this comparative example, the same procedure was used as in Example 1 except that an aqueous treatment solution containing 83.7 mmol/kg of oxalic acid as the acid was used. I got it.

Next, a polyetherimide composite material as a glass fiber reinforced resin molded article of this comparative example was obtained in exactly the same manner as in Example 1 except that the surface-treated glass cloth obtained in this comparative example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the resin-reinforcing glass fiber obtained in this comparative example. The normal bending strength of the polyetherimide composite material as a molded article was measured, and the rate of increase in strength was calculated. The results are shown in Table 2. In this comparative example, the "glass fiber reinforced resin molded product to which no acid is attached" corresponds to the glass fiber reinforced resin molded product obtained in Comparative Example 1 above.

[Comparative example 4]
In this comparative example, a surface-treated glass cloth as a resin-reinforcing glass fiber was obtained in exactly the same manner as in comparative example 1.

Next, a polyether ether ketone composite material as a glass fiber reinforced resin molded article of this comparative example was obtained in exactly the same manner as in Example 8 except that the surface-treated glass cloth obtained in this comparative example was used. .

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the resin-reinforcing glass fiber obtained in this comparative example. The normal bending strength of the polyetheretherketone composite material as a molded article was measured. The results are shown in Table 2.

[Comparative example 5]
In this comparative example, a surface-treated glass cloth as a resin-reinforcing glass fiber was obtained in exactly the same manner as in comparative example 2.

Next, a polyether ether ketone composite material as a glass fiber reinforced resin molded article of this comparative example was obtained in exactly the same manner as in Example 8 except that the surface-treated glass cloth obtained in this comparative example was used. .

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the resin-reinforcing glass fiber obtained in this comparative example. The normal bending strength of the polyetheretherketone composite material as a molded article was measured, and the rate of increase in strength was calculated. The results are shown in Table 2. In this comparative example, the "glass fiber reinforced resin molded product to which no acid is attached" corresponds to the glass fiber reinforced resin molded product obtained in Comparative Example 4.

[Comparative example 6]
In this comparative example, a surface-treated glass cloth as a resin-reinforcing glass fiber was obtained in exactly the same manner as in Example 1.

Next, 10 sheets of surface-treated glass cloth obtained in this comparative example and 17 sheets of polybutylene terephthalate film (manufactured by Polyplastics, trade name: DURANEX 2000, deflection temperature under load of 68°C) with a thickness of 100 μm were used. were stacked together and held at 260°C for 5 minutes under contact pressure, then the surface pressure was set to 20 kgw/cm ² and held for 3 minutes, and cooled to room temperature to form the glass fiber reinforced resin molded product of this comparative example. A polybutylene terephthalate composite material having a volume content of 40% and a thickness of 2 mm was obtained.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the resin-reinforcing glass fiber obtained in this comparative example. The normal bending strength of the polybutylene terephthalate composite material as a molded article was measured, and the rate of increase in strength was calculated. The results are shown in Table 2. In addition, in this comparative example, the "glass fiber reinforced resin molded product to which no acid is attached" corresponds to the glass fiber reinforced resin molded product obtained in Comparative Example 7 below.

In addition, in Table 2, "PBT" means polybutylene terephthalate.

[Comparative example 7]
In this comparative example, a surface-treated glass cloth as a resin-reinforcing glass fiber was obtained in exactly the same manner as in comparative example 1.

Next, a polybutylene terephthalate composite material as a glass fiber reinforced resin molded article of this comparative example was obtained in exactly the same manner as in comparative example 6 except that the surface-treated glass cloth obtained in this comparative example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the resin-reinforcing glass fiber obtained in this comparative example. The normal bending strength of the polybutylene terephthalate composite material as a molded article was measured. The results are shown in Table 2.

[Comparative example 8]
In this comparative example, a surface-treated glass cloth as a resin-reinforcing glass fiber was obtained in exactly the same manner as in comparative example 2.

Next, a polybutylene terephthalate composite material as a glass fiber reinforced resin molded article of this comparative example was obtained in exactly the same manner as in comparative example 6 except that the surface-treated glass cloth obtained in this comparative example was used.

Next, in exactly the same manner as in Example 1, the amount of acid adhesion was calculated for the surface-treated glass cloth as the resin-reinforcing glass fiber obtained in this comparative example. The normal bending strength of the polybutylene terephthalate composite material as a molded article was measured, and the rate of increase in strength was calculated. The results are shown in Table 2. In this comparative example, the "glass fiber-reinforced resin molded product to which no acid is attached" corresponds to the glass fiber-reinforced resin molded product obtained in Comparative Example 7.

From Table 1, it can be seen that an acid having an average hydrogen number of 0.5 or more at the alpha carbon position of a carboxyl group and a silane coupling agent containing an amine are attached to the surface of the resin-reinforced glass. According to the glass fibers of Examples 1 to 8, in which the content is in the range of 42 to 400 ppm based on the total amount of fibers, a glass fiber reinforced resin molded product using the glass fibers and a high heat resistant resin with a deflection temperature under load of 120° C. or higher. It is clear that the mechanical strength of

On the other hand, Table 2 shows that either an acid with an average hydrogen number of less than 0.5 at the alpha carbon position of a carboxyl group and a silane coupling agent containing an amine are attached to the surface, or no acid is attached at all. According to the glass fibers of Comparative Examples 1 to 5 , the mechanical strength of glass fiber-reinforced resin molded products using the glass fibers and a highly heat-resistant resin with a deflection temperature under load of 120° C. or higher cannot be improved. is clear.

Claims (7)

Used to strengthen resins with a deflection temperature under load of 120°C or higher, selected from the group consisting of thermoplastic polyimide, polyaryletherketone, polyarylene sulfide, liquid crystalline polyester, polyethersulfone, semi-aromatic nylon, and syndiotactic polystyrene. A glass fiber for resin reinforcement,
Acid and silane coupling agent are attached to the surface,
The acid is an acid in which the average number of hydrogen atoms at the α carbon position of the carboxyl group is 0.5 or more,
A glass fiber for resin reinforcement, characterized in that the amount of the acid attached is in the range of 42 to 400 ppm based on the total amount of the glass fiber for resin reinforcement. 2. The glass fiber for resin reinforcement according to claim 1, wherein the acid has an average hydrogen number of 1.2 or more at the alpha carbon position of the carboxyl group. The glass fiber for resin reinforcement according to claim 1 or 2, wherein the acid is an acid having an average number of hydrogens at the α carbon position of the carboxyl group of 2.0 or more. . The glass fiber for resin reinforcement according to any one of claims 1 to 3, wherein the acid is acetic acid. The glass fiber for resin reinforcement according to any one of claims 1 to 4, wherein the amount of the acid attached is in the range of 90 to 200 ppm based on the total amount of the glass fiber for resin reinforcement. glass fiber. The glass fiber for resin reinforcement according to any one of claims 1 to 5, wherein the silane coupling agent is a silane coupling agent containing an amine. Consisting of the glass fiber for resin reinforcement according to any one of claims 1 to 6, thermoplastic polyimide, polyaryletherketone, polyarylene sulfide, liquid crystal polyester, polyether sulfone, semi-aromatic nylon, syndiotactic polystyrene. A glass fiber-reinforced resin molded article, characterized in that it contains a resin selected from the group consisting of a resin having a deflection temperature under load of 120° C. or higher.