JP5195232B2 - Manufacturing method of glass fiber fabric - Google Patents

Description

  The present invention relates to a manufacturing method for manufacturing a glass fiber fabric.

Conventionally, glass fiber fabric has been widely used as a reinforcing material for laminated boards for printed wiring boards. In order to improve the impregnation property of the resin into the glass fiber woven fabric when producing this laminated sheet, the glass fiber woven fabric before deoiling or the glass fiber woven fabric deoiled after deoiling is used. The fiber opening process may be performed. For example, the example of Patent Document 1 describes a method for performing fiber opening treatment by immersing a glass fiber woven fabric deoiling solution in a colloidal silica-containing liquid.
Japanese Patent Laid-Open No. 11-117168

  With the recent miniaturization of electronic devices, the demand for thinner laminates has become stronger, and in order to reduce the thickness of laminates, glass fiber fabrics having a small mass and a small thickness are used. Moreover, in such a glass fiber fabric, it is preferable that the glass fiber yarns are widened, the glass fibers are uniformly arranged in the laminate, and the glass fiber fabric is smoothed. In addition, as the printed wiring board becomes denser and thinner, CAF (Conductive Anodic Filament) tends to become a problem, so the resin impregnation is further improved to improve the CAF resistance. There is a need. In these respects, further improvement is desired with respect to the above-described conventional technology.

  This invention is made | formed in view of the above problem, and it aims at providing the manufacturing method which manufactures the glass fiber fabric which has favorable smoothness and was excellent in especially resin impregnation property.

  As a result of studying the method of opening the glass fiber fabric, the present inventor has demonstrated a remarkable opening effect as compared with the conventional opening processing for the glass fiber fabric, and in particular, a glass fiber fabric excellent in resin impregnation property. An open fiber treatment method was obtained and the present invention was achieved.

  That is, the method for producing a glass fiber fabric according to the present invention includes a deoiling step in which a glass fiber fabric original fabric obtained by weaving a glass fiber yarn to which a sizing agent is attached is heat-treated to obtain a glass fiber fabric deoiling reaction. A method for producing a glass fiber fabric having a glass fiber fabric original soaked in a colloidal silica-containing liquid before the deoiling step, and the colloidal silica-containing liquid is vibrated in the front and back directions of the glass fiber fabric original fabric. And it has further the 1st fiber-spreading process process which makes the pressure wave of a colloidal silica containing liquid act with respect to a glass fiber fabric original fabric, It is characterized by the above-mentioned.

  According to the method for producing a glass fiber fabric of the present invention, since the first fiber opening process is performed before the deoiling process, the sizing agent acts as a lubricant in the fiber opening process to increase the fiber opening effect. Further, since the colloidal silica fine particles sufficiently penetrate into the glass fiber yarn and serve as a spacer between the filaments, a remarkable fiber opening effect, particularly excellent resin impregnation property can be obtained. Further, in the conventional fiberglass fabric opening process, even if the glass fiber yarn is unwound, the subsequent heat treatment in the deoiling process causes the filament to contact again, and in some cases the glass fiber yarn A part of the inner glass filament is softened and the adjacent glass filaments are partially fused. According to the method for producing a glass fiber fabric of the present invention, the colloidal silica fine particles that have entered between the glass filaments secure a gap between the glass filaments, so that contact and fusion between the glass filaments in the deoiling step are suppressed.

  Further, in the conventional method for producing a glass fiber fabric, a silane coupling agent treatment is performed for the purpose of improving the affinity between the glass fiber fabric and the resin. In this silane coupling agent treatment, the gaps between the glass filaments widened by the opening treatment tend to be narrowed. According to the method for producing a glass fiber fabric of the present invention, the colloidal silica fine particles enter between the glass filaments, thereby preventing the gap between the glass filaments from being narrowed in the silane coupling agent treatment. Therefore, in the glass fiber fabric manufactured according to the present invention, the gap between the glass filaments is ensured by the colloidal silica fine particles, so that the resin impregnation property of the glass fiber fabric is greatly improved.

