JP6866626B2 - Prepreg and its manufacturing method, fiber reinforced thermoplastic resin sheet manufacturing method, metal-clad laminated sheet manufacturing method, and wiring board manufacturing method - Google Patents

Description

The present invention relates to a fiber-reinforced thermoplastic resin sheet and a method for producing the same, a metal-clad laminated sheet, a composite and a silica fine particle-supported glass fiber non-woven fabric and a method for producing the same.

The sheet obtained by heat-press molding a composite (prepreg) containing fibers and resin is also called a fiber-reinforced resin sheet, and has higher mechanical strength than a resin sheet containing no fibers. There are advantages. The fiber-reinforced resin sheet containing non-conductive fibers is used as an insulating sheet, for example, as a base material for a wiring board or a metal-clad laminated sheet.

Patent Document 1 discloses a fiber-containing resin composition layer containing a thermosetting resin and a fiber base material and a laminate including a glass substrate layer as an insulating laminate useful for a semiconductor package or a printed wiring board. Has been done. Patent Document 1 describes that an inorganic filler is added to the fiber-containing resin composition layer. In Patent Document 1, as a method for forming a fiber-containing resin composition (prepreg) containing an inorganic filler, a resin composition containing an inorganic filler is impregnated or coated on a fiber base material, and then heat-dried to B. The method of staging (semi-curing) is described.

International Publication No. 2013/042751

As one of the uses of the fiber reinforced resin sheet, it is known to be used as a base material (insulating sheet) for a wiring board or a metal-clad laminated sheet. In this application, a thermosetting resin typified by an epoxy resin is widely used as a matrix resin material. However, thermosetting resins generally tend to have lower moldability than thermoplastic resins. On the other hand, a thermoplastic resin having a melting point and a thermal decomposition temperature higher than a general reflow soldering temperature (for example, 260 ° C.) such as polyetherimide and having excellent heat resistance has been developed. Some such thermoplastic resins have excellent properties such as low smoke emission and low dielectric constant, which cannot be realized by thermosetting resins typified by epoxy resins that have been used so far, and are used for wiring boards and metals. It is preferable that it can be used as a resin material for a stretched laminated sheet.

However, according to the study of the inventor of the present invention, the fiber-reinforced resin sheet using the thermoplastic resin as the matrix resin material is in the thickness direction of the sheet in a high temperature environment as compared with the one using the thermosetting resin. It was found that it easily expands thermally. If the base material of the wiring board or the metal-clad laminated sheet repeats thermal expansion and contraction in the thickness direction, the wiring (metal foil) may peel off from the base material and cause disconnection. Further, in a laminated wiring board in which a plurality of wiring boards are laminated, each wiring board constituting the laminated wiring board repeats thermal expansion and contraction in the thickness direction, which may cause the wiring board to peel off and break. is there. Therefore, it is desirable that the fiber-reinforced resin sheet used as the base material of the wiring board or the metal-clad laminated sheet has low thermal expansion in the thickness direction in a high temperature environment.

The present invention has been made in view of the above circumstances, and is fiber reinforced thermoplastic in which thermal expansion in the thickness direction in a high temperature environment is reduced while using a thermoplastic resin as a matrix resin component. It is an object of the present invention to provide a resin sheet and a metal-clad laminated sheet using the fiber-reinforced thermoplastic resin sheet. Another object of the present invention is to provide a composite (prepreg) containing a thermoplastic matrix resin and fibers, which can be used as a material for producing the fiber-reinforced thermoplastic resin sheet. Another object of the present invention is to provide a non-woven fabric that can be used as a fiber supply source for the fiber-reinforced thermoplastic resin sheet. Furthermore, it is also an object of the present invention to provide the above-mentioned method for producing a non-woven fabric and a method for producing a fiber-reinforced thermoplastic resin sheet.

The present inventor has prepared a fiber-reinforced thermoplastic resin sheet containing a thermoplastic matrix resin and glass fibers and silica fine particles having an average primary particle diameter in the range of 1 to 100 nm contained in the matrix resin. It was found that the thermal expansion in the thickness direction in a high temperature environment is reduced. In particular, the fiber-reinforced thermoplastic resin sheet using the silica fine particle-supporting glass fiber non-woven fabric in which the silica fine particles are supported on the glass fiber non-woven fabric as the supply source of the silica fine particles and the glass fiber is heat in the thickness direction in a high temperature environment. The present invention has been completed by finding that the swelling is significantly reduced. The reason why the thermal expansion of the fiber-reinforced thermoplastic resin sheet in the thickness direction is reduced is not necessarily clear, but it is to prevent the thermoplastic resin softened by heating of the silica fine particles from flowing in the thickness direction. It is believed that there is. In particular, when the silica fine particle-supporting glass fiber non-woven fabric is used, the silica fine particles are fixed by the glass fiber and become difficult to move, so that the effect of suppressing the flow of the thermoplastic resin in the thickness direction is enhanced. Therefore, it is considered that the fiber-reinforced thermoplastic resin sheet using the silica fine particle-supported glass fiber non-woven fabric significantly reduces the thermal expansion in the thickness direction in a high temperature environment.

Therefore, in order to achieve the above problems, the present invention has adopted the following configuration.
[1] A fiber-reinforced thermoplastic resin sheet containing a thermoplastic matrix resin, glass fibers contained in the matrix resin, and silica fine particles having an average primary particle size in the range of 1 to 100 nm.
[2] The fiber-reinforced thermoplastic resin sheet according to the item [1], wherein the silica fine particles are supported on the glass fiber.
[3] The fiber-reinforced thermoplastic resin sheet according to the item [1] or [2], wherein the glass fibers form a non-woven fabric.
[4] The fiber reinforcing heat according to any one of the items [1] to [3], wherein the content of the silica fine particles is in the range of 10 to 50 parts by mass with respect to 100 parts by mass of the glass fiber. Plastic resin sheet.
[5] The fiber-reinforced thermoplastic resin sheet according to any one of the items [1] to [4] and a metal foil bonded to at least one surface of the fiber-reinforced thermoplastic resin sheet are included. Metal-clad laminated sheet.
[6] A composite containing a silica fine particle-supported glass fiber non-woven fabric containing glass fibers and silica fine particles having an average primary particle diameter in the range of 1 to 100 nm supported on the glass fibers, and a thermoplastic matrix resin. A method for producing a fiber-reinforced thermoplastic resin sheet, which comprises a step of preparing the composite and a step of heat-press molding the composite.

