JP2003321247A - Glass composition for glass fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass fiber capable of widening a working temperature range, further obtaining glass fibers having high strength and a high elastic modulus, and reducing the amount of bubbles in the glass fibers. Provide a glass composition for use. SOLUTION: The glass composition for glass fiber having a basic composition consisting of SiO ₂ , Al ₂ O ₃ and MgO,
The content of SiO ₂ is 5 based on the total weight of the composition.
5-68 wt%, the content of Al ₂ O ₃ is 17 to 28 wt%, the content of MgO is 7-15 wt%, and SiO _2,
The total content of Al ₂ O ₃ and MgO is 94 to 98% by weight, and the remaining 70% by weight or more excluding the basic composition is Ti
A glass composition for glass fibers, which is O ₂ and / or ZrO ₂ .

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glass composition for glass fiber and glass fiber.

[0002]

2. Description of the Related Art Glass fibers used in printed wiring boards and the like are required to have high strength. As a glass material for high strength glass fiber, for example, a composition essentially consisting of SiO ₂ and Al ₂ O ₃ with about 4 to 25% by weight of MgO added, and specifically, SiO ₂ 55 on a weight basis. ~ 85
%, Al ₂ O ₃ 10 to 35% and MgO 4 to 25% (S glass) are known (Japanese Patent Publication No.
8-30125).

[0003]

However, the above S
Glass has a problem that the working temperature range, which is a value obtained by subtracting the liquidus temperature from the 1000 poise temperature, is narrow, making it very difficult to manufacture glass fibers. Where 100
The 0 poise temperature refers to a temperature at which the melt viscosity of glass becomes 1000 poise, and the liquidus temperature refers to a temperature at which crystal precipitation first occurs when the temperature of the molten glass is lowered.
In general, glass fibers can be efficiently produced when the glass is melted at a melt viscosity of around 1000 poises. Therefore, the 1000 poise temperature is a temperature used as an index during spinning, and the liquidus temperature is It is a temperature that is an index of the homogeneity of the molten state of glass.

Further, when the glass fiber is produced by using the S glass, there is a problem that bubbles tend to remain in the glass composition. When the bubble diameter of the bubbles is small, so-called hollow fibers containing the bubbles in the glass fibers are generated, and when the glass fibers containing the hollow fibers are used as reinforcing fibers in, for example, a printed wiring board. In some cases, the insulation resistance was reduced, which could cause insulation failure. On the other hand, when the bubble diameter is large, there is a problem that the glass fiber is cut by bubbles during spinning.

The present invention has been made in view of the above problems, and it is possible to sufficiently widen the working temperature range in the production of glass fiber and to obtain glass fiber having high strength and high elastic modulus. It is possible to sufficiently reduce the bubbles in the glass fiber, and an object thereof is to provide a glass composition for glass fiber which does not accompany cutting of the glass fiber or formation of hollow fiber during spinning. .

The present invention also provides a high-strength and high-modulus glass fiber comprising the glass composition for glass fiber, a glass fiber braid formed by braiding the glass fiber, a glass fiber reinforced resin containing the glass fiber, It is an object of the present invention to provide a printed wiring board including a glass fiber reinforced resin layer made of this glass fiber reinforced resin.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to achieve the above object, the basic composition S
It has been found that the above object can be achieved by adjusting the contents of iO ₂ , Al ₂ O ₃ and MgO within the specific ranges and further adding TiO ₂ and / or ZrO ₂ .

Further, a glass fiber braid can be obtained by braiding such glass fibers, and a glass fiber reinforced resin can be formed from such glass fibers. By using such glass fiber reinforced resin, a print having a high insulating property can be obtained. The inventors have found that a wiring board can be obtained and completed the present invention.

That is, the glass composition for glass fibers of the present invention is a glass composition for glass fibers having a basic composition consisting of SiO ₂ , Al ₂ O ₃ and MgO, and the whole glass composition for glass fibers is SiO _{2 based on} weight
Content of 55 to 68% by weight and Al ₂ O ₃ content of 17
˜28% by weight, the content of MgO is 7 to 15% by weight, and the total content of SiO ₂ , Al ₂ O ₃ and MgO is 94 to 98% by weight, and the remaining 7 except the basic composition is 7% by weight.
It is characterized in that 0% by weight or more is TiO ₂ and / or ZrO ₂ .

