JPH01210429A - Production of woven glass fiber fabric - Google Patents

Abstract

PURPOSE:To produce the title woven fabric capable of giving a laminate having improved in heat resistance, dimensional stability, surface smoothness and drilling machinability, by injecting a liquid organic compound in the form of a high-pressure jet stream against a woven glass fiber fabric. CONSTITUTION:A glass yarn obtained by doubling a plurality of glass fibers of a diameter of several mum to several tens of mum is warped, sized and woven into a woven glass fiber fabric (A) of a thickness of 20-300mum and a weight per unit area of 20-350g/m<2>. A liquid organic compound (B) of a specific gravity of 0.6-2.0, a boiling point of -130-250 deg.C, preferably, 20-150 deg.C (e.g., trichlorofluoromethane) is injected against component A in the form of a high- pressure jet stream at a pressure of 20-1000kg/cm<2>, and is removed by drying.

Description

Detailed Description of the Invention (°Industrial Field of Application) The present invention relates to a method for manufacturing glass fiber woven fabric used in composite materials such as laminates, and in particular to computers, various electrical devices, electronic devices, communication devices, etc. The present invention relates to a method for manufacturing a glass fiber woven fabric suitable for use in printed wiring boards.

(Prior Art) Conventionally, printed wiring boards for industrial use are made by laminating prepreg, which is made by impregnating woven glass fiber cloth with thermosetting resin such as epoxy resin, on metal foil, and bonding it by heating and pressing. It is manufactured into a so-called metal-clad laminate and used as a printed wiring board.

Printed wiring boards are divided into single-sided metal-clad laminates and multilayer printed wiring boards depending on the structure of the board, and depending on the number of laminated sheets, some are suitable for flexible printed wiring boards and others are suitable for rigid printed wiring boards. In either case, the printed wiring board uses prepreg, which is a glass fiber woven fabric treated with a surface treatment agent such as an organic silane compound and impregnated with a thermosetting resin.

The reason why glass fiber woven fabric is used for printed wiring boards is to take advantage of the excellent properties of glass fiber, such as mechanical strength, dimensional stability, and heat resistance.

Conventional glass fiber woven fabrics have not always been sufficient in terms of various properties. For example, the dimensional change rate of a substrate is extremely important in improving the accuracy of circuit formation, and especially in multilayer printed wiring boards, the occurrence of interlayer misalignment at one circuit position is fatal. In recent years, as the density of circuit patterns has increased and the number of layers per layer has increased, tolerances for interlayer misalignment have become stricter, and substrate materials with less dimensional change are required. The glass fiber woven fabric of the base material has a great influence on the dimensional change rate of such a substrate. Therefore, various attempts have been made to manufacture printed wiring boards with little dimensional change. For example, efforts have been made to consider the pressure conditions during lamination and to improve the circuit pattern, but the results are still not fully satisfactory. In addition, for glass fiber woven fabrics, proposals have been made that specify the filament diameter of the fibers, the ratio of warp and weft weaving density, the weight per unit area, the thickness, etc., but these are not sufficient. . Furthermore, multilayer printed wiring boards are formed with through holes using a drilling machine, and there is a strong demand for a base material that improves the finishing accuracy of the hole wall surface and extends the life of the drill. In response to this, there have been attempts to improve perforation processability by specifying the strength and elastic modulus of glass fiber woven fabrics, but these efforts have not been sufficient.

It is also known that when circuits are formed on metal-clad laminates to increase circuit density, surface roughness affects fine circuit printing, and the surface is required to be as smooth as possible. In response to such demands, it is known that the fibers constituting the glass fiber woven fabric are opened using a water jet in order to smooth out the unevenness on the surface of the glass fiber woven fabric. Glass fiber woven fabrics are required.

(Problems to be Solved by the Invention) The present invention attempts to solve the above-mentioned problems, and its purpose is to provide excellent impregnation properties of resin varnish, and to improve perforation processability, 9 dimensional stability, and 5 surface smoothness. Another object of the present invention is to provide a method for producing a glass fiber woven fabric that can easily produce a glass fiber woven fabric that can produce a laminate with excellent heat resistance.

(Means for Solving the Problems) In order to solve the above problems, the inventors of the present invention, as a result of extensive studies, have discovered that a high-pressure jet stream of a liquid organic compound is injected onto a glass fiber woven fabric. This book was developed based on the discovery that the glass fiber bundles that make up the glass fiber woven fabric are loosened, and that the wetting properties of the glass fibers with respect to the resin varnish are significantly improved, improving the resin impregnation properties, thereby solving the above problems. invention has been achieved.

That is, one aspect of the present invention is a method for producing a glass fiber woven fabric, which is characterized by injecting a high-pressure jet stream of a liquid organic compound onto the glass fiber woven fabric.

