JP7320697B2 - Surface-treated glass cloth and prepreg - Google Patents

Description

TECHNICAL FIELD The present invention relates to a surface- treated glass cloth and a prepreg using the surface-treated glass cloth.

BACKGROUND ART Conventionally, surface-treated glass cloth used for prepregs constituting printed wiring boards is known. Further, as glass fibers constituting the surface-treated glass cloth, those having a composition containing 15% by mass or more of B ₂ O ₃ are known (see, for example, Patent Documents 1 and 2).

Japanese Patent No. 4269194 Japanese Patent No. 6468409

However, the present inventors have found that a glass cloth woven using glass fibers having a B ₂ O ₃ content of 15% by mass or more is surface-treated with a silane coupling agent having a methacrylic group. It has been found that when the surface-treated glass cloth is used as a prepreg, interfacial peeling occurs at the interface between the glass and the resin, resulting in a decrease in insulation reliability.

An object of the present invention is to provide a surface -treated glass cloth and a prepreg using the surface-treated glass cloth that can eliminate such inconveniences and improve insulation reliability when made into a prepreg. do.

In order to achieve such an object, the present inventors conducted extensive studies and found that when the surface is treated with a silane coupling agent having a methacrylic group, the interface between the glass and the resin does not delaminate by not containing a surfactant. can be suppressed.

A surfactant is generally used to uniformly disperse the silane coupling agent in the surface treatment agent, thereby forming a uniform surface treatment layer on the surface of the glass cloth. By forming a uniform surface treatment layer, peeling at the interface between the glass and the resin is suppressed. Therefore, it is common to add a surfactant to the surface treatment agent for the glass cloth. Surprisingly, however, the present inventors have found that the surface treatment layer of a glass cloth that satisfies certain requirements and is composed of glass fibers having a B ₂ O ₃ content of 15% by mass or more contains methacrylic groups. The present inventors have discovered the previously unpredictable fact that interfacial peeling between the glass and the resin can be suppressed only when a silane coupling agent containing a surfactant is used.

The surface-treated glass cloth of the present invention is a surface-treated glass cloth having a surface-treated layer on its surface, and the glass constituting the glass cloth contains 52.0 to 60.0% by mass of SiO ₂ , B ₂ O ₃ in the range of 15.0 to 26.0% by weight, Al ₂ O ₃ in the range of 9.0 to 18.0% by weight, and 1.0 to 8.0% by weight. of MgO, CaO in the range of 1.0 to 10.0% by mass, SrO in the range of 0 to 6.0% by mass, and TiO ₂ in the range of 0 to 6.0% by mass, for a total of 0. A composition comprising F ₂ and Cl ₂ in the range of 1 to 3.0% by weight;
The glass cloth has a surface coverage in the range of 75.0 to 98.5% and a thickness in the range of 8 to 95 μm, and the surface treatment layer contains a silane coupling agent having a methacrylic group, It does not contain a surfactant, and the surface coverage is 100 x (25000 (μm) x warp width (μm) x warp weave density (thread/25 mm) + 25000 (μm) x weft width ( μm)×weft weaving density (number/25 mm)−warp yarn width (μm)×warp weaving density (number/25 mm)×weft yarn width (μm)×weft weaving density (number/25 mm))/ (25000 (μm)×25000 (μm)) , and the resin with which the surface-treated glass cloth is impregnated is a polyphenylene ether resin or a modified polyphenylene ether resin .

The surface-treated glass cloth of the present invention has a composition in which the glass constituting the glass cloth contains 15% by mass or more of B ₂ O ₃ , specifically, 52.0 to 60.0% by mass of the total amount. SiO ₂ in the range of 15.0-26.0 wt.% B ₂ O ₃ in the range of 9.0-18.0 wt.% Al ₂ O ₃ in the range of 9.0-18.0 wt. % in the range of MgO, CaO in the range of 1.0-10.0 _wt . and the surface treatment layer contains a silane coupling agent having _{a methacrylic} group and does not contain a surfactant. As a result, interfacial peeling that occurs at the interface between the glass and the resin can be suppressed when the prepreg is formed, and the insulation reliability can be improved.

When the surface- treated glass cloth contains a silane coupling agent other than a silane coupling agent having a methacrylic group, the surface-treated glass cloth has the effect of suppressing interfacial peeling due to the fact that it does not contain a surfactant. can't get

In the surface-treated glass cloth of the present invention, it is preferable that silica fine particles adhere to the surfaces of the glass filaments constituting the glass cloth. In the surface-treated glass cloth of the present invention, silica fine particles are attached to the surface of the glass filaments constituting the glass cloth, so that even when the surface-treated layer contains a surfactant, Interfacial peeling that occurs at the interface with the resin can be suppressed, and the surface treatment layer does not contain a surfactant, so that insulation reliability can be further improved.