[7] A composite containing a silica fine particle-supported glass fiber non-woven fabric containing glass fibers and silica fine particles supported on the glass fibers having an average primary particle diameter in the range of 1 to 100 nm, and a thermoplastic matrix resin. ..
[8] The complex according to the item [7], wherein the matrix resin is arranged in a layer on at least one surface of the silica fine particle-supporting glass fiber nonwoven fabric.
[9] The composite according to the item [7], wherein the matrix resin is arranged in the state of beads or fibers inside the silica fine particle-supporting glass fiber non-woven fabric.

[10] A silica fine particle-supporting glass fiber non-woven fabric containing a glass fiber and silica fine particles having an average primary particle diameter supported on the glass fiber in the range of 1 to 100 nm.
[11] A step of preparing a glass fiber non-woven fabric containing glass fibers and a silica dispersion liquid in which silica fine particles having an average primary particle diameter in the range of 1 to 100 nm are dispersed in a solvent, and the glass fiber non-woven fabric and the silica. A method for producing a silica fine particle-supporting glass fiber non-woven fabric, which comprises a step of contacting a dispersion liquid to carry silica fine particles on the glass fiber.

According to the present invention, a fiber-reinforced thermoplastic resin sheet in which thermal expansion in the thickness direction in a high temperature environment is reduced while using a thermoplastic resin as a matrix resin component, and this fiber-reinforced thermoplastic resin sheet. It becomes possible to provide a metal-clad laminated sheet using. In addition, the composite of the present invention can be advantageously used as a material (prepreg) for producing the fiber-reinforced thermoplastic resin sheet. Further, the nonwoven fabric of the present invention can be advantageously used as a fiber supply source for the fiber-reinforced thermoplastic resin sheet. Furthermore, according to the method for producing a glass fiber non-woven fabric of the present invention, the above-mentioned glass fiber non-woven fabric can be industrially advantageously produced. Then, according to the method for producing a fiber-reinforced thermoplastic resin sheet of the present invention, the above-mentioned fiber-reinforced thermoplastic resin sheet can be industrially advantageously produced.

It is sectional drawing of an example of the silica fine particle-supporting glass fiber nonwoven fabric which is one Embodiment of this invention. It is sectional drawing of another example of the silica fine particle-supporting glass fiber nonwoven fabric which is one Embodiment of this invention. It is sectional drawing of an example of the complex which is one Embodiment of this invention. It is sectional drawing of another example of the complex which is one Embodiment of this invention. It is a cross-sectional view of still another example of the complex which is one Embodiment of this invention. It is sectional drawing of an example of the fiber reinforced thermoplastic resin sheet which is one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

<Silica fine particle-supported glass fiber non-woven fabric>
First, a silica fine particle-supporting glass fiber non-woven fabric that can be advantageously used as a source of silica fine particles and glass fibers contained in the fiber-reinforced thermoplastic resin sheet of the present invention will be described.
FIG. 1 is a cross-sectional view of a silica fine particle-supporting glass fiber nonwoven fabric according to an embodiment of the present invention. As shown in FIG. 1, the silica fine particle-supporting glass fiber non-woven fabric 10a of the present embodiment contains the glass fiber 11 and the silica fine particle 12 supported on the glass fiber 11.

The length of the glass fiber 11 in the present invention is not particularly limited as long as it can form a non-woven fabric and can support the silica fine particles 12, but in the present embodiment, the glass fiber 11 has a length of 3 to 25 mm. It is said to be in the range of. The diameter of the glass fiber 11 is generally in the range of 3 to 18 μm, preferably in the range of 6 to 15 μm, more preferably in the range of 6 to 13 μm. The aspect ratio (length / diameter) of the glass fiber 11 is generally in the range of 100 to 20000, preferably in the range of 160 to 18000, and more preferably in the range of 200 to 15000. The glass fiber 11 is preferably a chopped strand.

As shown in FIG. 1, most of the glass fibers 11 are preferably oriented horizontally with respect to the plane direction of the silica fine particle-supporting glass fiber non-woven fabric 10a. Here, "horizontally oriented" means that the angle θ ₁ with respect to the plane direction is oriented to be 0 degrees, and the angle θ ₁ with respect to the plane direction is within ± 30 degrees. Including the case of orientation. _{The amount of the glass fibers 11 oriented so that the angle θ 1} with respect to the plane direction is within ± 30 degrees is preferably 80% or more, preferably 90% or more, based on the total amount of the glass fibers 11. More preferably. When the non-woven fabric in which the glass fibers 11 are oriented in the plane direction within the above angle is used, the strength of the fiber-reinforced thermoplastic resin sheet in the plane direction can be increased and the thermal expansion in the plane direction can be reduced.

The silica fine particles 12 have an average primary particle diameter in the range of 1 to 100 nm, preferably in the range of 1 to 50 nm, and more preferably in the range of 1 to 30 nm. The average primary particle size of the silica fine particles 12 is measured by a method of measuring the particle size by magnifying and observing 1000 to 5000 particles. As a method of magnifying and observing the particles, a method using an electron microscope, an interatomic force microscope, or a transmission electron microscope can be considered, but the particle size of the silica particles to be observed and a large number of particles must be observed quickly. Considering that this is not the case, the method using a transmission electron microscope is preferable. The silica fine particles 12 may form aggregated particles. The silica fine particles 12 may be adhered to the glass fiber 11 via a binder. Acrylic resin can be used as the binder.

The silica fine particles 12 may be crystalline or non-crystalline, and the effects of the present invention can be obtained. From the viewpoint of further enhancing the effect of the present invention, that is, further enhancing the effect of reducing the coefficient of thermal expansion in the thickness direction, it is more preferable to use non-crystalline silica fine particles. It is considered that non-crystalline silica tends to be bulky and has various particle shapes. The shape of the silica fine particles 12 is not particularly limited, and may be any of a spherical shape, an elliptical spherical shape, a polygonal columnar shape, a plate shape, and an indefinite shape. Examples of the type of silica fine particles 12 include dry silica (fumed silica), wet silica, and colloidal silica. As the silica fine particles 12, one type may be used alone, or two or more types may be used in combination.

The content of the silica fine particles 12 in the silica fine particle-supporting glass fiber non-woven fabric 10a is preferably in the range of 5 to 50 parts by mass, more preferably in the range of 5 to 45 parts by mass, with the content of the glass fiber 11 as 100 parts by mass. Particularly preferably, it is in the range of 10 to 40 parts by mass. When the silica fine particle-supporting glass fiber non-woven fabric in which the content of the silica fine particles 12 is in the above range is used, the thermal expansion of the fiber-reinforced thermoplastic resin sheet in the thickness direction can be more reliably reduced.