  In the manufacturing method of the glass fiber fabric of this invention, it is preferable that the temperature of the colloidal silica containing liquid of a 1st fiber-spreading process process is 50 degreeC or more. At a temperature of 50 ° C. or higher, the lubricant component of the sizing agent adhering to the glass fiber fabric is liquefied, so that the lubricity of the glass fiber yarn is improved and the glass fiber yarn is easily opened. Colloidal silica fine particles can easily enter the glass fiber yarn. Therefore, the smoothness and resin impregnation property of the glass fiber fabric are further improved by the first fiber opening treatment step.

In the manufacturing method of the glass fiber fabric which concerns on this invention, it is preferable that the mass per unit area of a glass fiber fabric is 50 g / m < ² > or less. A glass fiber fabric having a mass as small as 50 g / m ² or less and a very thin thickness is often used as a reinforcing material for a laminated board for a high-density printed wiring board in which CAF is a serious problem. Such a glass fiber fabric has a large gap between the glass fiber yarns and a small binding force between the glass fiber yarns, so that the colloidal silica fine particles can easily enter between the glass filaments by the method for producing a glass fiber fabric according to the present invention. The resin impregnation property of the glass fiber fabric can be greatly improved.

  Moreover, it is preferable that the manufacturing method of the glass fiber fabric which concerns on this invention further has the 2nd fiber-spreading process process which injects high pressure water to the glass fiber fabric deoiling reaction after a deoiling process. In this case, since the fiber-opening process is performed by spraying high-pressure water in response to the degreasing of the glass fiber fabric, the glass fiber yarn is unwound and the gap between the glass filaments is widened. Moreover, even if it is a case where some glass filaments are contacted in the deoiling process, or it is partially fused, glass filaments are unwound by jetting of high-pressure water. Therefore, the resin impregnation property of the glass fiber fabric is further improved.

  ADVANTAGE OF THE INVENTION According to this invention, while having favorable smoothness, it becomes possible to provide the manufacturing method which manufactures the glass fiber fabric excellent in resin impregnation property. As a result, the CAF resistance of a printed wiring board produced using a laminated board using the glass fiber fabric as a reinforcing material is improved.

  Hereinafter, an embodiment of a method for producing a glass fiber fabric according to the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals.

FIG. 1 is a flowchart for explaining the steps of the method for producing a glass fiber fabric according to the present embodiment. Each process is demonstrated along the flowchart of Fig.1 (a). First, in the weaving process of step S10, glass fiber yarns made by bundling glass filaments are woven to obtain a glass fiber fabric raw fabric. As the weaving method, for example, plain weaving is adopted, but not particularly limited thereto, and other weaving methods include, for example, double weaving, satin weaving and twill weaving. The driving density of the glass fiber yarn when weaving the glass fiber fabric raw fabric is, for example, 10 to 150 pieces / 25 mm, and preferably 40 to 100 pieces / 25 mm. Mass per unit area of the glass fiber fabric after deoiling process, for example, preferably a 5 to 100 g / ^{m 2,} and more preferably 50 g / ^{m 2} or less. In addition, in a high-density printed wiring board manufactured using a glass fiber fabric having a mass per unit area of 50 g / m ² or less, CAF generation often becomes a problem. According to the manufacturing method of this embodiment, since the resin impregnation property of the glass fiber fabric is greatly improved, the CAF resistance of a printed wiring board produced using this glass fiber fabric is improved. In addition, it is preferable that the mass per unit area of a glass fiber fabric is 8 g / m < ² > or more from a woven viewpoint.

  The number of glass filaments contained in the glass fiber yarn is preferably 25 to 500, for example, and more preferably 40 to 300. The count of the glass fiber yarn is preferably 0.8 to 135 tex, for example, and more preferably 1 to 25 tex. The count (tex) of the glass fiber bundle corresponds to the mass (gram number) per 1000 m of the glass fiber.

  The composition of the glass used for the glass filament is not particularly limited. For example, E glass, low dielectric constant glass, high elastic modulus glass or the like, which is a typical alkali-free glass, is used. The diameter of the glass filament is preferably 3 to 9 μm, for example, and more preferably 5 μm or less. By using a glass fiber fabric made of glass fiber yarns having a glass filament diameter of 9 μm or less, preferably 5 μm or less, a thin glass fiber fabric can be obtained, and the laminated printed wiring board is made thinner. A plate can be produced.