Moreover, in the surface-treated glass cloth of the present invention, the glass cloth preferably has a surface coverage in the range of 85.5 to 98.5 %. The surface-treated glass cloth of the present invention has a surface coverage in the range of 85.5 to 98.5 %, so that even when the surface-treated layer contains a surfactant, Interfacial peeling that occurs at the interface between the glass and the resin can be suppressed, and the surface treatment layer does not contain a surfactant, so that insulation reliability can be further improved.

The surface coverage can be calculated by the following formula.
Surface coverage = 100 x (25000 (μm) x width of warp (μm) x weaving density of warp (thread/25mm) + 25000 (μm) x width of weft (μm) x weaving density of weft (thread/25mm) )-warp thread width (μm)×warp weave density (threads/25 mm)×weft thread width (μm)×weft thread density (threads/25 mm))/(25000 (μm)×25000 (μm))

Here, the yarn width of the warp and weft is determined by cutting out three samples of 60 mm × 100 mm from the surface- treated glass cloth, and measuring 30 warps or wefts for each sample with a microscope (manufactured by Keyence Corporation, product name: VHX-2000, magnification: 200 times), the average value of the measured values can be adopted. In addition, the weave density of the warp and weft can be obtained by counting the number of warp (weft) yarns in a range of 25 mm in the warp (weft) direction using a fabric disassembling mirror in accordance with JIS R 3420. .

Further, in the surface-treated glass cloth of the present invention, when the glass cloth has a surface coverage in the range of 85.5 to 98.5 %, the glass cloth has a thickness in the range of 8 to 60 μm. more preferably with a thickness in the range of 8-40 μm. In the surface-treated glass cloth of the present invention, when the glass cloth has a surface coverage in the range of 85.5 to 98.5 %, the glass cloth has a surface coverage of 8 to 60 μm, more preferably 8 to 40 μm. By providing the thickness of , the effect of improving the insulation reliability due to the fact that the surface treatment layer does not contain a surfactant can be further enhanced.

Further, in the surface-treated glass cloth of the present invention, the composition of the glass constituting the glass cloth is, for example, SiO ₂ in the range of 52.0 to 60.0% by mass and 15.0% by mass. B ₂ O ₃ in the range of 20.0% by mass or more, Al ₂ O ₃ in the range of 9.0 to 18.0% by mass, MgO in the range of 1.0 to 6.0% by mass, and 1 CaO in the range of 0 to 9.0 wt%, SrO in the range of 0 to less than 0.5 wt%, and _TiO in the range of 1.0 to 6.0 wt%, in total 0 A first embodiment comprising F ₂ and Cl ₂ in the range of .1 to 2.5% by weight, or SiO ₂ in the range of 52.0 to 60.0% by weight, based on the total amount, and 20.0 to B ₂ O ₃ in the range of less than 26.0 wt %, Al ₂ O ₃ in the range of 9.0 to 18.0 wt %, MgO in the range of 1.0 to 6.0 wt %,1. CaO in the range from 0 to 9.0 wt%, SrO in the range from 0.5 to less than 6.0 wt%, and TiO ₂ in the range from 0 to 6.0 wt%, for a total of 0.1 to 2 A second embodiment comprising F ₂ and Cl ₂ in the range of 0.5% by weight is preferred.

The surface-treated glass cloth of the present invention can obtain a higher tensile strength when the composition of the glass constituting the glass cloth is in the first aspect than in the second aspect. Further, the surface-treated glass cloth of the present invention, when the composition of the glass constituting the glass cloth is in the second aspect, exhibits insulation reliability due to the fact that the surface-treated layer does not contain a surfactant. The improved effect can be made greater than when the composition of the glass constituting the glass cloth is in the first aspect.

A prepreg of the present invention is characterized by including the surface-treated glass cloth of the present invention.

The top view which shows the shape of the test piece used for an alkali whitening test.

Embodiments of the present invention will now be described in more detail with reference to the accompanying drawings.

The surface-treated glass cloth of the present embodiment has a surface-treated layer on the surface, and the glass constituting the glass cloth contains SiO ₂ in a range of 52.0 to 60.0% by mass with respect to the total amount; B ₂ O ₃ in the range of 0 to 26.0% by weight; Al ₂ O ₃ in the range of 9.0 to 18.0% by weight; MgO in the range of 1.0 to 8.0% by weight; CaO in the range of 0 to 10.0 wt%, SrO in the range of 0 to 6.0 wt%, and _TiO in the range of 0 to 6.0 wt%, for a total of 0.1 to 3.0 A composition comprising F ₂ and Cl ₂ in the range of mass %.

