JP2003253558A - Woven fabric or nonwoven fabric and method for producing the same and laminate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electric circuit board having a low dielectric constant and especially useful in the high frequency region without largely changing production steps after prepreg step, compared with a conventional production process and being relatively simply produceable. <P>SOLUTION: The woven fabric or nonwoven fabric is obtained by attaching a porous body to a fiber such as glass fiber. The porous body comprises preferably silicon dioxide. The porous body has 3.5-100 Å pore diameter. The pore volume of the woven fabric or nonwoven fabric is preferably 0.05-1.2 cm<SP>3</SP>/g. The method for producing the woven fabric or the nonwoven fabric comprises feeding alkoxysilanes to a fiber woven fabric or a fiber nonwoven fabric, hydrolyzing and condensing the alkoxysilanes and attaching the resultant porous body onto the fiber. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-woven fabric, a prepreg and a laminated plate thereof used for an electric circuit board. More specifically, the present invention relates to an electric circuit board having a low dielectric constant and excellent solder heat resistance.

[0002]

2. Description of the Related Art Frequencies used in recent fields of electronics industry, telecommunications industry and computers are gradually shifting to high frequency range. However, in the high frequency region, the influence of the circuit performance on the signal speed and the signal loss is large, and therefore, it is required to improve the signal speed and reduce the loss in the high frequency region for the electric components and the electric circuit board to be used. ing.

Generally, the signal speed and loss of a circuit depend on the dielectric constant of the electric circuit board. The lower the dielectric constant, the faster the signal speed and the smaller the loss. Therefore, an electric circuit board used in a high frequency region is required to have a low dielectric constant. As a method of lowering the dielectric constant of an electric circuit board, a method of using a fluororesin, a method of lowering the dielectric constant of a thermosetting resin itself as a matrix resin, a method of using air, etc. have been conventionally devised.

The method using a fluororesin utilizes the fact that the dielectric constant of the fluororesin itself (for example, the dielectric constant of polytetrafluoroethylene is about 2.1) is small, but the adhesiveness and handling are poor. They are problematic and tend to be shunned.

In the method using air, the permittivity of air is close to that of vacuum and is about 1. Therefore, the dielectric constant can be reduced by including air in the laminated plate. For example, in Japanese Unexamined Patent Publication No. 5-198903, hollow particles such as hollow balloons are dispersed as a filler in a matrix resin to reduce the dielectric constant. However, the particle diameter of the hollow balloon is about several tens of μm, and the thickness between layers is 30
The laminated plate having a thickness of about 60 μm has a problem that the hollow balloon is large and if the hollow balloon is damaged, the upper and lower copper foils are easily connected to each other.

As a method of avoiding the problem of vertical conduction, there is a method of reducing the diameter of air. As such a method, for example, JP-A-5-182518 can be cited. Japanese Unexamined Patent Publication (Kokai) No. 5-182518 discloses a technique relating to a laminated plate filled and dispersed in a matrix resin with a porous pigment having a void of a molecular level as a filler, and its purpose is to: Low coefficient of thermal expansion (C
TE), high glass transition temperature (Tg), and low dielectric constant. The air in the porosity of the filler can reduce the dielectric constant of the laminate. In the paragraph "0003" of the description, the present invention relates to a material comprising a polymer matrix composite material having sol-gel derived glassy microspheres having nanoscale porosity and a printed circuit board comprising the same. , The dispersed phase is composed of molecularly porous airgel microspheres. ”As described above, the porous airgel microspheres as a filler are dispersed and contained in the matrix resin, so that a low CTE and a high CTE are obtained. I'm getting Tg.

[0007] That is, in the words of the paragraph "0012" of the specification, "when the CTE of a dielectric material (laminate) reaches a glass transition temperature (Tg), a bending point called a / k / a softening point, When reaching Tg, the coefficient of expansion of the dielectric material increases significantly, so to minimize stress it is necessary to have a Tg well above the temperature that the dielectric material will encounter in the lifetime of the device. Is desirable.
Dielectric materials based on epoxy novolacs, for example, are believed to have a relatively high Tg, typically 150 ° C or higher. Other properties associated with high Tg often include low hygroscopicity and chemical inertness. It should be noted that the presence of fillers in the polymer increases the softening point (Tg) of the polymer. In other words, dimensional stability at higher temperatures (albeit below Tg) is improved in the presence of fillers. Can be explained.

However, this method has two major problems in manufacturing. First, in the method for producing such a porous filler, there is drying under supercritical conditions. In order to perform such drying, a cell capable of withstanding high pressure is required, which is a disadvantageous method for mass production. Two
Second, the specific gravity of the porous filler is too low. According to the specification, the density of the porous filler is about 50-5
It is 00 kg / m ² , and when converted to specific gravity, it is about 0.05 to 0.
It is 5. Generally, the specific gravity of the thermosetting resin, which is a matrix resin coating, is about 0.7 to 1, and the porous airgel microspheres that are the filler in the matrix resin coating float up and are not preferable in manufacturing.