Since the glass composition for glass fiber of the present invention has the above-mentioned constitution, the working temperature range in the production of glass fiber can be sufficiently widened, and further, glass fiber having high strength and high elastic modulus can be obtained. It is possible. Further, the amount of bubbles in the glass fiber can be sufficiently reduced, and it becomes possible to prevent the cutting of the glass fiber and the production of hollow fiber during the production of the glass fiber.

The above glass composition for glass fiber is Al ₂ O ₃
The weight ratio of / MgO is preferably 2.30 or less.

By adjusting the above weight ratio, the amount of bubbles generated during the production of glass fiber can be further reduced, and the generated bubbles can be easily removed from the glass composition. Therefore, the amount of bubbles in the obtained glass fiber can be reduced. It can be further reduced.

In the glass composition for glass fibers of the present invention, it is preferable that 40% by weight or more of the weight excluding TiO ₂ and ZrO ₂ from the above balance is Fe ₂ O ₃ .

Fe ₂ O ₃ is further contained in the glass composition for glass fiber, which is composed of SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ and ZrO _2, to minimize the amount of bubbles in the glass fiber. Can be

The present invention also relates to a glass fiber characterized by comprising the above glass composition for glass fiber, a glass fiber braid characterized by braiding the above glass fiber, the above glass fiber, and a thermoplastic resin. At least one resin selected from the group consisting of resin and thermosetting resin, and a glass fiber reinforced resin characterized by containing, and a glass fiber reinforced resin layer comprising the glass fiber reinforced resin, the glass fiber reinforced A conductor layer formed on a resin layer is provided, and a printed wiring board is provided.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

As described above, the glass composition for glass fiber of the present invention is a glass composition for glass fiber having a basic composition consisting of SiO ₂ , Al ₂ O ₃ and MgO. Si based on the total weight of the object
The content of O ₂ is 55 to 68% by weight, the content of Al ₂ O ₃ is 17 to 28% by weight, the content of MgO is 7 to 15% by weight,
Moreover, the total content of SiO ₂ , Al ₂ O ₃ and MgO is 94.
Is 98% by weight, and 70% by weight or more of the balance excluding the basic composition is TiO ₂ and / or ZrO ₂ .

Since the glass composition for glass fibers of the present invention has the above constitution, it is possible to sufficiently widen the working temperature range during the production of glass fibers. Specifically, the working temperature range can be set to around 20 ° C.

S disclosed in Japanese Patent Publication No. 48-30125
The 1000 poise temperature of glass is about 1470 ° C and the liquidus temperature is about 1465 ° C. The spinning temperature when the 1000 poise temperature is adopted is about 1470 ° C, and the working temperature range is about 5 ° C. Therefore, the glass composition for glass fibers of the present invention has a sufficiently wide working temperature range as compared with the glass compositions disclosed in the above publications, so that it is easy to produce glass fibers having high strength and high elastic modulus. Is possible.

Since the glass composition for glass fibers of the present invention has the above-mentioned constitution, it becomes possible to obtain glass fibers having high tensile strength and tensile elastic modulus. Specifically, as the glass fiber monofilament, a glass fiber exhibiting a tensile strength of more than 4 GPa and a tensile elastic modulus of more than 84 GPa can be obtained. Since such tensile strength and tensile elastic modulus are equal to or higher than those of S glass (Japanese Patent Publication No. 48-30125) known as a glass material for high-strength glass fibers, for example, thin glass fiber cloth (glass fiber woven fabric). Etc.), the occurrence of bending and wrinkles can be prevented.

In the glass composition for glass fiber of the present invention, SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ and ZrO _{2 are used.}
If the content of is out of the above range, the above effect cannot be obtained.

That is, in the glass composition for glass fiber of the present invention, when the content of SiO ₂ is less than 55% by weight based on the total weight, the tensile strength and tensile elastic modulus of the obtained glass fiber are insufficient. become. On the other hand, when it exceeds 68% by weight, the 1000 poise temperature becomes too high, the energy required for spinning becomes excessive, and the production efficiency of glass fiber decreases. In the present invention, Si
The content of O ₂ is 61 to 67% by weight based on the total weight.
Is preferable, and more preferably 64 to 66% by weight.