Hereinafter, nine aspects of the present invention will be described in detail.

In the present invention, a liquid organic compound is injected as a high-pressure jet stream onto a glass fiber woven fabric, and the liquid organic compound has a specific gravity of 0.6 to 2.0. Organic compounds having a boiling point of 1130°C to 250°C are preferably used. A lower boiling point is preferable from the viewpoint of ease of removal when the organic compound is applied by spraying and then removed from the glass fiber woven fabric. From the viewpoint of ease of handling, organic compounds having a boiling point of about 20°C to 150°C are particularly preferred.

Not only one type of the above-mentioned liquid organic compound may be used, but two or more types may be used.

Examples of such liquid organic compounds include alcohols, ethers, ketones, and esters.

Examples include aromatic hydrocarbons and halogenated hydrocarbons.

Examples of alcohols include methanol.

Ethanol, isopropyl alcohol, butyl alcohol, ethers include diethyl ether, methyl cellosolve, ethyl cellosolve, phenyl cellosolve, and ketones include acetone.

Propion, butylone, methyl ethyl ketone, and esters include ethyl acetate, ethyl propionate, methyl formate, and the like. Further, aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, chlorobenzene, and halogenated hydrocarbons include methylene chloride, chloroform, carbon tetrachloride, trichlene, tetrachloroethylene, dichlorodifluoromethane (Freon-12), Monochlorodifluoromethane (Freon-22
).

Trichlorotrifluoromethane (Freon-113).

Examples include dichlorotetrafluoroethane (Freon-114).

It is preferable to recover the organic compound used in the present invention, and when considering the workability and safety in that case, fluorinated hydrocarbon-based organic compounds, so-called fluorocarbon-based compounds, are particularly preferable. .

In the present invention, the liquid organic compound as described above is injected as a high-pressure jet onto the glass fiber woven fabric, and the injection pressure of the high-pressure jet is 20 to 1000.
kg/crl, preferably 50-500 kg
/ci range. When an organic compound having a relatively high specific gravity is used as the liquid organic compound, the injection pressure can be reduced. If the injection pressure is too small, the improvement in the wettability of the glass fiber woven fabric to the resin varnish will be small; on the other hand, if the injection pressure is too large.

Local roughening or cutting of the woven fabric may occur.

When injecting the high-pressure jet stream onto the woven fabric, it is preferable to arrange a plurality of small-diameter nozzles at equal intervals in the width direction of the woven fabric to be treated, and to inject the high-pressure jet stream while running the woven fabric. .

Further, when injecting the high-pressure jet stream onto the woven fabric, it is preferable to spray the jet stream as uniformly as possible.

In order to uniformize the energy received by the fluid from the nozzle on the woven fabric, 1. For example, there are methods such as rotating the nozzle eccentrically, spreading the fluid ejected from the nozzle into a fan shape, turning it into a spray, and spraying it onto the woven fabric. A method such as spraying from a nozzle with a slit in the width direction is adopted. If the woven fabric is hit by a high-pressure jet flow locally, roughness and unevenness will occur, so the number of nozzles, jetting method, etc. are appropriately selected depending on the required quality.

When using an eccentric rotating nozzle, the nozzle diameter should be 0.1~
It is preferably about 0.61, the degree of eccentricity is about 10 to 20+n from the center of the shaft, and the rotation speed is 1000 to 4000 r.
It is preferably about pm.

If the running speed of the woven fabric is too fast, the processing may become uneven and the woven fabric may remain in the trajectory of the nozzle. Therefore, it is preferable to set the running speed to a relatively low speed such that the trajectory cannot be visually recognized. For example, 0.1m/min to 200nI/lll1
Approximately n is appropriate.

When using a spray nozzle, its diameter is preferably about 0.1 to 0.6 fins, as in the case of a rotating nozzle, and the spray angle is preferably 10 to 60''.
As a spraying method, a method may be adopted in which nozzles are arranged at equal intervals in 11 directions of the woven fabric and the nozzles are reciprocated in the middle direction to spray.

In the present invention, the liquid organic compound sprayed onto the glass fiber woven fabric as described above is usually used. 1 The cloth is dried and removed by hot air drying or vacuum drying. The amount of organic compounds after drying.

5% or less, preferably 2% or less based on the total weight of the woven fabric,
Particularly preferably, it is 1% or less. If there is a large amount of remaining liquid organic compound, voids etc. tend to be more likely to occur during molding of a laminate such as a printed wiring board. In the case of organic compounds, they have less adverse effects than water, and even if they exist to some extent, there is no problem, which is also an advantage of the present invention.