In the paragraph "0041" of the description, "the porous microspheres have a lower density than the resin / solvent mixture so that they usually tend to float. However, the microspheres of the present invention are small in size. Because, they have little buoyancy with respect to the resistance due to the liquid resin, and require minimal agitation when mixing with a rotating paddle stirrer in order to suspend them fully and uniformly. , It can be carried out by ultrasonic agitation using a high-power ultrasonic probe. ", As a minimum, an agitator is required, and a prepreg is prepared by impregnating with a matrix resin paint without a filler. Compared to the case, it is complicated in terms of equipment and manufacturing.

Japanese Unexamined Patent Publication No. 2001-98224 discloses a method in which a condensate film of a siloxane oligomer is made porous by thermally decomposing and removing a sacrificial organic substance to reduce the dielectric constant. This method is not a method using supercritical drying and a filler having a small specific gravity, and therefore, JP-A-5-182.
The problem of Japanese Patent No. 518 does not occur. JP 2001-9
The electronic component disclosed in Japanese Patent No. 8224 is mainly an interlayer insulating film of an LSI, and in addition to this, in the specification, "a multilayer wiring board in the present invention includes a high-density wiring board such as MCM.
By applying the coating film formed from the composition of the present invention as an interlayer insulating film, it is possible to achieve high performance such as reduction of signal propagation delay time and high reliability at the same time as described above. "
Therefore, it can be seen that even in a multilayer wiring board, the porous silica coating is used as an interlayer insulating film to reduce the dielectric constant.

However, in the manufacturing process of a multilayer laminate represented by a glass epoxy laminate, a prepreg impregnated with epoxy on a glass cloth is used as an interlayer insulating film, and the prepreg (interlayer insulating film) and a copper foil are superposed on each other at 180 ° C. A method of forming a multi-layer structure by pressing at a temperature of about 100 ° C. and repeating thermocompression bonding work is employed. When the porous silica film is used as the interlayer insulating film as in JP-A-2001-98224, the porous silica film does not have adhesiveness due to thermocompression bonding, so that in the multilayering step, the copper foil and the other interlayer insulating film are used. It cannot be thermocompression-bonded to the porous silica coating, and some adhesive layer must be provided between the copper foil or the other interlayer insulating film, which not only increases the number of steps but also increases the distance between the upper and lower copper foils. However, there is a problem in that the performance of the low dielectric constant interlayer insulating film cannot be sufficiently exhibited.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electric circuit board which has a low dielectric constant and is easy to manufacture and can be multilayered.

[0013]

In order to solve the above problems, the present invention includes the following inventions. (1) A woven or non-woven fabric characterized in that a porous body is attached to the fibers. (2) The woven or non-woven fabric according to (1) above, wherein the fiber is a glass fiber. (3) A woven or non-woven fabric according to (1) or (2) above, wherein the porous body has an average pore diameter of 3.5 to 100 liters. (4) A woven or non-woven fabric according to any one of (1) to (3) above, wherein the woven or non-woven fabric has a pore volume of 0.05 to 1.2 cm ³ / g. (5) A woven or non-woven fabric according to any of (1) to (4) above, wherein the main component of the porous body is silicon dioxide. (6) A non-woven fabric formed by adhering fibers to each other with a binder by a wet method, wherein the porous body according to any one of (3) to (5) is used as a binder (1 ) To (5). (7) A precursor containing at least one selected from alkoxysilanes and multimers thereof is supplied to a woven or non-woven fiber fabric, and the precursor is hydrolyzed and condensed to deposit a porous body on the fiber. A method for producing a woven or non-woven fabric, which comprises: (8) The method for producing a woven or non-woven fabric according to (7), wherein the precursor contains a sacrificial organic substance, and the sacrificial organic substance is removed to form the porous body. (9) The method for producing a woven or non-woven fabric according to (8), wherein the sacrificial organic matter is removed by thermal decomposition at 200 to 600 ° C. (10) A prepreg obtained by impregnating a woven or non-woven fabric having the porous body described in (1) to (9) attached to fibers with a thermosetting resin, and a laminate thereof. (11) A laminated board in which one or more prepregs according to (10) above are used in at least a part of the laminated board.

[0014]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, as a result of extensive studies, a laminate using a prepreg obtained by impregnating a woven or non-woven fabric having a porous body on the surface of a fiber with a thermosetting resin is used as an electric circuit board. By doing so, the above-mentioned problems were solved. The principle of reducing the permittivity by including air in the laminate is that the permittivity (ε _r ) 1 of the lowest vacuum is almost the same as air. General glass epoxy (FR-
4) The permittivity (ε _r ) of the laminated plate is about 4.2, and the permittivity of the entire laminated plate can be reduced by including air.