In the glass composition for glass fiber of the present invention, the content of Al ₂ O ₃ is 17% by weight based on the total weight.
If it is less than the above range, the tensile strength and tensile modulus of the resulting glass fiber will be insufficient. On the other hand, when it exceeds 28% by weight, the liquidus temperature becomes too high and spinning becomes difficult. In the present invention, the content of Al ₂ O ₃ is preferably 20 to 24% by weight, more preferably 21 to 23% by weight.

Further, in the glass composition for glass fiber of the present invention, when the content of MgO is less than 7% by weight based on the total weight, the 1000 poise temperature becomes too high and the production efficiency of glass fiber is lowered. To do. On the other hand, when it exceeds 15% by weight, it becomes difficult to secure the working temperature range during the production of glass fiber. In the present invention, the content of MgO is preferably 9 to 13% by weight, more preferably 10 to 12% by weight.

Further, in the glass composition for glass fiber of the present invention, when the content of TiO ₂ and / or ZrO _{2 in} the balance excluding the above basic composition is less than 70% by weight based on the total weight, it is obtained. The tensile strength and tensile modulus of the glass fiber will be insufficient.

TiO ₂ and ZrO ₂ are preferably added in the same weight, and the addition amount of each is preferably 2% by weight or less based on the total weight of the glass composition for glass fiber. If the added amount of ZrO ₂ exceeds 2% by weight, the meltability of the glass composition for glass fibers tends to be lowered.

The glass composition for glass fiber comprises Al ₂ O ₃ /
It is preferable that the weight ratio of MgO (that is, the value obtained by dividing the weight of Al ₂ O _{3 by} the weight of MgO) is 2.30 or less.

The present inventors have identified the crystal (devitrification initial phase) formed first when the glass is devitrified with Mullite.
It has been found that the formation of bubbles at the time of devitrification can be suppressed by using cordierite or tridymite instead of Al ₂ in the glass composition for glass fiber of the present invention. O ₃ / M
When the weight ratio of gO is 2.30 or less, the devitrification primary phase can be cordierite or tridymite. Therefore, it becomes possible to sufficiently reduce the generation of bubbles at the time of devitrification, and to significantly reduce the amount of bubbles in the obtained glass fiber.

In the present invention, a glass set for glass fiber
From the total weight of the product to SiO₂, Al₂O ₃, MgO, TiO₂
And ZrO₂Fe in weight excluding₂O₃The weight of 4
It is preferably 0% by weight or more.

The glass composition for glass fiber has the above-mentioned weight percentage.
It becomes possible to further reduce the amount of bubbles in the glass fiber obtained by containing Fe ₂ O ₃ of.

The glass composition for glass fiber contains CaO, Na ₂ O and B as components other than the above components.
₂ O ₃ , K ₂ O, MnO ₂ and Cr ₂ O ₃ may be further contained.

The glass fiber of the present invention comprises the glass composition for glass fiber described above. The glass fiber is a monofilament of glass fiber, a glass fiber strand composed of a plurality of glass fiber monofilaments,
Any mode of a glass fiber yarn obtained by twisting a glass fiber strand may be adopted. The fiber diameter of the monofilament of the glass fiber can be, for example, 3 to 30 μm, and the glass fiber strand can be obtained by focusing 50 to 800 of the monofilament. Further, the glass fiber yarn can be produced by twisting the glass fiber strand at a rate of once / 25 mm or less, for example. The glass fiber of the present invention may be provided as roving, and the glass fiber may be provided around the core material made of paper or plastic.
It may be provided as a wound body wound up to about 100 km, or may be provided as glass fiber (glass fiber chopped strand etc.) cut into about 1 inch.

The glass fiber of the present invention typically has a tensile strength of 4 GPa or more and 84 GP as a monofilament.
A tensile modulus of a or more is shown. Such values of tensile strength and tensile elastic modulus are significantly higher than those of commonly used glass fibers (glass fibers made of E glass).

The method for producing the glass fiber of the present invention includes:
Known methods such as a remelting method and a direct melting method can be adopted, and according to these known methods, a molten glass composition is usually drawn at a high speed from hundreds to thousands of platinum nozzles. The glass composition is made into a fiber.