The composition of the glass constituting the glass fiber woven fabric used in the present invention is not particularly limited, but for example, E glass, C glass, S glass, etc. are preferably used. In particular, for printed wiring boards, E glass, which is a non-alkali glass, is preferable.

Further, the fiber diameter of the glass fibers constituting the glass fiber woven fabric may be any fiber diameter as long as the glass fiber woven fabric can be woven, but it is preferably in the range of several μm to several tens of μm.

The glass fiber woven fabric used in the present invention is:

Usually, it is obtained by weaving a glass yarn obtained by combining a plurality of the above-mentioned glass fibers, after subjecting it to a warping process and a sizing process.

The weave structure of the glass fiber woven fabric may be, for example, plain weave, twill weave, satin weave, tricycle weave, or any other weave.

Number of warp and weft threads per unit length of glass fiber woven fabric,
Thickness and weight per unit area: 1 Japanese Industrial Standards R-3
414 or the United States military standard (MIL standard), but is not limited thereto. The thickness of fibers other than glass fibers that meet these standards is about 20 μm to about 300 μm, and the weight of one piece is about 20 g1rd.
~350 g/m.

The glass fiber woven fabrics used in the present invention include not only glass fiber woven fabrics that do not meet the above standards, but also woven fabrics made of glass fibers and fibers other than glass fibers, such as mixed fibers of glass fibers and carbon fibers. , a mixed fiber of glass fiber and organic fiber, a mixed fiber of glass fiber and ceramic fiber, etc. may be used. In addition, in the case of a mixed fiber of glass fiber and organic fiber, fibers that are not likely to be swollen by the above-mentioned liquid organic compound are selected as the organic fiber.

The glass fiber fabric used in the present invention is:

Glass fiber woven fabric with a sizing agent necessary for weaving attached (hereinafter referred to as gray fabric), glass fiber woven fabric in a stage where the sizing agent has been removed (hereinafter referred to as cleaned glass fiber woven fabric), gray fabric or cleaned Any glass fiber woven fabric may be used, such as a glass fiber woven fabric obtained by treating a finished glass fiber woven fabric with an organic silane compound (hereinafter referred to as a silanized woven fabric).

(Function) In the method for producing a glass fiber woven fabric of the present invention, a high-pressure jet stream of a liquid organic compound is injected onto the glass fiber woven fabric as described above, so that the energy of the fluid and the liquid organic compound cause swelling and cleaning. By action.

The physical structure of the fiber bundle is improved. Furthermore, when impregnated with a resin such as resin varnish, the permeability of the resin into the filaments increases, the polarity of the interface is improved, and the adhesion of the resin between the filaments is significantly improved.

According to such woven fabrics.

A laminate having excellent heat resistance, dimensional stability, surface smoothness, and perforation processability is obtained.

When woven glass fiber fabrics are treated according to the present invention.

Improvements in the interfacial properties of woven glass fiber fabrics that cannot be achieved with conventional water jet treatments are observed.

In particular, when used as a material for printed wiring boards, even the slightest amount of water adsorbed on the surface of glass fibers will cause various problems during varnish impregnation and laminate forming, so water must be completely removed. However, according to the method of the present invention, since a jet stream of liquid organic compounds is injected, such organic compounds can be easily removed, and even if organic compounds remain, they can be removed. , Wetting during varnish impregnation is good, and there is no problem at all.

(Example) Next, the present invention will be explained in detail based on examples.

The performance of the glass fiber woven fabric and the preparation conditions and properties of the prepreg obtained from the woven fabric in the following Examples are as follows.

(1) Varnish impregnation into glass fiber woven fabric The varnish impregnation into the woven fabric was evaluated by light transmittance.

Light transmittance was measured as follows.

First, the intensity of transmitted light through the glass plate with the triacetate film pasted was measured. Next, a glass fiber woven cloth was placed on the glass plate with the triacetate film pasted, and epoxy resin varnish was poured onto the glass fiber woven cloth. After 3 minutes, the intensity of the transmitted light was measured, and the light transmittance was calculated from the following equation. In this case, the larger the light transmittance value, the better the impregnating property. In addition, as an epoxy resin varnish, epoxy resin 5 of FR-4 composition according to NEMA standards is used.
A 0-heavy methyl cellosolve solution is also used.

■.

Light transmittance (%) = -X100 O where +10 indicates the intensity of light transmitted through the triacetate film and the glass plate, +11 indicates the intensity of light transmitted through the glass fiber woven fabric and the epoxy resin.

(2) Prepreg Preparation Conditions A prepreg was prepared by impregnating a glass fiber woven fabric with a resin having the composition shown below. At that time, the resin content was adjusted to 42% by weight.