In the present invention, a woven or non-woven fabric having a porous material attached to fibers is impregnated with a thermosetting resin in the same manner as in the conventional method to prepare a prepreg, and the prepreg and the copper foil are heated. A laminated board can be manufactured by pressure-bonding and laminating with a press. The porous body attached to the fiber of the present invention needs to have continuous micropores on the molecular scale (the pores are not individually independent). The molecular scale means a size of about one molecule to several tens of tens, and as a specific numerical value, its average pore diameter is preferably 3.5 to 100Å, more preferably 5 to 50Å. preferable. If it is less than 3.5 Å, the effect may not be fully manifested, although the reason is unclear. If it is larger than 100Å, it becomes easy to absorb water. The reason for this is not clear, but it is considered that when the average pore diameter is 100 Å or less, when water enters the pores, it is difficult to replace the air already in the pores. This means that a laminated plate made of a woven or non-woven fabric of fibers attached with a porous body having an average pore size of more than 100Å easily absorbs moisture in the air and is passed through a reflow furnace in the soldering process. This causes a problem that the laminated plate is likely to cause blistering.

As a method for evaluating such solderability, the produced laminated plate is immersed in boiling water for several hours, and then,
There is a method of immersing in a solder bath at about 260 ° C. and inspecting the laminate for blistering (solder heat resistance). When the pore size of the porous body exceeds 100Å, it becomes easy to absorb water, and the water that has entered the porous body is rapidly vaporized by being immersed in the solder bath. As a result, the laminated plate burns. If unevenness such as a burr or the degree is not good, a rupture will occur.

The pore volume of the woven or non-woven fabric of the present invention is
It is preferably 0.05~1.2cm ³ / g, more preferably 0.09~1cm ³ / g. Pore volume is 0.0
If it is less than 5 cm ³ / g, air will not be sufficiently contained in the laminate, and the decrease in the dielectric constant tends to be insufficient. 1.2 cm ³ /
When it is larger than g, the strength of the porous body is weak and the woven or non-woven fabric is likely to collapse when impregnated with a thermosetting resin coating material or when pressure-bonded by a hot press. The average pore diameter in the present invention means an average pore diameter measured by N ₂ BET method, a pore volume is the pore volume as measured by N ₂ BET method. As a specific measuring device by the N ₂ -BET method,
For example, AUTOSORB-1-MP manufactured by Quantachrome can be used.

The main component of the porous material of the present invention is an inorganic oxide such as silicon dioxide, aluminum oxide (Al ₂ O ₃ ),
Inorganic oxides such as titanium dioxide and zirconium dioxide may be used alone or in combination. Particularly preferred is silicon dioxide. When the inorganic oxide is not contained as the main component, in other words, when the organic component is large, the water absorption of the porous body becomes too large, and the solder heat resistance is likely to deteriorate. The inorganic oxide content is preferably 60 to 100% by mass, more preferably 80 to 100% by mass.

As the organic component, for example, polycarbonates, polyethers, polyvinyl esters, polyvinyl alcohols, homopolymers of polymethacrylic acid and / or polyacrylic acid esters or their copolymers, polyanhydrides, etc. Can be mentioned. Of these, particularly preferred are polyethylene glycol, polypropylene glycol, polycaprolactone,
Polycaprolactone triol, polyethene carbonate, polypentamethylene carbonate, polyhexamethylene carbonate, polyadipoyl oxide, polyazeoyl oxide, polysebacyl oxide, tetramethylene oxide, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, poly Examples thereof include known organic polymers and oligomers such as methyl acrylate and polyethyleneimine.

The organic component referred to here also includes an organic group bonded to an inorganic oxide. What is an organic group?
Examples thereof include hydrocarbon groups such as alkyl groups (methyl group, ethyl group, propyl group, etc.), allyl groups (phenyl group, etc.). Furthermore, amino groups, halogen groups, epoxy groups, urethane groups, isocyanate groups,
Mercapto group, sulfide group, vinyl group, acrylo group,
It may be an organic functional group to which a functional group such as an acryloxy group or a methacryloxy group is bonded, or an organic group other than these.

The inorganic oxide in the present invention is prepared by hydrolyzing the precursor.
It is formed by decondensation and condensation. As a precursor of silicon dioxide
Select from alkoxysilane and alkoxysilane multimers
At least one species, a mixture of these
Is also good. As the alkoxysilane, for example, Si-
(OR)_Four, R-Si- (OR) ₃, R₂-Si- (O
R), R₃-Si-OR etc. are mentioned. In addition, the above
In the formula, R represents an organic group, and all must be the same organic group.
There is no. Examples of the organic group include the same groups as described above.
It Alkoxysilane multimers are
A multimer composed of a plurality of xysilanes bonded by Si-O-Si
(Dimer or more). Of course there is alkoxysilane
Or a known metal alkoxide for alkoxysilane multimers.
Can be added.