In the surface-treated glass cloth of the present embodiment, the composition of the glass constituting the glass cloth is, for example, SiO ₂ in the range of 52.0 to 60.0% by mass and 15.0% by mass with respect to the total amount of glass. B ₂ O ₃ in the range of 20.0% by mass or more, Al ₂ O ₃ in the range of 9.0 to 18.0% by mass, MgO in the range of 1.0 to 6.0% by mass, and 1 CaO in the range of 0 to 9.0 wt%, SrO in the range of 0 to less than 0.5 wt%, and _TiO in the range of 1.0 to 6.0 wt%, in total 0 A first embodiment comprising F ₂ and Cl ₂ in the range of .1 to 2.5% by weight, or SiO ₂ in the range of 52.0 to 60.0% by weight, based on the total amount of glass, and 20.0 B ₂ O ₃ in the range of less than ˜26.0 wt %, Al ₂ O ₃ in the range of 9.0 to 18.0 wt %, MgO in the range of 1.0 to 6.0 wt %, 1 CaO in the range of 0 to 9.0% by weight, SrO in the range of 0.5 to less than 6.0% by weight, and TiO in the range of 0 to 6.0% by _weight , for a total of 0.1 to A second embodiment can include _F2 and _Cl2 in the range of 2.5% by weight.

In the first aspect, the content of SiO ₂ is preferably in the range of 52.5 to 59.0% by mass, more preferably in the range of 53.0 to 58.0% by mass, and even more preferably is in the range of 53.5 to 57.0% by weight. Also, the content of B ₂ O ₃ is preferably in the range of 16.0 to 19.8% by mass, more preferably in the range of 17.0 to 19.7% by mass, and still more preferably 18% by mass. .0 to 19.6% by mass. Also, the content of Al ₂ O ₃ is preferably in the range of 10.0 to 17.5% by mass, more preferably in the range of 11.0 to 17.0% by mass, further preferably It is in the range of 12.0 to 16.5% by mass. Also, the content of MgO is preferably in the range of 1.5 to 6.0% by mass, more preferably in the range of 2.0 to 5.5% by mass, and still more preferably 3.0% by mass. It is in the range of ~5.0% by mass. In addition, the content of CaO is preferably in the range of 1.5 to 8.0% by mass, more preferably in the range of 2.0 to 7.0% by mass, still more preferably 3.0 to It is in the range of 5.0% by mass. In addition, the content of SrO is preferably in the range of 0 to 0.1% by mass, more preferably in the range of 0 to 0.05% by mass, still more preferably 0 to 0.01% by mass. in the range of The content of TiO ₂ is preferably in the range of 1.0 to 5.5% by mass, more preferably in the range of 1.0 to 5.5% by mass, and even more preferably in the range of 1.5 to 5.5% by mass. It is in the range of 4.5% by weight. Also, the total content of F ₂ and Cl ₂ is preferably in the range of 0.1 to 2.0% by mass, more preferably in the range of 0.1 to 1.5% by mass, further preferably , in the range of 0.2 to 1.2% by weight.

In the second aspect, the content of SiO ₂ is preferably in the range of 52.5 to 59.0% by mass, more preferably in the range of 53.0 to 58.0% by mass, and even more preferably is in the range of 53.5 to 57.0% by weight. Also, the content of B ₂ O ₃ is preferably in the range of 21.0 to 24.8% by mass, more preferably in the range of 22.0 to 24.6% by mass, further preferably It is in the range of 23.0 to 24.4% by mass. Also, the content of Al ₂ O ₃ is preferably in the range of 9.5 to 17.0% by mass, more preferably in the range of 10.0 to 16.0% by mass, further preferably It is in the range of 10.5-14.5% by mass. In addition, the content of MgO is preferably in the range of 1.0 to 5.0% by mass, more preferably in the range of 1.0 to 4.0% by mass, and still more preferably 1.5 to 4.0% by mass. It is in the range of 3.0% by mass. The CaO content is preferably in the range of 1.0 to 7.0% by mass, more preferably in the range of 1.0 to 5.0% by mass, and still more preferably 1.5% by mass. It is in the range of ~3.0% by mass. In addition, the SrO content is preferably in the range of 1.0 to 6.0% by mass, more preferably in the range of 1.5 to 5.5% by mass, still more preferably 2.0 to 5% by mass. .0% by mass. Also, the content of TiO ₂ is preferably in the range of 0 to 4.5% by mass, more preferably in the range of 0 to 3.0% by mass, and still more preferably in the range of 0 to 1.0% by mass. in the range. Also, the total content of F ₂ and Cl ₂ is preferably in the range of 0.1 to 2.0% by mass, more preferably in the range of 0.1 to 1.5% by mass, still more preferably is in the range of 0.2 to 1.2% by weight.