The content of the silica fine particles 12 in the silica fine particle-supporting glass fiber nonwoven fabric 10a containing the binder can be determined, for example, as follows.
First, the mass of the silica fine particle-supported glass fiber nonwoven fabric 10a is measured (hereinafter, this mass is referred to as A).
Next, the binder in the silica fine particle-supported glass fiber non-woven fabric 10a is removed, and the mass is measured (hereinafter, this mass is referred to as B). The method of removing the binder is a method of thermally decomposing and removing the binder by heating at a temperature higher than the thermal decomposition temperature of the binder and lower than the thermal decomposition temperature of the glass fiber 11, or a method of immersing the binder in a solvent for dissolving the binder. Is exemplified.
Next, the silica fine particle-supported glass fiber non-woven fabric 10a from which the binder has been removed is immersed in water having a mass about 100 times that of the non-woven fabric and stirred. In this way, a slurry in which the glass fibers 11 and the silica fine particles 12 are dispersed in water can be obtained. The slurry is filtered through a 100 mesh sieve and the residue on the sieve is washed with water to remove the silica fine particles 12. Washing with water is carried out by observing the residue on the sieve under a microscope until no silica particles are confirmed in the residue. The residue from which the silica fine particles 12 have been removed in this manner is heated, dried, and cooled at a temperature of 105 to 200 ° C., and the mass is measured (hereinafter, this mass is referred to as C). The content of the silica fine particles 12 is calculated by the following formula.
Content of silica fine particles 12 (mass%) = (BC) ÷ A × 100 (%)

When the silica fine particle-supporting glass fiber non-woven fabric 10a does not contain a binder, the content of the silica fine particles 12 can be calculated from the following formula.
Content of silica fine particles 12 (mass%) = (AC) ÷ A × 100 (%)

The silica fine particle-supporting glass fiber non-woven fabric 10a may further contain short fibers having a length shorter than that of the glass fiber 11. The short fibers are preferably glass short fibers or heat-resistant resin short fibers.

FIG. 2 is a cross-sectional view of another example of the silica fine particle-supporting glass fiber nonwoven fabric according to the embodiment of the present invention. In the silica fine particle-supporting glass fiber non-woven fabric 10b of FIG. 2, in addition to the glass fiber 11 and the silica fine particle 12, the glass short fiber 13 and the heat-resistant resin short fiber 14 are inserted therein. Here, "inserted inside" means that a length of 1/2 or more of the length of the fiber is inside the silica fine particle-supported glass fiber non-woven fabric 10b. A preferred embodiment of the glass fiber 11 and the silica fine particle 12 is the same as that in the silica fine particle-supporting glass fiber non-woven fabric 10a shown in FIG.

The short glass fiber 13 preferably has a length in the range of 0.3 to 1 mm. The diameter of the glass short fibers 13 is preferably in the range of 3 to 18 μm, more preferably in the range of 6 to 15 μm, and particularly preferably in the range of 6 to 13 μm. The aspect ratio (length / diameter) of the glass short fibers 13 is preferably in the range of 30 to 7000, more preferably in the range of 50 to 6000, and particularly preferably in the range of 60 to 5000.

It is preferable that at least a part of the short glass fiber 13 is oriented in the thickness direction of the silica fine particle-supporting glass fiber non-woven fabric 10b. Here, "aligned in the thickness direction" means that the angle θ ₂ with respect to the plane direction is 90 degrees, and the angle θ ₂ with respect to the plane direction is in the range of 60 to 120 degrees. Including the case where it is oriented so as to be inside. The amount of the glass short fibers 13 oriented in the thickness direction is preferably 30% or more, more preferably 40% or more, based on the total amount of the glass short fibers 13. By using the silica fine particle-supporting glass fiber non-woven fabric 10b in which the short glass fibers 13 are inserted in the state of being oriented in the thickness direction, the flow of the thermoplastic resin softened by heating in the thickness direction is further suppressed. Therefore, the thermal expansion of the fiber-reinforced thermoplastic resin sheet in the thickness direction can be further reduced.

The heat-resistant resin short fibers 14 preferably have a negative coefficient of thermal expansion and do not melt or thermally decompose at a temperature of 260 ° C. or lower. Here, the "negative coefficient of thermal expansion" means that the volume contracts when the temperature rises and expands when the temperature falls. The coefficient of thermal expansion of the heat-resistant resin short fibers is preferably in the range of ^{-4 × 10 -6 to -6} × 10 -6 cm / cm / ° C. Further, "does not melt and thermally decompose at a temperature of 260 ° C. or lower" means that it does not melt and thermally decompose when heated at a temperature of 260 ° C. for 10 minutes.

The heat-resistant resin short fibers 14 preferably have a length in the range of 0.1 to 1 mm. The diameter of the heat-resistant resin short fibers 14 is preferably in the range of 0.1 to 30 μm, more preferably in the range of 0.0001 to 18 μm, and particularly preferably in the range of 0.001 to 15 μm. The aspect ratio (length / diameter) of the heat-resistant resin short fibers 14 is preferably in the range of 500 to 1,000,000, more preferably in the range of 2000 to 1,000,000, and particularly preferably in the range of 2000 to 1,000,000. When the length of the heat-resistant resin short fibers 14 is 0.1 mm or more, the heat-resistant resin short fibers do not easily fall off from the non-woven fabric during dehydration when the silica fine particle-supporting glass fiber non-woven fabric 10b is manufactured by the papermaking method, and the heat resistance is high. It is preferable because it is easy to obtain a non-woven fabric containing resin short fibers. On the other hand, when the length of the heat-resistant resin short fibers 14 is shorter than 1 mm, it is easy to obtain the silica fine particle-supporting glass fiber non-woven fabric 10b in which the heat-resistant resin short fibers are oriented in the thickness direction, and the effect of the heat-resistant resin fibers is ensured. Can be obtained.

Examples of the heat-resistant resin short fibers 14 include aramid fibers and PBO (polyparaphenylene benzoxazole) fibers. The heat-resistant resin short fibers 14 may be used alone or in combination of two or more. The heat-resistant resin short fibers 14 may be in the form of chopped strands or in the form of pulp. The pulp-like heat-resistant resin short fibers 14 are preferable in that they are more entangled with the glass fibers 11 as compared with the chopped strand-like ones.