Known gold as a precursor other than silicon dioxide
Mention may be made of genus alkoxides. Metal like this
Alkoxide is, for example, aluminum alkoxide
(R _nAl (OR)_3-n), Titanium alkoxide (R
_mTi (OR)_4-m), Zirconium alkoxide (R_m
Zr (OR)_4-m) And the like. Of course these
It is not limited to. In the above formula, R is
Represents similar organic groups and need not all be the same organic group.
Yes. In addition, n represents an integer of 0 to 3 and m represents an integer of 0 to 4.
You

An example of the porous body producing method of the present invention is as follows. That is, a silicon dioxide precursor or its hydrolyzate and a sacrificial organic substance are blended in a solvent to prepare a coating material, and the coating material (hereinafter, also referred to as a porous material coating material) is prepared by sufficiently hydrolyzing the precursor and then using a solvent. Are vaporized off and sufficient heat is applied to condense the precursor hydrolyzate to form a silicon dioxide / sacrificial organic mixture. Then, the sacrificial organic substance is removed to form a porous body of silicon dioxide.

The sacrificial organic matter removing method of the present invention may include thermal decomposition, plasma decomposition, dissolution extraction with a good solvent, and the like, and thermal decomposition at a temperature of 200 to 600 ° C. is particularly preferable.

The sacrificial organic material of the present invention is 200 to 6
There is no particular limitation as long as it is an organic polymer (including oligomer) that is decomposed by 85% by mass or more at 00 ° C. For example, but not limited to, polycarbonates, polyethers, polyvinyl esters, polyvinyl alcohols, polymethacrylic acid and / or polyacrylic acid esters homopolymers or copolymers, polyanhydrides, etc. Can be mentioned. Of these, particularly preferred are polyethylene glycol, polypropylene glycol, polycaprolactone, polycaprolactone triol, polyethene carbonate, polypentamethylene carbonate, polyhexamethylene carbonate, polyadipoyl oxide, polyazeoyl oxide, polysebacyl oxide. , Tetramethylene oxide, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polymethyl acrylate, polyethyleneimine and the like are preferable.

The fibers of the woven or non-woven fabric of the present invention are preferably heat resistant organic fibers, inorganic fibers and the like. Examples of the heat-resistant organic fiber include, but are not limited to, meta-aramid fiber, para-aramid fiber, wholly aromatic polyester fiber, polybenzazole fiber, polyimide fiber, polyamideimide fiber, melamine fiber, phenol fiber, and polyphenylene sulfite. Examples of the inorganic fibers include fibers, polyketone fibers, polyetheretherketone fibers, fluorine fibers, and the like, and glass fibers, alumina fibers, and the like, and two or more kinds may be mixed and mixed. In the present invention, glass fiber is more preferable because it is inexpensive. As the glass fiber, E glass fiber, D glass fiber, S
Glass fiber, NE glass fiber, C glass fiber, quartz glass fiber,
Examples thereof include high silicate glass fiber. Of course, it is not limited to these. The shape is not particularly limited whether the fiber cross section is a circle or other shapes (for example, an ellipse, a flat shape, a star shape, etc.), and any form such as chopped fiber, pulp, and fibrid can be used. I do not care. A plurality of types of fibers may be mixed and made. Also,
A cross-sectional area, 1μm ² ~500μm ² about the well, is impaired it larger than woven or suppleness of the nonwoven fabric. In the nonwoven fabric of the present invention, the fiber length is 1 to on average.
It is preferably about 50 mm. Below 1 mm,
When a non-woven fabric is produced by a wet method, retention of fibers due to wire making tends to be poor, and when it is larger than 50 mm, the texture of the non-woven fabric tends to be poor. The glass fiber of the present invention is preferably E glass fiber, D glass fiber, NE glass fiber, quartz fiber fiber or high silicic acid fiber fiber in view of characteristics when used as an electric circuit board.

The method for producing the woven fabric of the present invention can be produced by a known loom. The nonwoven fabric of the present invention is preferably produced by a wet method (paper making method). When produced by a wet method, fibers are preferably bonded to each other with a binder to form a nonwoven fabric.