In addition, in the surface-treated glass cloth of the present embodiment, the composition of the glass constituting the glass cloth includes P ₂ O ₅ in the range of 0 to 15.0% by mass based on the total amount of the glass, in addition to the above components. may be included in Further, the composition of the glass may contain Fe ₂ O ₃ in the range of 0 to 1.0% by mass, preferably in the range of 0.05 to 0.5% by mass, based on the total amount of the glass. Further, the composition of the glass may contain Li ₂ O, K ₂ O and Na ₂ O in a total amount of 0 to 1.0% by mass with respect to the total amount of the glass.

Here, the content of each component of the composition of the glass described above is measured using an ICP emission spectrometer for the light element Li, and for the other elements using a wavelength dispersive X-ray fluorescence spectrometer. be able to.

As a measuring method, glass cloth (when an organic substance is attached to the surface of the glass cloth, or when the glass cloth is mainly contained in the organic substance (resin) as a reinforcing material, for example, 300 to 600 ° C. After removing the organic matter by heating in a muffle furnace for about 2 to 24 hours, etc.), cut it into an appropriate size, put it in a platinum crucible, and hold it at a temperature of 1550 ° C. for 6 hours in an electric furnace. Homogeneous molten glass is obtained by melting while adding stirring. Next, the obtained molten glass is poured onto a carbon plate to produce glass cullet, which is then pulverized into powder. Li, which is a light element, is subjected to quantitative analysis using an ICP emission spectrometer after thermally decomposing the glass powder with an acid. Other elements are subjected to quantitative analysis using a wavelength dispersive X-ray fluorescence spectrometer after forming the glass powder into a disc shape with a pressing machine. These quantitative analysis results are converted into oxides to calculate the content and total amount of each component, and from these numerical values, the content (% by mass) of each component described above can be obtained.

Further, in the surface-treated glass cloth of the present embodiment, the glass cloth has a surface coverage in the range of 75.0 to 98.5 % and a thickness in the range of 8 to 95 μm, and the surface treatment layer is , contains a silane coupling agent having a methacrylic group and does not contain a surfactant.

In the surface-treated glass cloth of the present embodiment, the silane coupling agent having a methacryl group includes, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silanes, 3-methacryloxypropyltriethoxysilane, may be mentioned.

Here, the silane coupling agent having the methacryl group can be identified by, for example, GC-MS (eg, GC-MSQP2010 Ultra (trade name) manufactured by Shimadzu Corporation).

The surfactant is commonly used as a dispersing agent for a silane coupling agent in the surface treatment of glass cloth, and specifically includes nonionic surfactants, anionic surfactants, and cationic surfactants. , amphoteric surfactants. Surfactants are employed singly or in combination.

Nonionic surfactants include glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene glycol, fatty acid polyethylene glycol, fatty acid polyoxyethylene sorbitan , fatty acid alkanolamides, and the like.

Examples of anionic surfactants include fatty acid monocarboxylates, polyoxyethylene alkyl ether carboxylates, N-acylsarcosine salts, N-acylglutamates, dialkylsulfosuccinates, alkanesulfonates, alpha olefinsulfonic acids. Salt, linear alkylbenzenesulfonate, alkylbenzenesulfonate, naphthalenesulfonate-formaldehyde condensate, alkylnaphthalenesulfonate, N-methyl-N-acyl taurine salt, alkyl sulfate, polyoxyethylene alkyl ether sulfate , fat and oil sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and the like.

Cationic surfactants include monoalkylamine salts, dialkylamine salts, trialkylamine salts, alkyltrimethylammonium chlorides, alkylbenzalkonium chlorides and the like.

Amphoteric surfactants include alkyl betaine, fatty acid amidopropyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldiethylenetriaminoacetic acid, alkylamine oxide and the like.

Here, the fact that the surface-treated glass cloth of the present embodiment does not contain a surfactant can be confirmed, for example, by using GC-MS (for example, GC-MSQP2010 Ultra (trade name) manufactured by Shimadzu Corporation) on the surface. It can be confirmed by not detecting the aforementioned surfactant-derived component from the treated glass cloth.

In the surface-treated glass cloth of the present embodiment, the surface-treated layer is formed, for example , in a range of 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the surface- treated glass cloth. Further, the content of the silane coupling agent having a methacrylic group is, for example, in the range of 80 to 100% by mass, preferably in the range of 90 to 100% by mass, more preferably in the range of 90 to 100% by mass, with respect to the total amount of the surface treatment layer. is in the range of 95-100% by weight.