It is preferable that at least a part of the heat-resistant resin short fibers 14 is oriented in the thickness direction of the silica fine particle-supporting glass fiber non-woven fabric 10b. Here, "aligned in the thickness direction" means that the angle θ ₃ with respect to the plane direction is 90 degrees, and the angle θ ₃ with respect to the plane direction is in the range of 60 to 120 degrees. Including the case where it is oriented so as to be inside. The angle θ ₃ of the heat-resistant resin short fibers is the angle of a straight line connecting both ends of the heat-resistant resin short fibers in the length direction. The amount of the heat-resistant resin short fibers oriented in the thickness direction is preferably 30% or more, more preferably 40% or more, based on the total amount of the heat-resistant resin short fibers. With the heat-resistant resin short fibers oriented in the thickness direction, the heat-resistant resin short fibers are thermally expanded in the thickness direction of the thermoplastic resin by using the silica fine particle-supporting glass fiber non-woven fabric 10b inserted inside. Since it is offset by the heat shrinkage of the fiber-reinforced thermoplastic resin sheet, the thermal expansion in the thickness direction of the fiber-reinforced thermoplastic resin sheet can be further reduced.

The total content of the glass short fibers 13 and the heat-resistant resin short fibers 14 contained in the silica fine particle-supporting glass fiber non-woven fabric 10b is a mass ratio of the glass fibers 11 and is preferably in the range of 50:50 to 95: 5 (glass fibers). The content of 11: the total content of the glass short fibers 13 and the heat-resistant resin short fibers 14), more preferably in the range of 55:45 to 95: 5, and particularly preferably in the range of 60:40 to 90:10. That is, the total content of the glass short fibers 13 and the heat-resistant resin short fibers 14 with respect to the total amount of the glass fibers 11, the glass short fibers 13 and the heat-resistant resin short fibers 14 is preferably in the range of 5 to 50% by mass. It is preferably in the range of 5 to 45% by mass, particularly preferably in the range of 10 to 40% by mass.

The content ratio of the glass fiber 11, the glass short fiber 13, and the heat-resistant resin short fiber 14 in the silica fine particle-supporting glass fiber non-woven fabric 10b can be determined, for example, as follows.
Using an optical microscope, the silica fine particle-supporting glass fiber non-woven fabric 10b is observed, and a total of 100 fibers (including the glass fiber 11, the glass short fiber 13, and the heat-resistant resin short fiber 14) are arbitrarily selected from one observation area. Select, count the number of glass fibers 11, glass short fibers 13, and heat-resistant resin short fibers 14 in the 100 fibers, and measure the length and diameter of each fiber. The average number of lengths and diameters of the measured glass fibers 11, glass short fibers 13, and heat-resistant resin short fibers 14 is obtained. Using the obtained average length and average diameter, the content of the glass fiber 11 and the content of the short fiber are calculated from the following formulas, respectively. Then, the calculated ratio of the content of the glass fiber 11 to the content of the short fiber is obtained.
Content of glass fiber 11 = average length x (average diameter / 2) ² x π x density of glass fiber 11 x number of glass fibers 11 in 100 fibers Content of short glass fiber 13 = average length x (Average diameter / 2) ² × π × Density of glass short fibers 13 × Number of glass short fibers 13 in 100 fibers Heat-resistant resin short fibers 14 = Average length × (Average diameter / 2) ² × π × Density of heat-resistant resin short fibers 14 × number of heat-resistant resin short fibers 14 in 100 fibers

<Manufacturing method of silica fine particle-supported glass fiber non-woven fabric>
In the method for producing a silica fine particle-supporting glass fiber non-woven fabric according to an embodiment of the present invention, a glass fiber non-woven fabric containing glass fibers and silica in which silica fine particles having an average primary particle diameter in the range of 1 to 100 nm are dispersed in a solvent It has a step of preparing a dispersion liquid and a silica fine particle supporting treatment step of bringing the glass fiber non-woven fabric and the silica dispersion liquid into contact to support the silica fine particles on the glass fiber.

The glass fiber non-woven fabric containing glass fiber can be produced by making a paper by using an aqueous dispersion liquid containing glass fiber using a filter medium. Further, a glass fiber non-woven fabric containing glass short fibers or heat-resistant resin short fibers can be produced by making a paper by using an aqueous dispersion liquid containing glass fibers and those short fibers using a filter medium. A dispersant may be added to the aqueous dispersion in order to suppress the aggregation of fibers such as glass fibers, glass short fibers, and heat-resistant resin short fibers. In addition, a thickener may be added to the aqueous dispersion.

Papermaking of the aqueous dispersion can be carried out using a known paper machine used for producing a general wet non-woven fabric. As the paper machine, either a batch type paper machine or a continuous type paper machine can be used.

The batch type paper machine is a paper machine that repeats each process of supplying an aqueous dispersion liquid to a container for raw materials, forming a fiber layer by paper making (dehydration), and recovering the fiber layer as one cycle. When using a batch paper machine, the solid content of the aqueous dispersion in the raw material container (if it contains short fibers such as glass short fibers or heat-resistant resin short fibers, the total amount of glass fibers and short fibers) The concentration of is preferably 1% by mass or less, and more preferably in the range of 0.001 to 0.7% by mass. When the concentration of the solid content of the aqueous dispersion is in the above range, the degree of freedom of movement of the fibers in the aqueous dispersion is increased, and a sufficient dehydration rate can be obtained at the time of dehydration. Therefore, it becomes easy to orient the long glass fibers in the horizontal direction, and further, when the short fibers such as the glass short fibers or the heat-resistant resin short fibers are contained, these short fibers are easily oriented in the thickness direction. ..

The viscosity of the aqueous dispersion in the raw material container is preferably in the range of 0.9 mPa · s or more and 3.0 mPa · s or less by adding the above-mentioned thickener. When the viscosity of the aqueous dispersion is in this range, there is a tendency that a glass fiber non-woven fabric having excellent fiber dispersibility and less fiber breakage or breakage can be produced with high productivity even if the Reynolds number is the same. On the other hand, if the viscosity of the aqueous dispersion is too low, the fibers tend to aggregate, and the dispersibility of the fibers may decrease. Further, if the viscosity of the aqueous dispersion becomes too high, the dehydration resistance may increase, leading to a decrease in productivity. Therefore, it is preferable that the viscosity is set in consideration of suppression of fiber aggregation and productivity. That is, if the viscosity of the aqueous dispersion is 1.1 mPa · s, fiber aggregation can be suppressed, and if it is 1.0 mPa · s or less, productivity can be improved. As for the viscosity of the aqueous dispersion, the aqueous dispersion was filtered through an 80 mesh filter (flui) to collect a filtrate from which fibers had been removed, and a Canon Fenceke viscometer was used to collect JIS Z 8803 “Method for measuring the viscosity of liquid”. It can be measured according to the measuring method specified in the above.