By using the above-mentioned glass fiber,
A glass fiber braid, a glass fiber reinforced resin, and a printed wiring board are provided.

Here, the glass fiber braid is obtained by braiding the above glass fibers. In addition,
The term “braid” refers to a method in which glass fibers are knitted, braided, or the like to be assembled so as to be intertwined with each other or to be overlapped with each other. In the present invention, the glass fiber braid may have any of a glass fiber woven fabric, a glass fiber braid, a glass fiber braid, and a glass fiber nonwoven fabric.

The glass fiber reinforced resin contains the above glass fiber and at least one resin selected from the group consisting of thermoplastic resins and thermosetting resins. The glass fiber in the glass fiber reinforced resin of the present invention includes the above glass fiber and the above glass fiber braid. As the thermoplastic resin in the glass fiber reinforced resin of the present invention, polyamide (nylon), polyacetal, polycarbonate, polyvinyl chloride, ABS, polysulfone, polyethylene, polypropylene, polystyrene,
Examples of the (meth) acrylic resin, fluororesin, saturated polyester resin, and the like, and examples of the thermosetting resin include unsaturated polyester resin, epoxy resin, melamine resin, phenol resin, and polyimide resin. When the glass fiber reinforced resin contains a thermosetting resin, the glass fiber reinforced resin of the present invention includes a glass fiber reinforced resin in which the thermosetting resin is completely cured, and a thermosetting resin which is semi-cured. It also includes the prepreg that has been put into the state. Incidentally, the glass fiber reinforced resin of the present invention, if necessary, a low shrinkage material, a flame retardant, a flame retardant aid, a plasticizer, an antioxidant, an ultraviolet absorber,
You may contain additives, such as a coloring agent, a pigment, and a filler.

As a method for producing a glass fiber reinforced resin containing glass fibers and a thermoplastic resin, a known method such as a stampable sheet molding method can be adopted, and a glass fiber reinforced resin containing glass fibers and a thermosetting resin. Examples of the manufacturing method include a hand lay-up method, a spray-up method, a resin transfer method, a sheet molding compound method (SMC method), and a bulk mold compound method (BMC).
A known method such as a method) can be adopted.

The printed wiring board comprises a glass fiber reinforced resin layer made of the above glass fiber reinforced resin and a conductor layer formed on the glass fiber reinforced resin layer. The glass fiber reinforced resin used for such a printed wiring board preferably contains the glass fiber and a thermosetting resin, and the thermosetting resin is preferably a cured product of an epoxy resin. The conductor layer may be a conductor layer made of copper, silver, gold or the like. Since the printed wiring board of the present invention contains the glass fiber of the present invention which does not have defects such as inclusion of bubbles, insulation failure is reduced. Therefore, the printed wiring board of the present invention can be suitably used for home electric appliances, communication information equipment, and the like.

[0040]

EXAMPLES Hereinafter, preferred examples of the present invention will be described in more detail, but the present invention is not limited to these examples.

(Examples 1 to 5 and Comparative Examples 1 to 3) Glass raw materials were prepared so as to have the compositions shown in Table 1, put in a platinum crucible, and stirred in an electric furnace at 1600 ° C. for 8 hours. Melted. Next, the molten glass was cast onto a carbon plate to prepare a glass composition for glass fiber (glass cullet). It was confirmed with a microscope whether or not bubbles were generated when devitrification of the glass composition for glass fibers occurred during the production of the glass cullet. In addition, the crystal formed first at the time of devitrification (devitrification initial phase) was collected, and the crystal structure of the devitrification initial phase was X
It was identified by line diffraction. Further, using the obtained glass cullet, 1000 poise temperature, liquidus temperature, working temperature range, tensile strength and tensile elastic modulus were measured according to the following methods.

[1000 Poise Temperature] Glass cullet is melted, and 1 with a high temperature rotational viscometer (manufactured by Shibaura System Co., Ltd.)
The temperature (° C.) showing 000 poise was measured.