As the binder of the nonwoven fabric of the present invention,
In addition to known organic binders such as acrylic resin, polyimide resin, urethane resin, polyvinyl alcohol, and epoxy, a porous coating material can be used as the binder. The method of supplying these binders to the fiber is
Examples include known coating methods such as impregnation method, spray method, Mayer bar method, gravure method, microgravure method, die method, blade method, microrod method, air knife method, curtain method, slide method, and roll method. it can. Of course, if it is publicly known, it is not limited to these examples. Further, known thermoplastic fibers such as meta-aramid fiber, liquid crystal polymer fiber, thermoplastic polyimide fiber, polypropylene fiber, polyethylene terephthalate fiber and polystyrene fiber, and wood pulp such as KP, GP and TMP may be used as a binder in advance. It is also possible to mix it with heat resistant fibers such as liquid crystal polymer fibers and inorganic fibers for papermaking.

In the present invention, the method for attaching the porous coating material to the woven or non-woven fabric includes, for example, impregnation method, spray method, Meyer bar method, gravure method, microgravure method, die method, blade method, microrod method, Known coating methods such as an air knife method, a curtain method, a slide method and a roll method can be mentioned. Of course, if it is publicly known, it is not limited to these examples. Further, when the porous coating material is already used as the binder for the wet method, this step may be omitted or may be performed again.

As described above, the porous coating material is composed of the silicon dioxide precursor or its hydrolyzate, the sacrificial organic substance, and the solvent, but an auxiliary additive may be added if necessary. Examples of the auxiliary additives include known catalysts for smoothly performing hydrolysis / condensation in addition to water for hydrolysis / condensation of the silicon dioxide precursor. Examples thereof include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, acetic acid, ammonia, sodium hydroxide, potassium hydroxide, triethylamine, triethanolamine, pyridine and the like.

As the solvent, in addition to water, alcohol solvents (for example, monohydric alcohols having about 1 to 6 carbon atoms such as methanol, ethanol and isopropyl alcohol, divalent alcohols having about 1 to 6 carbon atoms, Trihydric alcohols such as glycerin, fluorine-containing alcohols, etc., acetate ester solvents (eg methyl acetate, ethyl acetate etc.), lactones (eg γ-butyl lactone etc.), glycol acetate solvents (eg ethylene glycol monomethyl acetate). , Ethylene glycol diacetate, etc.),
Glycol ether solvent, amide solvent (for example, N
-Methyl-2-pyrrolidone, N, N-dimethylformamide and the like), ketone-based solvents (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and the like can be mentioned. Of course, it is not limited to these.

In the present invention, a prepreg is prepared by impregnating a known thermosetting resin with the woven or non-woven fabric with a porous body prepared as described above. The prepreg and the copper foil are superposed on each other, a laminated board is produced by a hot press machine, and this step is repeated (multilayering step) to produce a multilayer laminated board. According to this method, a laminate having a low dielectric constant can be obtained by using almost the same steps as those of the conventional glass epoxy multilayer laminate. On the other hand, when a porous body containing silicon dioxide as a main component is used as an interlayer insulating film, the copper foil and / or the interlayer insulating films are laminated to each other by applying an adhesive to the porous body containing silicon dioxide as a main component. Since there is no property, use of an adhesive or the like is indispensable, and an extra step of providing the adhesive is necessary, and the superiority of the present invention is obvious.

The thermosetting resin to be impregnated is not particularly limited in the present invention as long as it is a known thermosetting resin.
For example, epoxy resin, phenol resin, polyimide resin, cyanate resin, thermosetting polyphenylene oxide resin, etc. are preferably used.

The laminated plate of the present invention can be used in one or more pieces in at least a part of the laminated plate. That is, the multilayer laminate of the present invention can be multilayered not only when using the same prepreg but also with prepregs or plates having different dielectric constants and / or core materials depending on the purpose. For example, a prepreg or a plate using a conventional woven fabric or non-woven fabric to which a porous body is not attached, a woven fabric or a non-woven fabric attached to a porous body, which is thermosetting Examples include prepregs or plates of different resins, polyimide films, fluororesin films, polymer liquid crystal films, ceramics and the like.

Further, the electric circuit board can be formed with all or only a part corresponding to a high frequency signal according to the purpose. That is, it can be dealt with by using at least one prepreg of the present invention for at least a part of a laminated board which is an electric circuit board. The laminated board of the present invention can be used without limitation in any known method for the method of punching, etching, multilayering, etc. for producing an electric circuit board.

[0036]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples. In the examples, "%" and "parts" all indicate "mass%" and "parts by mass" unless otherwise specified. In addition, (brand name, company name) is described inside the parentheses after the compound name.