A continuous paper machine is a paper machine that continuously performs the steps of supplying an aqueous dispersion liquid to an inlet, forming a fiber layer by paper making (dehydration), and recovering the fiber layer. Examples of continuous paper machines include tilted paper machines, circular net paper machines and long net paper machines. When producing a glass fiber non-woven fabric containing short fibers such as glass short fibers or heat-resistant resin short fibers, it is preferable to use an inclined paper machine capable of rapidly dehydrating by reducing the concentration in the inlet. .. This is because the short fibers are oriented in the thickness direction due to the water flow due to rapid dehydration. When using an inclined paper machine, the solid content concentration of the aqueous dispersion in the inlet is preferably in the range of 0.001 to 0.5% by mass, preferably in the range of 0.002 to 0.3% by mass. It is more preferable that it is in the range of 0.008 to 0.1% by mass. By setting the concentration of the solid content of the aqueous dispersion in the inlet within such a concentration range, a sufficient dehydration rate can be obtained, so that the short fibers can be sufficiently oriented in the thickness direction. Moreover, since the dehydration load does not become too high, the glass fiber non-woven fabric can be produced with energy efficiency. The viscosity of the aqueous dispersion in the inlet is preferably in the range of 0.9 mPa · s or more and 3.0 mPa · s or less, as in the case of using the batch type paper machine. As the filter medium, a filter medium having an opening in the range of 30 to 150 mesh can be used.

Then, the fiber layer (wet sheet) recovered from the paper machine is dried to obtain a glass fiber non-woven fabric. A heating dryer such as a hot air dryer can be used to dry the wet sheet.

The silica dispersion liquid can be prepared by stirring and mixing the silica fine particles and the dispersion medium. Water can be used as the dispersion medium. The concentration of the silica fine particles in the silica dispersion is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 0.2 to 25% by mass, and in the range of 0.5 to 20% by mass. It is particularly preferable to be in. The silica dispersion liquid may contain a binder in order to improve the adhesion of the silica fine particles to the glass fiber. As the binder, an acrylic emulsion can be used. The concentration of the binder is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 10% by mass, and in the range of 0.5 to 5% by mass with respect to the silica fine particles. It is particularly preferable to be in.

In the silica fine particle supporting treatment step, a dipping method, a coating method, a spraying method, or a printing method can be used as a method for bringing the glass fiber non-woven fabric into contact with the silica dispersion liquid.

Next, the silica fine particles are supported on the glass fibers of the glass fiber non-woven fabric by drying the silica dispersion liquid adhering to the glass fiber non-woven fabric. A heating dryer such as a hot air dryer can be used to dry the silica dispersion.
As described above, the silica fine particle-supported glass fiber non-woven fabric is produced.

<Complex>
The composite (blipreg) according to the embodiment of the present invention is a composite containing the above-mentioned silica fine particle-supporting glass fiber non-woven fabric and a thermoplastic matrix resin. The content of the silica fine particle-supported glass fiber non-woven fabric and the thermoplastic resin is preferably in the range of 50:50 to 10:90 (nonwoven fabric: thermoplastic resin), more preferably in the range of 45:55 to 15:85, in terms of mass ratio. Particularly preferably, it is in the range of 45:55 to 20:80. That is, the content of the matrix resin with respect to the total amount of the silica fine particle-supported glass fiber non-woven fabric and the matrix resin is preferably in the range of 50 to 90% by mass, more preferably in the range of 55 to 85% by mass, and particularly preferably in the range of 55 to 80. It is in the range of% by mass. When the content ratio of the silica fine particle-supported glass fiber non-woven fabric and the matrix resin is in the above range, the characteristics of the matrix resin (for example, low dielectric constant, low dielectric loss, etc.) and the characteristics of the non-woven fabric (for example, in a high temperature environment) (Suppression of thermal expansion, etc.) can be expressed in a well-balanced manner.

The thermoplastic matrix resin may be arranged in layers on the surface of the silica fine particle-supporting glass fiber non-woven fabric, may be arranged in the form of beads or fibers inside the silica fine particle-supporting glass fiber non-woven fabric, or further. It may be arranged on both the surface and the inside of the silica fine particle-supporting glass fiber non-woven fabric. Further, the beads and fibers of the thermoplastic matrix resin may be used in combination.

FIG. 3 is a cross-sectional view of an example of a complex according to an embodiment of the present invention. In FIG. 3, the thermoplastic matrix resin is arranged as the matrix resin layer 20 on the surface of the silica fine particle-supporting glass fiber non-woven fabric 10a. In FIG. 3, the matrix resin layer 20 is arranged on one surface (upper surface in FIG. 3) of the silica fine particle-supporting glass fiber non-woven fabric 10a, but is arranged on both surfaces of the silica fine particle-supporting glass fiber non-woven fabric 10a. You may. The matrix resin layer 20 may be simply laminated or adhered to the surface of the silica fine particle-supporting glass fiber non-woven fabric 10a.

In the composite of FIG. 3, for example, a silica fine particle-supported glass fiber non-woven fabric and a thermoplastic matrix resin sheet are laminated, and the obtained laminate is heated and pressed to melt the matrix resin sheet into the silica fine particle-supported glass fiber non-woven fabric. It can be manufactured by wearing it.

FIG. 4 is a cross-sectional view of another example of the complex according to the embodiment of the present invention. In FIG. 4, the thermoplastic matrix resin is arranged as matrix resin beads 21 inside the silica fine particle-supporting glass fiber non-woven fabric 10a. The shape of the matrix resin beads 21 is preferably a sphere, an elliptical sphere, or a cylinder. The matrix resin beads 21 preferably have a major axis length in the range of 0.1 to 2 mm, more preferably in the range of 0.3 to 1.0 mm, and preferably in the range of 0.4 to 0.7 mm. It is particularly preferable to have.

In the composite of FIG. 4, for example, first, a non-woven fabric containing the matrix resin beads 21 and the glass fiber 11 is prepared, and then the non-woven fabric and the silica dispersion liquid are brought into contact with each other to form the silica fine particles 12 on the glass fiber 11. It can be manufactured by carrying it. The non-woven fabric containing the matrix resin beads 21 and the glass fibers 11 can be produced by making a paper by using an aqueous dispersion liquid containing the matrix resin beads 21 and the glass fibers 11 using a filter medium. The aqueous dispersion containing the matrix resin beads 21 and the glass fibers 11 can be prepared by adding the matrix resin beads 21 to the above-mentioned aqueous dispersion containing the glass fibers 11. The concentration of the solid content (total of the matrix resin beads 21 and the glass fiber 11) of the aqueous dispersion liquid at the time of papermaking is preferably 1% by mass or less, and is in the range of 0.001 to 0.7% by mass. Is more preferable.