  The glass fiber yarn is produced by bundling a plurality of glass filaments with a sizing agent. A sizing agent is also applied to the aging of the warp. This sizing agent is, for example, a sizing agent in which the film-forming agent component is a starch or PVA (polyvinyl alcohol).

  Subsequently, in the first fiber opening process of step S11, the fiberglass fabric is subjected to a fiber opening process. The fiber opening process is a process for smoothing the glass fiber fabric original fabric by breaking the glass fiber yarns constituting the glass fiber fabric original fabric and increasing the width of the glass fiber yarn. The fiber opening treatment in the first fiber opening treatment step (S11) is performed by immersing the glass fiber fabric original fabric in the colloidal silica-containing solution and vibrating the colloidal silica-containing solution in the front and back directions of the glass fiber fabric original fabric. The pressure wave of the colloidal silica-containing liquid can act on the glass fiber fabric. This pressure wave is a pressure wave of liquid containing fine particles of colloidal silica, so it exhibits high fiber opening capability, and the sizing agent attached to the glass fiber surface acts as a lubricant. Fully opened.

  In addition, since the fiberglass fabric raw fabric is immersed in the colloidal silica-containing liquid and the fiber opening process is performed, the colloidal silica fine particles sufficiently enter between the glass filaments, and the fine particles secure a gap between the glass filaments. In particular, a glass fiber fabric excellent in resin impregnation property can be obtained.

  The colloidal silica-containing liquid is a colloidal solution of ultrahigh molecular weight anhydrous silicic acid composed of fine particles having a volume average particle diameter of, for example, about 10 to 300 nm. The mass ratio of the colloidal silica to the colloidal silica-containing liquid is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass.

  This fiber opening process is performed by, for example, a device called a vibratory oscher. FIG. 2 is a schematic cross-sectional view showing an example of a vibratory oscher device. The processing unit 10 of this apparatus includes a runner 11, a roll 12, and a rotor 13. The runner 11 is a substantially columnar member, can be rotated at a predetermined speed with the center thereof as an axis, and has an uneven outer peripheral surface. The roll 12 is a substantially cylindrical member disposed so as to cover the runner 11, and has a large number of small holes on the surface thereof. The rotor 13 is a substantially cylindrical member disposed so as to cover the roll 12 with a net-like and sheet-like material. The processing unit 10 is disposed in a processing liquid tank 14 filled with a colloidal silica-containing liquid 15.

  The glass fiber fabric 1 is disposed along the outer periphery of the rotor 13 via the guide 16. By rotating the rotatable rotor 13 independently of the runner 11, the glass fiber fabric 1 is continuously fed into the treatment liquid tank 14, moved along the outer periphery of the roll 12, and then processed. It is sent out of the liquid tank 14. The pressure generated in the colloidal silica-containing liquid 15 by the rotation of the runner 11 increases near the convex portion 11a of the runner 11, and decreases near the concave portion 11b. Due to the fluctuation of the pressure, the colloidal silica-containing liquid 15 alternately flows through the small holes of the roll 12 in the direction outward from the center of the rotation axis of the runner 11 and in the opposite direction. The alternating flow of the colloidal silica-containing liquid 15 acts as a pressure wave on the glass fiber fabric 1. According to this vibrator oscher, the colloidal silica-containing liquid can be vibrated in the front and back direction of the glass fiber fabric original fabric, and the pressure wave of the colloidal silica-containing liquid can act on the glass fiber fabric original fabric. When this pressure wave acts on the glass fiber fabric, the glass fiber yarn is widened and flattened.

In particular, when the mass per unit area of the glass fiber fabric is 50 g / m ² or less, the thickness of the glass fiber fabric is about 50 μm or less, and the binding force of the glass filament in the glass fiber yarn is small. The widening effect due to the above and the colloidal silica fine particles sufficiently enter between the glass filaments, so that the resin impregnation property can be particularly improved.