<Example 1> E glass fiber chop (manufactured by Nippon Electric Glass Co., Ltd., fiber diameter φ9 μm, fiber length 13 m)
m) was dispersed in water, and wet-paper-making was carried out by a square hand-making machine using a plastic wire having a wire mesh number of 80 mesh to prepare a dried sheet of fibers having a basis weight of 27 g / m ² . Paint A is applied to this fiber-only sheet by spraying, dried at 120 ° C. for 10 minutes to volatilize the solvent, and further left at 250 ° C. in a nitrogen atmosphere for 30 minutes,
The condensation of the paint A was promoted to obtain a paint-coated sheet having a weight of 50 g / m ² . This paint-coated sheet was put in an electric furnace in a nitrogen atmosphere at 450 ° C. for 30 minutes to thermally decompose and remove the sacrificial organic substances in the paint A to obtain a sheet. The average pore diameter and the pore volume of this sheet were measured with N ₂ by using AUTOSORB-1-MP manufactured by Quantachrome.
-Measured by the BET method. The results are shown in Table 1.

Paint A : Tetraalkoxylane (KBE0
4, manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts, polyethylene glycol average molecular weight 50000 as a sacrificial organic substance (Wako Pure Chemical Industries Catalog 168-12221) 17 parts, water 100 parts,
10 parts of 1N acetic acid and 100 parts of isopropyl alcohol were mixed, and the mixture was heated and stirred at 80 ° C. for 30 minutes in a reactor equipped with a reflux tube to obtain a paint A.

Example 2 E glass fiber chop (manufactured by Nippon Electric Glass Co., Ltd., fiber diameter φ9 μm, fiber length 13 m)
m) was dispersed in water, and wet-paper-making was carried out by a square hand-making machine using a plastic wire having a wire mesh number of 80 mesh to prepare a dried sheet of fibers having a basis weight of 27 g / m ² . The paint B is applied to this fiber-only sheet by spraying, dried at 120 ° C. for 10 minutes to volatilize the solvent, and further left at 250 ° C. in a nitrogen atmosphere for 30 minutes
The condensation of paint B was promoted to obtain a sheet with paint having a weight of 80 g / m ² . This paint-coated sheet was put in an electric furnace in a nitrogen atmosphere at 320 ° C. for 2 hours to thermally decompose and remove the sacrificial organic substances in the paint A to obtain a sheet. The average pore diameter and the pore volume of this sheet were measured with N ₂ by using AUTOSORB-1-MP manufactured by Quantachrome.
-Measured by the BET method. The results are shown in Table 1.

Paint B : Ethyl silicate as an alkoxysilane (ethyl silicate 40, manufactured by Colcoat) 5
0 parts, phenyltrimethoxysilane (KBM-103,
A total of 100 parts of alkoxysilane consisting of 40 parts of Shin-Etsu Chemical Co., Ltd. and 10 parts of dibenzyldimethoxysilane (KBM202SS, Shin-Etsu Chemical Co., Ltd.) and 65 parts of polyvinyl call (GL-05, Nippon Synthetic Chemical Co., Ltd.) as sacrificial organic substances
Normal hydrochloric acid 5 parts, water 50 parts, isopropyl alcohol 50
The parts were mixed, and the mixture was heated and stirred at 80 ° C. for 30 minutes in a reactor equipped with a reflux tube to obtain a coating material B.

Example 3 The same operation as in Example 1 was carried out except that the coating material C was used instead of the coating material A and the thermal decomposition treatment of the sacrificial organic material was carried out at 600 ° C. for 30 minutes. The results are shown in Table 1. Paint C : Tetraalkoxysilane oligomer (EMS-
(485, manufactured by Colcoat Co., Ltd.) 100 parts of water, 50 parts of water, 10 parts of 1N acetic acid, and 80 parts of γ-butyl lactone are mixed, and the mixture is heated and stirred at 80 ° C. for 60 minutes in a reactor equipped with a reflux tube. Polymethylmethacrylate 20 as sacrificial organic matter
(Wako Pure Chemical Industries Catalog 138-02735)
A total of 70 parts of a liquid dissolved in 100 parts of butyl lactone was added and mixed to prepare a coating material C.

Example 4 E glass fiber chop (manufactured by Nippon Electric Glass Co., Ltd., fiber diameter φ9 μm, fiber length 13 m)
m) was dispersed in water, and wet-paper-making was carried out by a square hand-making machine using a plastic wire having a wire mesh number of 80 mesh to prepare a dried sheet of fibers having a basis weight of 27 g / m ² . Acrylic emulsion (EK-72, manufactured by Saiden Chemical Co., Ltd.) 10 parts, water 400 parts, N-β-aminoethyl-γ-aminopropylmethoxysilane (KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 was added to a sheet of this fiber only.
Parts by stirring and mixing at room temperature for 1 hour, and apply by spraying so that the amount of the dried sheet increases by 1%, and the temperature is 105 ° C.
It was dried for 10 minutes. Paint D is applied to this sheet by spraying, dried at 120 ° C. for 10 minutes to volatilize the solvent, and further left for 60 minutes at 180 ° C. in a nitrogen atmosphere to promote the condensation of paint D to obtain 60 g / m ^{2 of} tsubo. To obtain a sheet with paint. This paint-coated sheet was put in a dryer at 250 ° C. in a nitrogen atmosphere for 5 hours to thermally decompose and remove the sacrificial organic substances in the paint D.
Got the sheet. The results of the average pore diameter and pore volume of this sheet are shown in Table 1.