FIG. 5 is a cross-sectional view of still another example of the complex according to the embodiment of the present invention. In FIG. 5, the thermoplastic matrix resin is arranged as the matrix resin fiber 22 inside the silica fine particle-supporting glass fiber non-woven fabric 10a. That is, this complex forms a non-woven fabric-like complex containing glass fibers 11, silica fine particles 12, and matrix resin fibers 22. The matrix resin fiber 22 preferably has a mass average fiber length in the range of 1.0 to 30 mm and a fiber diameter in the range of 0.1 to 100 dtex. The mass average fiber length of the matrix resin fiber 22 is more preferably in the range of 3.0 to 25 mm. Further, the fiber diameter is more preferably in the range of 1.0 to 3.0 dtex. In the present specification, the mass average fiber length is the mass average value of the fiber lengths measured for 100 matrix resin fibers.

In the non-woven fabric-like composite of FIG. 5, for example, first, a non-woven fabric containing the matrix resin fiber 22 and the glass fiber 11 is prepared, and then the non-woven fabric and the silica dispersion liquid are brought into contact with each other to form silica on the glass fiber 11. It can be produced by supporting the fine particles 12. The non-woven fabric containing the matrix resin fiber 22 and the glass fiber 11 can be produced by making a paper by using an aqueous dispersion liquid containing the matrix resin fiber 22 and the glass fiber 11 using a filter medium. The aqueous dispersion containing the matrix resin fiber 22 and the glass fiber 11 can be prepared by adding the matrix resin fiber 22 to the above-mentioned aqueous dispersion containing the glass fiber 11. The concentration of the solid content (total of the matrix resin fiber 22 and the glass fiber 11) of the aqueous dispersion liquid at the time of papermaking is preferably 1% by mass or less, and is in the range of 0.001 to 0.7% by mass. Is more preferable.

The thermoplastic matrix resin contained in the complex of the present embodiment can be appropriately selected depending on the intended use. For example, when the composite (prepreg) of the present embodiment is used as an intermediate of an insulating sheet of a wiring board or a metal-clad laminated sheet, the thermoplastic matrix resin heats the composite containing the thermoplastic matrix resin. It is preferable that the resin is a resin that does not melt, deform, or thermally decompose at a temperature equal to or lower than the soldering reflow temperature in the state of the compacted body that has been pressure-molded. "Does not melt, deform and pyrolyze at temperatures below the soldering reflow temperature" means that it does not melt, deform and pyrolyze when heated at the soldering reflow temperature for at least 1 minute.
The matrix resin used in the present invention, which is thermoplastic, has a melting point higher than the soldering reflow temperature, or in the case of a non-crystalline thermoplastic resin having no melting point, the glass transition temperature is sufficiently high, as described above. It is preferable that the molded product does not deform when heated at the soldering reflow temperature for at least 1 minute. The melting point or glass transition temperature of the matrix resin cannot be uniformly determined because the soldering reflow temperature differs depending on the conditions such as the type of solder used and the type of parts to be mounted, but it is preferably 220 ° C. or higher, more preferably. Is 260 ° C. or higher, more preferably 280 ° C. or higher. When the matrix resin is a non-crystalline thermoplastic resin, even if the glass transition temperature is lower than the soldering reflow temperature, in the state of the molded body described above, the soldering reflow temperature is affected by the reinforcing effect of the glass fiber. In some cases, it does not melt, deform, or thermally decompose even when heated, and in such cases, the thermoplastic resin can be used in the present invention.

When the composite contains heat-resistant resin short fibers, the melting point or glass transition temperature of the matrix resin is preferably lower than the thermal decomposition temperature of the heat-resistant resin short fibers. If the melting point of the matrix resin, which is a thermoplastic resin, or the glass transition temperature is higher than the thermal decomposition temperature of the heat-resistant resin short fibers, the heat-resistant resin short fibers may be thermally decomposed during heat-pressurization molding. Is. For example, when aramid fibers are contained as the heat-resistant resin short fibers, the melting point or the glass transition temperature of the matrix resin is preferably 400 ° C. or lower. Examples of such thermoplastic resins include polyetherimide (PEI), polyetheretherketone (PEEK), and polyphenylene sulfide (PPS). These thermoplastic resins may be used alone or in combination of two or more.

The composite may contain a binder resin in order to improve the adhesion between the matrix resin and the silica fine particle-supporting glass fiber non-woven fabric. The binder resin is preferably a resin that is compatible with the matrix resin when the composite is heat-press molded. Examples of the binder resin include polyvinyl alcohol (PVA). When the thermoplastic matrix resin is arranged in a layer on the surface of the silica fine particle-supporting glass fiber non-woven fabric, the binder resin is preferably arranged in a layer between the layer of the matrix resin and the surface of the non-woven fabric. When the thermoplastic matrix resin is arranged in the state of beads or fibers inside the silica fine particle-supporting glass fiber non-woven fabric, the binder resin is preferably arranged in the state of beads or fibers inside the non-woven fabric. ..

<Fiber reinforced thermoplastic resin sheet>
The fiber-reinforced thermoplastic resin sheet of the present invention contains a thermoplastic resin, glass fibers, and silica fine particles. The fiber-reinforced thermoplastic resin sheet of the present invention is preferably a heat-pressurized molded product obtained by heat-press molding the above-mentioned composite.

FIG. 6 is a cross-sectional view of an example of a fiber-reinforced thermoplastic resin sheet according to an embodiment of the present invention. The fiber-reinforced thermoplastic resin sheet 30 contains a thermoplastic matrix resin 23, glass fibers 11 and silica fine particles 12 contained in the matrix resin 23. The glass fiber 11 and the silica fine particle 12 maintain the state of the silica fine particle-supporting glass fiber non-woven fabric 10a. That is, the glass fibers 11 are oriented in the plane direction of the fiber-reinforced thermoplastic resin sheet 30. Further, the silica fine particles 12 are supported on the glass fiber 11. However, it is not necessary that all of the glass fibers 11 and the silica fine particles 12 maintain the state of the silica fine particles-supported glass fiber non-woven fabric 10a.

The fiber-reinforced thermoplastic resin sheet 30 of the present embodiment has low thermal expansion in the thickness direction in a high temperature environment. Therefore, it can be advantageously used as a base material (insulating sheet) for a wiring board or a metal-clad laminated sheet.

The metal-clad laminated sheet is a sheet containing a metal foil bonded to at least one surface of the fiber-reinforced thermoplastic resin sheet 30. The metal-clad laminated sheet can be produced by heat-press molding with a metal foil laminated on at least one surface of the composite. Examples of the material of the metal foil include copper, aluminum, silver, and gold.
A wiring board can be obtained by patterning the metal foil of this metal-clad laminated sheet by a method such as etching.