[Liquid phase temperature] 297
Powdered ~ 500 μm and placed in a platinum boat. This platinum boat is placed in an electric furnace with a temperature gradient (set temperature is 1
(In the range of 380 to 1470 ° C.) and kept for 14 hours, then cooled and observed with a microscope for the presence or absence of devitrification.
The set temperature at the place where devitrification was observed was defined as the liquidus temperature.

[Working temperature range] The working temperature range (° C) was defined as the value obtained by subtracting the liquidus temperature from the 1000 poise temperature obtained as described above.

[Tensile Strength and Tensile Modulus] Using a 1-hole platinum bushing, the fiber diameter was about 1 at a temperature of 1470 to 1560 ° C. and a spinning speed of 1000 to 1200 m / min.
3 μm monofilament glass fiber was obtained. The obtained monofilament was cut into a length of 25 cm and used as a sample for measuring tensile strength. This sample was mounted along a length direction of the monofilament on a paperboard having four openings of 2.5 cm × 1 cm, the end of the paperboard was cut off, and the diameter of the sample was measured by a laser outer diameter measuring instrument. Glue the monofilament between each opening of the paperboard, cut out each opening,
Tensilon U for 2.5 cm monofilament
Tensile strength (GPa) and tensile modulus (GP) using TM
a) was measured, and the median value of the 60 measurements was taken as the tensile strength and tensile elastic modulus of the monofilament.

The amount of bubbles generated, the crystal structure of the devitrification primary phase and the measurement results of the above characteristics are summarized in Table 1. In addition, Table 1 shows Al ₂ O _{3 in} each of Examples 1 to 5 and Comparative Examples 1 to _3.
/ MgO (weight ratio) is also described. Comparative Example 1 has a composition corresponding to Example 1 in Japanese Patent Publication No. 48-30125.

[0047]

[Table 1]

【The invention's effect】

As described above, according to the present invention, it is possible to sufficiently widen the working temperature range in the production of glass fiber, and it is possible to obtain glass fiber having high strength and high elastic modulus. Further, it is possible to provide a glass composition for glass fiber, which can sufficiently reduce bubbles in the glass fiber and which is not accompanied by cutting of glass fiber or formation of hollow fiber during spinning.

Further, it becomes possible to provide a glass fiber having a high strength and a high elastic modulus, which comprises the glass composition for a glass fiber, and further, a glass fiber braid obtained by braiding the glass fiber, and the glass fiber. It is possible to provide a glass fiber reinforced resin containing the above and a printed wiring board having a glass fiber reinforced resin layer made of this glass fiber reinforced resin.

Continued front page    F-term (reference) 4G062 AA05 BB01 DA06 DB04 DC01                       DC02 DD01 DE01 DF01 EA01                       EB01 EB02 EC01 EC02 ED03                       ED04 EE01 EE02 EF01 EG01                       FA01 FA10 FB01 FB02 FB03                       FC01 FC02 FC03 FD01 FE01                       FF01 FG01 FH01 FJ01 FK01                       FL01 GA01 GA10 GB01 GC01                       GD01 GE01 HH01 HH03 HH05                       HH07 HH08 HH09 HH10 HH11                       HH12 HH13 HH15 HH17 HH20                       JJ01 JJ03 JJ05 JJ07 JJ10                       KK01 KK03 KK05 KK07 KK10                       MM23 MM40 NN33 NN40

Claims (4)

[Claims] 1. A glass composition for glass fibers having a basic composition of SiO ₂ , Al ₂ O ₃ and MgO, wherein the content of SiO ₂ is based on the total weight of the glass composition for glass fibers. 55 to 68% by weight, Al ₂ O ₃ content of 17 to 28% by weight, MgO content of 7 to 15% by weight, and total content of SiO ₂ , Al ₂ O ₃ and MgO of 94% by weight or more. A glass composition for glass fiber, which is less than 98% by weight, and 70% by weight or more of the balance excluding the basic composition is TiO ₂ and / or ZrO ₂ . 2. The glass composition for glass fibers according to claim 1, wherein the weight ratio of Al ₂ O ₃ / MgO is 2.30 or less. 3. The glass composition for glass fiber according to claim 1, wherein 40% by weight or more of the weight of the balance excluding TiO ₂ and ZrO ₂ is Fe ₂ O ₃ . 4. A glass fiber comprising the glass composition for glass fiber according to any one of claims 1 to 3.