  Here, the temperature of the colloidal silica-containing liquid is preferably 50 ° C. or higher. At a temperature of 50 ° C. or higher, the lubricant component in the sizing agent adhering to the glass fiber fabric is liquefied, and at a temperature of 60 ° C. or higher, the film forming agent component of the sizing agent (starch or polyvinyl alcohol). Swells or gelatinizes, improving the lubricity between the glass filaments. For this reason, the widening and flattening of the glass fiber yarn in the fiber-opening process is further promoted, the smoothness of the glass fiber fabric is further improved, and the resin impregnation property is further improved. For the above reasons, the temperature of the colloidal silica-containing liquid is more preferably 60 ° C. or higher, and the temperature of the colloidal silica-containing liquid is preferably 95 ° C. or lower from the workability of the opening process.

  In the present embodiment, the fiber-opening process is performed by the vibratory washer, but the present invention is not limited to this mode. For example, the vibrator is disposed in the colloidal silica-containing liquid, the glass fiber fabric original is immersed in the colloidal silica-containing liquid, the glass fiber fabric original is immersed in the colloidal silica-containing liquid, ultrasonic vibration, acoustic vibration, Or it can also be set as the aspect which performs a fiber-spreading process by making a low frequency vibration act.

  Subsequently, in the oil removal step of step S12, the glass fiber fabric is heat-treated in a heating furnace or the like. By this heat treatment, the sizing agent adhering to the glass fiber fabric is removed. The heating temperature during this heat treatment is, for example, about 300 to 450 ° C.

  In the conventional heat treatment in the deoiling process, contact between the glass filaments proceeds, and even if the glass fiber fabric is opened before the deoiling process and the glass fiber yarn is released, the heat treatment in the deoiling process As a result, the glass filaments in the glass fiber yarn come into contact with each other again. Further, in some cases, a part of the glass filament is softened and a phenomenon occurs in which the adjacent glass filaments are partially fused. In addition, when the opening treatment is performed on the glass fiber fabric after the oil removal step, there is no sizing agent that acts as a lubricant, and the glass filaments are contacted or partially fused as described above. As a result, the action of the fiber opening treatment such as widening and flattening the glass fiber yarn and widening the gap between the glass filaments is weakened.

  On the other hand, in this embodiment, as shown in FIG. 1A, the first fiber opening process (S11) is performed before the oil removal process (S12). The action of processing is not weakened. Moreover, since the colloidal silica fine particles enter between the filaments to ensure a gap between the filaments, the glass filament contact and partial fusion can be suppressed by heat treatment in the oil removal step. Therefore, the glass fiber yarn is sufficiently widened and flattened by the opening process, and a glass fiber fabric having excellent resin impregnation property can be obtained.

  Subsequently, in the silane coupling agent treatment step of Step S13, the surface treatment of the glass fiber fabric original is performed with the silane coupling agent. By this surface treatment, the affinity between the glass fiber and the resin is improved in the production of a printed wiring board laminate using a glass fiber fabric. Examples of the silane coupling agent used for the silane coupling agent treatment include epoxy silane, amino silane, cationic silane, vinyl silane, acryloxy silane, methacryloxy silane, ureido silane, mercapto silane, sulfide silane, and isocyanate silane. There is no particular limitation.

  In the conventional method for producing a glass fiber fabric, in the silane coupling agent treatment, the gap between the glass filaments widened by the fiber opening treatment tends to be narrowed. However, according to the method for producing a glass fiber fabric of the present invention, since the colloidal silica fine particles have entered between the glass filaments, it is possible to prevent the gap between the glass filaments from being narrowed in the silane coupling agent treatment step, and the resin Impregnation does not decrease.

  Although a glass fiber fabric is manufactured by the process demonstrated above, as FIG.1 (b) shows, you may implement a 2nd fiber-opening process process (S24) further. In a 2nd fiber-opening process process (S24), it is performed by injecting high pressure water to a glass fiber fabric deoiling reaction. By this opening process, the glass fiber yarn is unwound and the gap between the glass filaments is widened. Further, even if the glass filaments are in contact in the deoiling step (S22), or even if some of the glass filaments are partially fused together, the glass filament contact portion or The fused part is cut. Therefore, the resin impregnation property of the glass fiber fabric is further improved.