Here , the ratio of the mass of the surface -treated layer to the mass of the surface-treated glass cloth can be obtained by measuring the mass of the test piece before and after heat drying in accordance with JIS R 3420. In addition, the ratio of the silane coupling agent having a methacrylic group to the mass of the surface treatment layer can be determined using, for example, GC-MS (eg, GC-MSQP2010Ultra (trade name) manufactured by Shimadzu Corporation). It can be obtained by quantifying and comparing with the mass of the surface treatment layer.

In the surface-treated glass cloth of the present embodiment, the surface treatment layer includes, in addition to a silane coupling agent having a methacrylic group, a silane coupling agent other than a silane coupling agent having a methacrylic group (for example, an amino group). Silane coupling agent having a glycidoxy group, Silane coupling agent having a vinyl group, Silane coupling agent having an acrylic group, Silane coupling agent having an isocyanate group, Silane coupling agent having a mercapto group , styryl group-containing silane coupling agents, ureido group-containing silane coupling agents), weak acids (e.g., acetic acid, citric acid, formic acid), antifoaming agents (silicon antifoaming agents, emulsion antifoaming agents, surfactant agent-based antifoaming agent, oil-based antifoaming agent) may be included in a total amount of 20% by mass or less with respect to the total amount of the surface treatment layer.

Further, in the surface-treated glass cloth of the present embodiment, it is preferable that silica fine particles adhere to the surfaces of the glass filaments constituting the glass cloth.

Here, as the silica fine particles, silica fine particles having a volume average particle diameter of 30 to 300 nm can be used. In addition, the amount of the silica fine particles attached can be, for example, 0.001 to 1 part by mass of the silica fine particles with respect to 100 parts by mass of the non-surface-treated glass cloth.

Adherence of silica fine particles to the surface-treated glass cloth of the present embodiment can be confirmed by observation with a SEM (Scanning Electron Microscope). Also, the amount of silica fine particles attached can be obtained by observing with a SEM (Scanning Electron Microscope) and counting the number of silica fine particles.

Further, in the surface-treated glass cloth of the present embodiment, the glass cloth preferably has a surface coverage in the range of 85.5 to 98.5 %. More preferably, it has a thickness in the range of 8-40 μm.

In the surface-treated glass cloth of the present embodiment, the surface coverage is more preferably in the range of 87.0 to 98.5 %, more preferably in the range of 89.0 to 98.5 %. , in the range of 90.0 to 98.5 %, most preferably in the range of 90.5 to 98.5 %.

Further, it is more preferable that the thickness of the surface-treated glass cloth of the present embodiment is in the range of 9 to 35 μm.

Here , as the thickness of the surface -treated glass cloth, the average value of the measured values when the thickness is measured at 15 points in the surface- treated glass cloth with a micrometer is adopted in accordance with JIS R 3420. be able to.

The surface-treated glass cloth of this embodiment can be manufactured, for example, as follows.

First, a glass filament is obtained by melting a predetermined glass batch (glass raw material) and fiberizing it. The glass filament comprises, for example, the composition of the first aspect or the second aspect.

Although the filament diameter of the glass filament is not particularly limited, it is preferably 10 μm or less, more preferably 8 μm or less, and in the range of 3 to 5 μm for use as a reinforcing material for thin fiber-reinforced resin molded products. is particularly preferred.

The number of the glass filaments, for example, in the range of 25 to 500, preferably 40 to 300, is bundled by a method known per se to form a glass fiber thread. Spinning refers to melting a glass batch, converting it into fibers to obtain glass filaments, and then bundling a plurality of the glass filaments to obtain a glass fiber yarn.

The count of the glass fiber yarn is preferably 0.8 to 135 tex, more preferably 1 to 25 tex. The count (tex) of the glass fiber thread corresponds to the mass (unit: g) of the glass fiber per 1000 m.

Next, a glass cloth is obtained by weaving the glass fiber yarns as warp yarns or weft yarns. The weaving method is not particularly limited, and examples thereof include plain weave, satin weave, and twill weave, and plain weave is preferred. The weaving density of the glass fiber yarns during the weaving is not particularly limited, but is preferably 10 to 150 threads/25 mm, more preferably 40 to 100 threads/25 mm.

During the weaving, a sizing agent is used for bundling the glass filaments, warping the warp yarns, and the like. Examples of the sizing agent include starch-based or PVA (polyvinyl alcohol)-based film-forming agent components. The sizing agent may contain an oil agent, a softening agent, or the like.