<Manufacturing method of fiber reinforced thermoplastic resin sheet>
The fiber-reinforced thermoplastic resin sheet can be produced by heat-press molding the above-mentioned composite. Only one composite may be heat-press molded, or two or more composites may be heat-press molded, and the composite may be determined according to the application of the fiber-reinforced thermoplastic resin sheet to be molded. The heating temperature is equal to or higher than the temperature at which the thermoplastic matrix resin contained in the complex softens and becomes plastic. The optimum temperature range varies depending on conditions such as the type and content of the thermoplastic matrix resin, so it cannot be set uniformly, but it is usually in the range of 260 to 600 ° C, preferably 280 to 450 ° C. The range, more preferably the range of 280 ° C to 400 ° C.

The pressurizing pressure can be appropriately set according to conditions such as the thickness of the complex and the thickness of the target fiber-reinforced thermoplastic resin sheet. The pressurizing pressure is usually in the range of 3 to 50 MPa, preferably in the range of 5 to 20 MPa.
The heating and pressurizing time is not particularly limited, but is usually in the range of 1 to 100 minutes, preferably 1 to 30 minutes.

Although the embodiments of the present invention have been described above, these embodiments are presented as examples and can be appropriately modified without departing from the technical idea of the present invention.
For example, in the fiber-reinforced thermoplastic resin sheet of the present embodiment, an example in which the glass fiber and the heat-resistant resin fiber form a silica fine particle-supporting glass fiber non-woven fabric has been described, but the glass fiber and the heat-resistant resin fiber are non-woven fabrics. Does not have to be formed. However, in this case, it is preferable that the glass fibers are oriented in the plane direction of the fiber-reinforced thermoplastic resin sheet and the silica fine particles are supported on the glass fibers.

[Example 1]
(1) Preparation of Aqueous Fiber Dispersion Weigh 50 g of glass fiber having a mass average fiber length of 10 mm and a mass average fiber diameter of 10 μm, and add 0.15 g of a dispersant (0.3 mass% with respect to the glass fiber). The mixture was poured into 20 L of water and stirred using a laboratory stirrer to disperse the glass fiber aqueous dispersion. As the glass fiber, CS10JAJP195, a glass fiber chopped strand manufactured by Owens Corning, was used. As the dispersant, Laccol AL manufactured by Meisei Chemical Works, Ltd. was used. As the laboratory stirrer, an ultra stirrer DC-CHRM25 manufactured by AS ONE Corporation was used.

85 g of polyetherimide (PEI) fiber and 5 g of polyvinyl alcohol (PVA) fiber as a binder were added to the above glass fiber aqueous dispersion, and the mixture was stirred using the laboratory stirrer. As the PEI fiber, a chopped strand (manufactured by Kuraray Co., Ltd.) having a mass average fiber length of 15 mm and a fiber diameter of 2.2 dtex was used. As the PVA fiber, one having a mass average fiber length of 3 mm (manufactured by Kuraray Co., Ltd., VPB105) was used.

Next, 500 mL of a thickener aqueous solution having a thickener concentration of 0.1% by mass was added to the dispersion liquid containing the PEI fibers and PVA fibers, and the mixture was stirred with the laboratory stirrer. As the thickener, an anionic polymer polyacrylamide-based thickener (manufactured by MT Aquapolymer, Sumiflock) was used.
Finally, water was added so that the total amount was 28 kg, and the mixture was stirred with the laboratory stirrer. In this way, a fibrous aqueous dispersion having a solid content concentration of 0.5% by mass in which glass fibers, PEI fibers and PVA fibers were uniformly dispersed was prepared. The fibrous aqueous dispersion was prepared twice.

(2) Preparation of Nonwoven Fabric Complex Sheet 1250 g (solid content: 6.25 g) of the fibrous aqueous dispersion prepared in (1) above was separated. The separated fibrous aqueous dispersion was put into a container for raw materials of a 25 cm square hand-made sheet machine (manufactured by Kumagai Riki Kogyo Co., Ltd.), and papermaking was performed by a method according to JIS P 8222. That is, water was put into the raw material container to dilute it to 16 L, and the inside of the raw material container was stirred and then dehydrated to obtain a wet sheet. Then, the obtained wet sheet was dried with a hot air dryer at 160 ° C. to obtain a non-woven composite sheet (length 25 cm × width 25 cm, basis weight 100 g / m ² ).

(3) Preparation of Aqueous Silica Fine Particle Dispersion 200 mL of water was put into a plastic beaker having a capacity of 500 mL. Next, while stirring this water at 4000 rpm using a desktop chorus stirrer, silica fine particles (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter: 12 nm) are added little by little, and the silica fine particle concentration is 10 mass by mass. % Silica was prepared. An acrylic emulsion (manufactured by DIC, GM-1000) was added to the obtained slurry as a binder so that the acrylic resin solid content was 2% by mass with respect to the solid content (silica fine particles). Next, water was added to the slurry so that the concentration of the silica fine particles was 5% by mass, and then the slurry was stirred for 10 minutes at 2000 rpm using a tabletop chores stirrer to prepare an aqueous dispersion of silica fine particles.

(4) Treatment of Supporting Silica Fine Particles of Nonwoven Fabric Composite Sheet While stirring the silica fine particle aqueous dispersion prepared in (3) above, one non-woven fabric composite sheet prepared in (2) above is added to the dispersion. Soaked for 5 minutes. Then, the non-woven fabric-like composite was taken out from the silica fine particle aqueous dispersion and dried at 160 ° C. to support the silica fine particles on the non-woven fabric-like composite sheet.

The content of the silica fine particles supported on the non-woven composite sheet after the silica fine particle supporting treatment was measured by the following two methods, Method 1 and Method 2.
(Method 1)
The mass of the non-woven fabric-like composite sheet produced in (2) above (hereinafter, this mass is referred to as X) and the mass of the non-woven fabric-like composite sheet after the silica fine particle-supporting treatment performed in (4) (hereinafter, this mass is Y). ) And was measured. Then, the content of the silica fine particles was calculated using the following formula.
Content of silica fine particles (mass%) = (YX) ÷ Y × 100

(Method 2)
First, the mass of the nonwoven fabric-like composite sheet after the silica fine particle-supporting treatment was measured (hereinafter, this mass is referred to as A).
Next, the binder in the non-woven composite sheet was removed, and the mass was measured (hereinafter, this mass is referred to as B). To remove the binder, a non-woven fabric sheet is immersed in a methyl ethyl ketone reagent (manufactured by Wako Pure Chemical Industries, Ltd.), which is a solvent for dissolving the binder, for 24 hours, and then the non-woven fabric sheet after immersion is placed on a 100-mesh sieve. It was carried out by a method of placing, washing with a methyl ethyl ketone reagent, and drying.
The non-woven fabric-like composite sheet after removing the binder is immersed in water having a mass about 100 times that of the non-woven fabric-like composite sheet and stirred to obtain a slurry in which silica fine particles, glass fibers and thermoplastic resin fibers are dispersed. Obtained. The slurry was filtered through a 100 mesh sieve and the residue on the sieve was washed with water to remove silica particles. Washing with water was carried out by observing the residue on the sieve under a microscope until no silica particles were confirmed in the residue.
The residue from which the silica particles had been removed was heated at about 105 ° C., dried, cooled and measured by mass (hereinafter, this mass is referred to as C).
Then, the content of the silica fine particles was calculated using the following formula.
Content of silica fine particles (mass%) = (BC) ÷ A × 100 (%)

As a result of measurement by the above two methods, the content of the silica fine particles in the non-woven composite sheet was 6.7% by mass, and the content of the silica fine particles with respect to 100 parts by mass of the glass fiber was 20 in either method. It was a mass part.