  The second fiber opening treatment step (S24) is preferably performed after the deoiling step (S22), but as shown in FIG. 1B, it is performed after the silane coupling agent treatment step (S23). It is more preferable. By performing the second fiber opening treatment step (S24) after the silane coupling agent treatment step (S23), the occurrence of fluff on the glass fiber fabric deoiled anti-surface in the second fiber opening treatment step (S24) is suppressed. At the same time, the uniform adhesion of the silane compound is promoted while the glass fiber fabric is deoiled, and the heat resistance of the glass fiber fabric is improved. Moreover, the silane compound adhering excessively to the glass fiber fabric deoiling process in the silane coupling agent treatment step (S23) can be washed away in the second fiber opening treatment step (S24). Therefore, the resin impregnation property of the glass fiber fabric can be further improved as compared with the case where the fiber opening treatment is performed before the silane coupling agent treatment step (S23).

  Hereinafter, preferred examples of the present invention will be described, but the present invention is not limited to the following examples.

Example 1
[Glass fiber fabric fabric]
As the glass fiber fabric, a glass cloth of IPC standard 1078 was used. The count of the glass fiber yarn constituting the glass cloth is 11 tex. The driving density of the glass fiber yarn is 53 pieces / 25 mm for both the warp and the weft. The amount of adhesion was 1 part by mass.

[Opening process before deoiling process]
The glass fiber fabric original fabric was immersed in a colloidal silica-containing solution and subjected to fiber opening treatment with a vibratory oscher. The vibration frequency of the pressure wave given to the glass fiber fabric original fabric by this vibratory washer was 150 Hz. The ratio of the mass of the colloidal silica to the colloidal silica-containing liquid was 1% by mass, and the particle diameter of the colloidal silica was a volume average particle size of 100 nm. The temperature of the colloidal silica-containing liquid was 40 ° C.

[Deoiling process]
The wound body of the glass fiber fabric original fabric subjected to the fiber opening treatment was heat-treated to obtain a glass fiber fabric deoiled mass having a mass of 48 g / m ² . The temperature of the heat treatment was 400 ° C. The heating time was 48 hours.

[Silane coupling agent treatment process]
After the deoiling step, the glass fiber fabric was surface-treated with a silane coupling agent. As the silane coupling agent, N-β- (N-vinylbenzylamino) ethyl-aminopropyltrimethoxysilane was used, and the silane coupling agent concentration was adjusted to PH = 3.5 and the silane coupling agent concentration was 0.3% by mass. A glass fiber fabric was dipped in the aqueous solution and squeezed and treated with a silane coupling agent. In the glass fiber fabric, the amount of colloidal silica attached was 0.5 parts by mass and the amount of silane coupling agent attached was 0.5 parts by mass with respect to 100 parts by mass of the glass fiber yarn.

(Example 2)
A glass fiber fabric was produced in the same manner as in Example 1 except that the temperature of the colloidal silica-containing liquid in the fiber opening treatment step before the deoiling step was 70 ° C.

(Example 3)
Under the same conditions as in Example 1, a fiberglass fabric was produced by performing a fiber opening treatment step before the deoiling step, a deoiling step, and a silane coupling agent treatment step, followed by a fiber opening treatment after the deoiling step. . The fiber opening treatment after the deoiling step was performed by jetting high-pressure water after the silane coupling agent treatment step. The pressure of the high pressure water was 2 MPa.

Example 4
A glass fiber fabric was produced in the same manner as in Example 3, except that the temperature of the colloidal silica-containing liquid in the fiber opening treatment step before the deoiling step was 70 ° C.

(Comparative Example 1)
After the deoiling step and the silane coupling agent treatment step, the glass fiber fabric deoiling solution is immersed in a colloidal silica-containing liquid and the fiber blower is used to perform the fiber opening treatment without performing the fiber opening treatment before the deoiling step. A glass fiber fabric was produced. The processing conditions in this fiber opening treatment were the same as those in the fiber opening treatment before the deoiling step in Example 1.

(Comparative Example 2)
A glass fiber fabric was produced in the same manner as in Example 4 except that water was used instead of the colloidal silica-containing liquid in the fiber opening treatment step before the deoiling step.

(Comparative Example 3)
A glass fiber fabric was produced through the same deoiling step and silane coupling agent treatment step as in Example 1 without performing any fiber opening treatment before and after the deoiling step.