The amount of the sizing agent attached to the glass cloth is preferably 0.1 to 3 parts by mass, more preferably 0.5 to 1.5 parts by mass, with respect to 100 parts by mass of the glass fiber yarn. Part is more preferred. The range of the sizing agent adhesion amount and the sizing agent adhesion amount unless otherwise specified represent the average sizing agent adhesion amount with respect to the warp or the weft.

The glass cloth obtained by the weaving preferably has a mass per unit area of 110 g/m ² or less, more preferably 50 g/m ² or less, from the viewpoint of use as a base material for printed wiring boards. . On the other hand, from the viewpoint of weaving, the mass per unit area of the glass cloth is preferably 8 g/m ² or more.

Next, the glass cloth is subjected to a fiber opening treatment. Examples of the fiber-spreading treatment include fiber-spreading by water flow pressure, fiber-spreading by high-frequency vibration using liquid as a medium, fiber-spreading by pressure of fluid having surface pressure, and fiber-spreading by pressurization by rolls. can be done. In the above-described fiber-spreading process, the use of water-jet pressure-spreading or high-frequency vibration-spreading using liquid as a medium reduces the variation in yarn width after the spread process in each of the warp and weft. It is preferable because Moreover, the fiber-opening treatment may be performed by combining a plurality of treatment methods.

Next, a deoiling treatment is applied to the glass cloth subjected to the opening treatment. In the deoiling treatment, for example, the glass cloth is placed in a heating furnace at an atmospheric temperature of 350° C. to 450° C. for 40 to 80 hours, and the spinning sizing agent and the weaving sizing agent attached to the glass cloth are removed. can be carried out by thermally decomposing.

Next, the deoiled glass cloth is immersed in an aqueous solution of a surface treatment agent, and after excess water is squeezed out, the temperature is in the range of 80 to 180 ° C. for 1 to 30 minutes, for example. By drying by heating at 110° C. for 5 minutes, the surface-treated glass cloth of the present embodiment is obtained.

The aqueous solution of the surface treatment agent contains 0.1 to 2.0% by mass of the silane coupling agent having a methacrylic group as a solid content with respect to the total amount of the aqueous solution of the surface treatment agent, and a weak acid ( For example, acetic acid, citric acid, etc.) can be used in an amount of 0.1 to 1.0% by mass. Since the weak acid evaporates during the heating and drying process , it may not remain in the surface-treated layer of the surface -treated glass cloth.

The prepreg of this embodiment includes the surface-treated glass cloth of this embodiment described above.

The prepreg of the present embodiment is obtained by impregnating the surface -treated glass cloth described above with a resin by a method known per se and semi-curing it.

In the prepreg of the present embodiment, a polyphenylene ether resin or a modified polyphenylene ether resin is used as the resin impregnated in the surface-treated glass cloth described above, because the effect of improving insulation reliability is particularly large. can be done.

The prepreg or fiber-reinforced resin molded product containing the surface-treated glass cloth of the present embodiment can be used for applications other than printed wiring boards, such as antennas, radars, housings for electronic equipment, and the like.

Next, examples of the present invention and comparative examples are shown.

[Example 1]
In this example, first, IPC4412 standard cross style #1078 (yarn used: D450 (filament diameter 5.0 μm, yarn weight 11.0 tex), warp weave density: 53 / 25 mm, weft weave density: 53 / 25 mm ) was passed through a silica fine particle adhesion tank containing a dispersion liquid in which silica fine particles having a volume average particle diameter of about 100 nm were dispersed in water to obtain a glass cloth with silica fine particles adhered.

The glass constituting the glass cloth contains 54.5% by mass of _SiO2 , 19.4% by mass of _B2O3 , 14.6% by mass of _Al2O3 , and _4.2 % by mass _{of the} total amount of glass. wt% MgO, 4.1 wt% CaO, 0 wt% SrO, 1.9 wt% _TiO2 , 0.1 _wt % _Fe2O3 , totaling 0.2 wt% % Li ₂ O, Na ₂ O and K ₂ O, and 1.0% by mass of F ₂ (hereinafter referred to as glass composition A), and the glass composition A is the first aspect It has a composition corresponding to

Next, a high-pressure water stream at 40°C having a pressure of 2 MPa is sprayed onto the glass cloth to which the silica fine particles have adhered to perform fiber opening treatment by the water stream pressure, and then deoiled by heating at 360°C for 60 hours. rice field.

Next, with respect to the total amount, as a silane coupling agent having a methacryl group, 3-methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd.) as a solid content is 1.0% by mass, and acetic acid is 0.1% by mass. % and stirred with a magnetic stirrer for 1 hour to prepare an aqueous surface treatment agent solution. The surface treatment agent aqueous solution does not contain a surfactant at all.