(5) Preparation of Fiber Reinforced Thermoplastic Resin Sheet 28 sheets of non-woven fabric-like composite sheet after performing the silica fine particle supporting treatment of (4) above were laminated to obtain a laminated body. This laminate was heat-press molded at 300 ° C. and 10 MPa for 10 minutes using a heat-pressurized press device, then cooled to 70 ° C., and then taken out from the heat-pressurized press device. The obtained fiber-reinforced thermoplastic resin sheet had a length of 25 cm, a width of 25 cm, and a thickness of 1.8 mm.

[Comparative Example 1]
In the preparation of the (1) aqueous fibrous dispersion of Example 1, the amount of glass fiber was set to 60 g, and finally, water was added so that the total amount was 30 kg, and the fiber having a solid content concentration of 0.5% by mass was added. A non-woven composite sheet was prepared in the same manner as in Example 1 except that the aqueous dispersion was prepared. Then, a fiber-reinforced thermoplastic resin sheet was produced in the same manner as in Example 1 except that (4) the silica fine particle supporting treatment of the non-woven composite sheet was not carried out.

The coefficient of thermal expansion in the plane direction and the coefficient of thermal expansion in the thickness direction of the fiber-reinforced thermoplastic resin sheets obtained in Example 1 and Comparative Example 1 were measured.
The coefficient of thermal expansion in the plane direction was measured in a tension mode under the conditions of a heating rate of 5 ° C./min and a measurement temperature range of 30 to 210 ° C. in accordance with JIS K 7197.
The coefficient of thermal expansion in the thickness direction was measured in a compression mode under the conditions of a heating rate of 5 ° C./min and a measurement temperature range of 30 to 210 ° C. in accordance with JIS K 7197.

Table 1 below shows the input amount of each fiber material of the fibrous aqueous dispersion prepared in Example 1 and Comparative Example 1, the composition of the non-woven composite sheet, and the coefficient of thermal expansion of the fiber-reinforced thermoplastic resin sheet.

The fiber-reinforced thermoplastic resin sheet containing glass fibers and silica fine particles (Example 1) is in the thickness direction as compared with the fiber-reinforced thermoplastic resin sheet containing glass fibers but not containing silica fine particles (Comparative Example 1). It can be seen that the thermal expansion coefficient of is significantly reduced.

From the results of the above examples, by using the method for producing a silica fine particle-supporting glass fiber non-woven fabric of the present invention, the glass fibers are oriented in the plane direction, and the silica fine particles are supported on the glass fibers. It was confirmed that non-woven fabric can be manufactured. The fiber-reinforced thermoplastic resin sheet, which is a heat-press molded body of a composite containing the silica fine particle-supporting glass fiber non-woven fabric and the thermoplastic resin, has a significantly reduced thermal expansion in the thickness direction, and is further subjected to a high temperature environment. It was confirmed that it is useful for forming wiring boards, especially laminated wiring boards, because of its high shape stability.

10a, 10b Silica fine particle-supporting glass fiber non-woven fabric 11 Glass fiber 12 Silica fine particle 13 Glass short fiber 14 Heat-resistant resin short fiber 20 Thermoplastic matrix resin layer 21 Thermoplastic matrix resin beads 22 Thermoplastic matrix resin fiber 23 Thermoplastic Matrix resin 30 Fiberglass reinforced thermoplastic resin sheet

Claims (10)

A prepreg containing glass fiber and a thermoplastic matrix resin to obtain a fiber-reinforced thermoplastic resin sheet, the non-woven fabric containing the glass fiber and the fibrous thermoplastic matrix resin , and the average primary particles supported on the non-woven fabric. A prepreg containing silica fine particles having a diameter in the range of 1 to 100 nm, and the content of the silica fine particles is 5 to 50 parts by mass with respect to 100 parts by mass of the glass fiber . The prepreg according to claim 1, wherein a layered thermoplastic matrix resin is further arranged on at least one surface of the non-woven fabric. The prepreg according to claim 1 or 2, wherein the content of the thermoplastic matrix resin with respect to the total amount of the glass fiber, the thermoplastic matrix resin and the silica fine particles is 50 to 90% by mass. The method for producing a prepreg according to any one of claims 1 to 3.
And glass fibers, the steps of providing a nonwoven fabric you containing a thermoplastic matrix resin fibrous, the average primary particle diameter of the silica dispersion silica fine particles are dispersed in a solvent in the range of 1 to 100 nm,
Before SL is contacted with non-woven fabric and the silica dispersion, with respect to 100 parts by weight of the glass fibers, the production method of the prepreg and a step of supporting 5-50 parts by weight of silica fine particles. The glass fibers and an aqueous dispersion containing a thermoplastic matrix resin of the fiber, to produce a pre-Symbol nonwoven fabric by papermaking, method of producing the prepreg according to claim 4. A method for producing a fiber-reinforced thermoplastic resin sheet in which the prepreg according to any one of claims 1 to 3 is heat-press molded. Claim 4 or obtain a prepreg by the production method of the prepreg according to 5, the resulting prepreg method for producing a fiber-reinforced thermoplastic resin sheet for molding heat and pressure. A method for producing a metal-clad laminated sheet, which is heat-press molded with a metal foil laminated on at least one surface of the prepreg according to any one of claims 1 to 3. A method for producing a metal-clad laminated sheet, which is obtained by obtaining a prepreg by the method for producing a prepreg according to claim 4 or 5 , and is heat-pressed molded with a metal foil laminated on at least one surface of the obtained prepreg. A method for manufacturing a wiring board in which a metal-clad laminate is obtained by the method for manufacturing a metal-clad laminate according to claim 8 or 9, and the metal foil of the obtained metal-clad laminate is patterned.

Images