Paint D : 40 parts of ethyl silicate (ethyl silicate 40, manufactured by Colcoat), N-β-aminoethyl-γ-aminopropylmethoxysilane (KBM60
3, 100 parts of alkoxysilane consisting of 60 parts of Shin-Etsu Chemical Co., Ltd., polyvinyl alcohol (G
L-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 80 parts, 1N hydrochloric acid 5
Parts, 100 parts of water, and 80 parts of isopropyl alcohol were mixed, and the mixture was heated and stirred at 80 ° C. for 30 minutes in a reactor equipped with a reflux tube to obtain a coating material D.

Comparative Example 1 The same operation as in Example 1 was carried out except that the sacrificial organic substance was not thermally decomposed at 450 ° C. The results are shown in Table 1.

Comparative Example 2 The same treatment as in Example 1 was carried out except that the coating material E was used instead of the coating material A. The results are shown in Table 1. Paint E : 100 parts of ethyl silicate (ethyl silicate 40, manufactured by Colcoat), 5 parts of 1N hydrochloric acid, 100 parts of water
Parts and 50 parts of isopropyl alcohol are mixed, and the mixture is heated and stirred at 80 ° C. for 30 minutes in a reactor equipped with a reflux tube, and paint E is added.
And

Comparative Example 3 The same process as in Example 4 was carried out except that the coating material F was used. The results are shown in Table 1. Paint F : 40 parts of ethyl silicate (ethyl silicate 40, manufactured by Colcoat), 60 parts of N-β-aminoethyl-γ-aminopropylmethoxysilane (KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.), and 1 part in 100 parts in total of alkoxysilane.
Normal hydrochloric acid 5 parts, water 100 parts, isopropyl alcohol 5
0 parts were mixed, and the resulting mixture was heated and stirred at 80 ° C. for 30 minutes in a reactor equipped with a reflux tube to give a coating material E.

[0047]

[Table 1]

<Example 5> N-β-aminoethyl-γ-
1 part of aminopropylmethoxysilane (KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts of water and mixed for 1 hour at room temperature. The liquid prepared by spraying the sheet prepared in Example 1 had a sheet weight of 0.1. Apply to increase the amount by 10% and
It was dried at 5 ° C. for 10 minutes. Epoxy resin (Epicoat E5048, made by Yuka Shell Epoxy Co., Ltd.) 100 on this sheet
And 0.15 parts of phenylimidazole were impregnated with a thermosetting resin coating material prepared by dissolving 60 parts of methyl ethyl ketone to obtain a prepreg having a thermosetting resin content of 42%. This prepreg 8
The sheets were stacked, a copper foil having a thickness of 50 μm was placed on both sides thereof, and a laminated plate was produced under the conditions of 180 ° C. for 1 hour and 40 kgf / cm ² with a vacuum heat press machine. The thermosetting resin amount of the produced laminated board was 39%.

The dielectric constant and dielectric loss tangent of this laminated plate at 1 GHz were measured by a vector measurement system MS4623B (manufactured by Anritsu). The results are shown in Table 2. Also, only half of the copper foil on both sides of the 5 cm square sample of this laminated plate (same position on both sides) was removed by etching and further washed with water.
A solder heat resistance test sample was prepared by drying for 1 hour in a dryer at ℃. This sample was left for 1 hour under steam at 121 ° C. under 2 atm (PCT treatment), and then immersed in a solder bath at 260 ° C. for 20 seconds to perform a solder heat resistance test. After the solder heat resistance test, the appearance of the sample was visually checked for abnormalities such as swelling.

<Example 6> The same operation as in Example 5 was carried out except that the sheet prepared in Example 2 was used to obtain a laminate having a thermosetting resin content of 30%. The results of the dielectric properties and solder heat resistance of this laminate are shown in Table 2.

<Example 7> The same operation as in Example 5 was carried out except that the sheet prepared in Example 3 was used to obtain a laminate having a thermosetting resin content of 41%. The results of the dielectric properties and solder heat resistance of this laminate are shown in Table 2.