Next, the deoiled glass cloth was immersed in an aqueous solution of a surface treatment agent, and after excess water was squeezed out, the surface-treated glass cloth of this example was dried by heating at 110°C for 5 minutes. got The obtained glass cloth was cut into a size of 350 mm×400 mm to obtain a surface- treated glass cloth piece. At this time, the amount of the silane coupling agent adhered to the glass cloth was 0.53 parts by weight with respect to 100 parts by weight of the surface -treated glass cloth. In addition, in the surface-treated glass cloth of Example 1, the surface-treated layer is composed only of a silane coupling agent having a methacrylic group.

Next, the surface- treated glass cloth piece was immersed in a polyphenylene ether resin varnish and dried at 150° C. for 10 minutes to obtain a surfactant- free prepreg . The polyphenylene ether resin varnish includes OPE-2St/toluene (trade name, manufactured by Mitsubishi Gas Chemical Company, Inc.) 450 parts by mass, TAICROS triallyl isocyanurate (trade name, manufactured by Evonik Japan Co., Ltd.) 100 parts by mass, Perbutyl P (trade name, manufactured by NOF Corporation) 4 parts by mass and toluene (manufactured by Wako Co., Ltd.) 250 parts by mass.

Next, four sheets of the surfactant- free prepreg are laminated, cellophane films are layered on the top and bottom, and a vacuum hot press (manufactured by Kitagawa Seiki Co., Ltd.) is used to heat at 205 ° C. and 1.8 MPa in a vacuum. After heating and pressing for a period of time, a surfactant-free laminate having a thickness of about 0.3 mm was obtained.

Next, instead of the aqueous solution of the surface treatment agent, 3-methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd.) of 1.0% by mass as a solid content, 0.1% by mass of acetic acid, and a surfactant Polyoxyethylene alkyl ether (manufactured by Toho Chemical Industry Co., Ltd.) as 0.05% by mass was mixed with water and stirred for 1 hour with a magnetic stirrer except for using an aqueous solution of a surface treatment agent prepared was exactly the same as that of the surfactant-free laminate to obtain a surfactant-containing laminate having a thickness of about 0.3 mm.

Next, the surfactant-free laminate and the surfactant-containing laminate were each cut into pieces of 7 cm x 4 cm, and two slits each having a length of 2 cm were made vertically and horizontally using a diamond cutter, A test piece shown in FIG. 1 was obtained. The specimen shown in FIG. 1 has A=4 cm, B=7 cm, slit length L=2 cm and slit width D=2 mm.

Next, put a 1 mol / L NaOH (manufactured by Wako Co., Ltd.) aqueous solution in a beaker, heat to 60 ° C., immerse each test piece in the NaOH aqueous solution for 30 hours, then use a digital microscope (Keyence Corporation) (manufacturer) at a magnification of 100 times, an alkali whitening test was conducted to measure the whitening distance due to peeling of the interface between the resin and the glass in the warp and weft directions. In the alkali whitening test, the whitening distance was measured at 24 points in each of the warp and weft directions, and the average value was taken as the whitening distance. The whitening distance due to peeling between the resin and the glass interface has a correlation with the insulation reliability of the printed wiring board, and the smaller the whitening distance, the better the insulation reliability. Table 1 shows the results.

[Example 2]
In this example, a surface -treated glass cloth was obtained in exactly the same manner as in Example 1, except that silica fine particles were not adhered to the glass cloth. Next, an alkali whitening test was performed in exactly the same manner as in Example 1 except that the surface- treated glass cloth obtained in this example was used, and the whitening distance was measured.

In addition, the tensile strength in the weft direction of the surface- treated glass cloth obtained in this example was measured according to JIS R 3420 with N=5 samples. Table 1 shows the results.

[Example 3]
In this example, a surface- treated glass cloth was obtained in exactly the same manner as in Example 2, except that a high-pressure water stream at 40°C having a pressure of 0.1 MPa was sprayed to perform the fiber opening treatment by the water stream pressure. . Next, an alkali whitening test was performed in exactly the same manner as in Example 1 except that the surface- treated glass cloth obtained in this example was used, and the whitening distance was measured. Table 1 shows the results.

[ Reference Example 1 ]
In this reference example, IPC4412 standard cross style #2116 (yarn used: E225 (filament diameter 7.0 μm, yarn weight 22.0 tex), warp weave density: 59.1 / 25 mm, weft weave density: 57.1 A surface -treated glass cloth was obtained in exactly the same manner as in Example 2, except that a glass cloth having a thickness of 1/25 mm was used. The amount of the silane coupling agent attached to the glass cloth was 0.36 parts by weight with respect to 100 parts by weight of the surface -treated glass cloth. In addition, in the surface-treated glass cloth of this reference example, the surface-treated layer is composed only of a silane coupling agent having a methacrylic group.