[Evaluation of glass fiber fabric]
About each glass fiber fabric of Examples 1-4 and Comparative Examples 1-3, the yarn width of the glass fiber yarn and the resin impregnation property were evaluated. Regarding the yarn width of the glass fiber yarn, the width of the glass fiber yarn of each of the warp and the weft was measured. In addition, evaluation of resin impregnation is performed by impregnating a glass fiber fabric into an epoxy resin varnish having a viscosity of 100 CPS, applying light of LED light to the glass fiber fabric, and visually observing voids between the glass filaments inside the glass fiber yarn, The time until the void disappeared was measured. The yarn width of the glass fiber yarn indicates the widening state of the glass fiber yarn, and is an index of the smoothness of the glass fiber fabric. The resin impregnation reflects the degree of unraveling of the glass fiber yarn and the size of the gap between the glass filaments.

  Table 1 shows production conditions and evaluation results of the glass fiber fabric production methods in the above Examples and Comparative Examples. The abbreviation V in the table represents a fiber-opening treatment with a vibratory oscher, and the abbreviation S represents a fiber-opening treatment by injecting high-pressure water onto a glass fiber fabric original fabric.

  The yarn width of the glass fiber yarn of Example 1 was almost the same as that of Comparative Example 2, and was larger than that of Comparative Examples 1 and 3. Moreover, the resin impregnation property of Example 1 was remarkably good as compared with Comparative Examples 1 to 3.

  The yarn width of the glass fiber yarn of Example 2 was slightly larger than the yarn width of Example 1. Further, the resin impregnation property of Example 2 was slightly better than that of Example 1.

  The yarn width of the glass fiber yarn of Example 3 was about the same as that of Example 1. Further, the resin impregnation property of Example 3 was slightly better than that of Example 1.

  The yarn width of the glass fiber yarn of Example 4 was equivalent to the yarn width of Example 2. Further, the resin impregnation property of Example 4 was slightly better than that of Example 2.

  The yarn widths of the glass fiber yarns of Examples 1 to 4 were larger than those of Comparative Examples 1 and 3. Therefore, it was confirmed that the glass fiber fabric manufactured by the manufacturing method of the present invention has good smoothness. Moreover, the resin impregnation property of Examples 1-4 was remarkably favorable compared with Comparative Examples 1-3. Therefore, it was confirmed that the resin fiber impregnation property of the glass fiber fabric manufactured by the manufacturing method of the present invention is very good.

It is a figure which shows the flowchart of the manufacturing method of the glass fiber fabric which concerns on embodiment. FIG. 2 is a schematic cross-sectional view showing an example of a vibratory oscher device.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Glass fiber fabric original fabric, 11 ... Runner, 12 ... Roll, 13 ... Rotor, 14 ... Treatment liquid tank, 15 ... Colloidal silica containing liquid, 16 ... Guide, S10, S20 ... Weaving process, S11, S21 ... 1st S12, S22 ... deoiling step, S13, S23 ... silane coupling agent treatment step, S24 ... second fiber opening treatment step.

Claims (4)

A method for producing a glass fiber fabric having a deoiling step in which a glass fiber fabric original fabric obtained by weaving a glass fiber yarn to which a sizing agent is adhered is heat-treated to obtain a glass fiber fabric deoiling process,
Before the deoiling step, the glass fiber fabric raw material is immersed in the colloidal silica-containing liquid, and the colloidal silica-containing liquid is vibrated in the front and back direction of the glass fiber fabric raw material, thereby the glass fiber fabric raw material is vibrated. On the other hand, the manufacturing method of the glass fiber fabric characterized by further having the 1st fiber-spreading process process which makes the pressure wave of the said colloidal silica containing liquid act.   The manufacturing method according to claim 1, wherein the temperature of the colloidal silica-containing liquid in the first fiber opening treatment step is 50 ° C or higher. The mass per unit area of the said glass fiber fabric is 50 g / m < ² > or less, The manufacturing method of Claim 1 or 2 characterized by the above-mentioned.   The manufacturing method according to any one of claims 1 to 3, further comprising a second fiber opening treatment step of spraying high-pressure water on the glass fiber fabric deoiling step after the deoiling step. .

Images