Epicort 5045 (brominated bisphenol A type epoxy resin; trade name manufactured by Yuka Shell Co., Ltd.) 100 parts by weight Epicort 54 (novolak type fatty epoxy resin; trade name manufactured by Yuka Shell Co., Ltd.) 30 parts by weight dicyandiamide (curing agent) 4 parts by weight benzyldimethylamine (hardening accelerator) 0.2 parts by weight methyl cellosolve (solvent) (3) Dimensional stability Measured in accordance with JIS C-6486.

(4) Solder heat resistance 8 sheets of prepreg are stacked, copper foil (18 μm thick) is laminated on the outside of both sides, and a press pressure of 40 μm is applied.
kg/Ct&+ A copper-clad substrate was prepared by heating and pressing at a curing temperature of 170° C. and a curing time of 90 minutes.

Next, after etching the copper foil, the board was boiled under normal pressure for a certain period of time, then immersed in a 260°C solder bath for 30 seconds, and the interfacial peeling (blister) of the laminate after being taken out from the solder bath.
, to investigate separation (measling) at the intersection of the warp and weft yarns that make up the glass fiber woven fabric.

The boiling time is gradually increased, and the boiling time at which peeling begins is defined as the heat resistance time. Therefore, the longer this time,
It is determined that the heat resistance is good.

(5) Surface smoothness The surface smoothness of the copper-clad board prepared in the same manner as in (4) above was measured in accordance with the JIS B-0601r Surface Roughness Measurement Method. The length was measured as 10+u.

(6) 122 sheets of perforated prepreg were stacked, and copper foil (thickness: 18 μm) was layered on top and bottom, and a press pressure of 40 kg/c was applied.
nl.

A copper-clad substrate was prepared by heating and pressing at a curing temperature of 170° C. and a curing time of 100 minutes.

The above copper-clad substrate was perforated under the following perforation conditions.

The roughness (μ) of the hole wall surface was measured as a result of changes in drill rotation speed (rpm) and drill feed (drilling length per drill revolution; μm/rev), and the drilling workability was evaluated using this. At this time, the number of hits by the drill was approximately 5,000, and measurements were taken after approximately 5,000 hits. Moreover, this measurement was performed by microscopic observation of the cross section.

Drilling processing conditions〉 Drilling machine manufactured by Exelon (Product name: Exelon Mark 5)
Using this method, four of the above copper-clad substrates were stacked and perforated. A straight drill with a diameter of 1+U is used as the drilling machine, and a Bakelite plate is used as a backing plate.The top side of the board is placed with a 0.8mm thick backing plate, and the bottom side is placed with a 1.6mm thick backing plate for drilling. did.

Examples 1-4. Comparative Example 1.2 Glass yarn ECG75 as warp and weft respectively
Width: 107 cm, weight: 210 woven with warp density of 44 threads/25 cm and weft thread density of 33 threads/25 cm using 110 threads.
Silane treated plain weave glass fiber woven fabric (Unitika ■
(trade name: 20134K) was treated under various conditions shown in Table 1.

The fluid ejecting nozzle is a spray nozzle that ejects a fan-shaped jet stream, and its shape is approximately 511 mm thick in the running direction of the woven fabric. A jet with an ejection angle of 40'' in the width direction was used, the nozzle diameter was 0.1 mm, and the nozzle spacing was 50mm.The distance between the nozzle and the fabric was 70mm, and the running speed of the fabric was 10 m/min. A jet stream of high-pressure liquid was ejected.

After the fluid was injected, the glass fiber fabric was dried with hot air at 130° C. for 5 minutes to remove the liquid in the glass fiber woven fabric.

Table 1 Table 2 shows the varnish impregnation properties of each of the treated woven fabrics obtained and the characteristics of the substrates made from each of the treated woven fabrics.

In Example 1, the woven fabric before the liquid jet treatment was directly subjected to measurement.

As is clear from Table 2, the glass fiber woven fabrics obtained in Examples 1 to 4 according to the method of the present invention have significantly improved varnish impregnation properties, and all substrates made using the same have significantly improved varnish impregnation properties. 9 Dimensional change rate 1 It can be seen that the material is excellent in all of surface smoothness, solder heat resistance, and perforation workability.

(Effects of the Invention) According to the production method of the present invention, the impregnation of varnish into glass fiber woven fabric can be significantly improved. Furthermore, according to the glass fiber woven fabric obtained by the method of the present invention,
Laminated boards such as printed wiring boards having excellent heat resistance, dimensional stability, surface smoothness, and perforation workability can be easily obtained. Furthermore, according to the glass fiber woven fabric according to the present invention, mechanical properties.

A structural composite material with excellent thermal properties can be obtained.

Claims (1)

[Claims] (1) A method for producing a glass fiber woven fabric, which comprises injecting a high-pressure jet stream of a liquid organic compound onto the glass fiber woven fabric.