Example 8 A thermosetting resin coating prepared by dissolving 100 parts of an epoxy resin (Epicoat E5048, manufactured by Yuka Shell Epoxy Co., Ltd.) in the sheet prepared in Example 4 in 0.15 parts of phenylimidazole in 60 parts of methyl ethyl ketone. Was impregnated into a prepreg having a thermosetting resin content of 42%. 8 pieces of this prepreg are piled up and the thickness is 50μm on both sides.
Place the copper foil of No.4 and use a vacuum heat press machine at 180 ℃ for 1 hour 4
A laminate was prepared under the condition of 0 kgf / cm ² to obtain a laminate having a thermosetting resin content of 36%. The results of the dielectric properties and solder heat resistance of this laminate are shown in Table 2.

<Comparative Example 4> The same operation as in Example 5 was carried out except that the sheet prepared in Comparative Example 1 was used to obtain a laminate having a thermosetting resin content of 39%. The results of the dielectric properties and solder heat resistance of this laminate are shown in Table 2.

<Comparative Example 5> The same operation as in Example 5 was carried out except that the sheet prepared in Comparative Example 2 was used to obtain a laminate having a thermosetting resin content of 39%. The results of the dielectric properties and solder heat resistance of this laminate are shown in Table 2.

Comparative Example 6 The same operation as in Example 8 was carried out except that the sheet prepared in Comparative Example 3 was used to obtain a laminate having a thermosetting resin content of 39%. The results of the dielectric properties and solder heat resistance of this laminate are shown in Table 2.

<Example 9> As a thermosetting resin, a thermosetting resin coating composition prepared by dissolving 100 parts of a polyimide resin (BANI-M, manufactured by Maruzen Petrochemical Co., Ltd.) in 60 parts of methyl ethyl ketone instead of an epoxy resin was used. The same operation as in Example 8 was carried out except that the prepreg was prepared by impregnating the sheet prepared in 1. to obtain a laminate having a thermosetting resin content of 39%.
The results are shown in Table 2.

Comparative Example 7 As a thermosetting resin, a thermosetting resin coating prepared by dissolving 100 parts of a polyimide resin (BANI-M, manufactured by Maruzen Petrochemical Co., Ltd.) in 60 parts of methyl ethyl ketone instead of the epoxy resin was used. The same operation as in Comparative Example 6 was carried out except that the prepreg was prepared by impregnating the sheet prepared in 1. to obtain a laminate having a thermosetting resin content of 39%.
The results are shown in Table 2.

[0058]

[Table 2]

[0059]

According to the present invention, an electric circuit which is relatively simple to manufacture, has a low dielectric constant, and is useful especially in a high frequency region without largely changing the manufacturing process after the prepreg as compared with the conventional one. It is possible to provide a substrate, which is extremely useful industrially.

Continued front page    F-term (reference) 4F100 AA20A AA20B AG00A AG00B                       AK01A AK01B AK52A AK52B                       BA14 DG12A DG12B DG15A                       DG15B DH01A DH01B DJ00A                       DJ00B EJ42A EJ42B EJ81A                       EJ81B GB43 JA20A JA20B                       JB13A JB13B JG05 JJ03                       YY00A YY00B                 4L031 AA26 AB32 AB34 BA20 CA08                       DA21                 4L033 AA09 AB05 AB07 AC11 AC15                       BA96

Claims (11)

[Claims] 1. A woven or non-woven fabric, characterized in that a porous material is attached to the fibers. 2. The woven or non-woven fabric according to claim 1, wherein the fiber is a glass fiber. 3. The average pore size of the porous body is 3.5 to 1.
It is 00Å, It is characterized by the above-mentioned.
The woven or non-woven fabric according to. 4. The pore volume of the woven or non-woven fabric is 0.
05-1.2 cm ³ / g, characterized in that
The woven or non-woven fabric according to claim 3. 5. The woven or non-woven fabric according to any one of claims 1 to 4, wherein the main component of the porous body is silicon dioxide. 6. A non-woven fabric formed by adhering fibers to each other with a binder by a wet method, wherein the porous body according to any one of claims 3 to 5 is used as a binder. The non-woven fabric according to any one of claims 1 to 5. 7. A woven or non-woven fiber fabric is supplied with a precursor containing at least one selected from alkoxysilanes and multimers thereof, and the precursor is hydrolyzed and condensed to form a porous body on the fiber. Characterized by attaching
Method for manufacturing woven or non-woven fabric. 8. The method for producing a woven or non-woven fabric according to claim 7, wherein the precursor contains a sacrificial organic substance, and the sacrificial organic substance is removed to form the porous body. 9. The removal of the sacrificial organic material from 200 to 600.
The method for producing a woven fabric or a non-woven fabric according to claim 8, which is performed by thermal decomposition at ℃. 10. A prepreg obtained by impregnating a woven or non-woven fabric having the porous body according to claim 1 attached to a fiber with a thermosetting resin, and a laminate thereof. 11. A laminated board using at least one prepreg according to claim 10 in at least a part of the laminated board.