Next, an alkali whitening test was performed in exactly the same manner as in Example 1 except that the surface -treated glass cloth obtained in this reference example was used, and the whitening distance was measured. Table 1 shows the results.

[Example 4 ]
In this embodiment, IPC4412 standard cross style #1035 (yarn used: D900 (filament diameter 5.0 μm, yarn weight 5.5 tex), warp weave density: 65 / 25 mm, weft weave density: 67 / 25 mm) A surface -treated glass cloth was obtained in exactly the same manner as in Example 2, except that the glass cloth was used. The amount of the silane coupling agent attached to the glass cloth was 0.47 parts by weight with respect to 100 parts by weight of the surface -treated glass cloth. In addition, in the surface-treated glass cloth of this example, the surface-treated layer is composed only of a silane coupling agent having a methacrylic group.

Next, an alkali whitening test was performed in exactly the same manner as in Example 1 except that the surface- treated glass cloth obtained in this example was used, and the whitening distance was measured. Table 1 shows the results.

[ Reference example 2 ]
In this reference example, the glass constituting the glass cloth is composed of 55.0% by mass of SiO ₂ , 24.0% by mass of B ₂ O ₃ and 12.0% by mass of Al ₂ O ₃ with respect to the total amount. , 2.0 wt.% MgO, 2.0 wt.% CaO, 4.0 wt.% SrO, 0.0 wt.% _TiO2 , _0.0 wt.% _Fe2O3 ; Except for a composition containing 0.0% by mass of Li ₂ O, Na ₂ O and K ₂ O in total and 1.0% by mass of F ₂ (hereinafter referred to as glass composition B), A surface- treated glass cloth was obtained in exactly the same manner as in Example 2. The glass composition B has a composition corresponding to the second aspect. The amount of the silane coupling agent attached to the glass cloth was 0.70 parts by weight with respect to 100 parts by weight of the surface -treated glass cloth. In addition, in the surface-treated glass cloth of this reference example, the surface-treated layer is composed only of a silane coupling agent having a methacrylic group.

Next, an alkali whitening test was performed in exactly the same manner as in Example 1 except that the surface -treated glass cloth obtained in this reference example was used, and the whitening distance was measured.

Further, the tensile strength was measured in exactly the same manner as in Example 2, except that the surface-treated glass cloth obtained in this reference example was used. Table 1 shows the results.

[Comparative Example 1]
In this comparative example, the procedure was exactly the same as in Example 2, except that an aqueous surface treatment agent solution containing N-β-(N-vinylbenzylamino)ethyl-aminopropylmethoxysilane was used as the silane coupling agent . A surface-treated glass cloth was obtained. The amount of the silane coupling agent adhered to the glass cloth was 0.44 parts by mass with respect to 100 parts by mass of the glass fiber thread.

Next, an alkali whitening test was performed in exactly the same manner as in Example 1 except that the surface- treated glass cloth obtained in this comparative example was used, and the whitening distance was measured. Table 2 shows the results.

[Comparative Example 2]
In this comparative example, a surface- treated glass cloth was obtained in exactly the same manner as in Example 2, except that an aqueous surface treatment agent solution containing 3-aminopropyltrimethoxysilane was used as the silane coupling agent. The amount of the silane coupling agent adhered to the glass cloth was 0.35 parts by mass with respect to 100 parts by mass of the glass fiber thread.

Next, an alkali whitening test was performed in exactly the same manner as in Example 1 except that the surface- treated glass cloth obtained in this comparative example was used, and the whitening distance was measured. Table 2 shows the results.

[Comparative Example 3]
In this comparative example, the glass constituting the glass cloth was composed of 54.6% by mass of SiO ₂ , 6.1% by mass of B ₂ O ₃ and 14.1% by mass of Al ₂ O ₃ with respect to the total amount. , 1.2 wt.% MgO, 22.4 wt.% CaO, 0 wt.% SrO, 0.3 wt.% _TiO2 , and _0.2 wt.% _Fe2O3 , in total Example except that a composition containing 0.5% by mass of Li ₂ O, Na ₂ O and K ₂ O and 0.6% by mass of F ₂ (hereinafter referred to as glass composition C) was provided. A surface- treated glass cloth was obtained in exactly the same manner as in 2. The amount of the silane coupling agent attached to the glass cloth was 0.21 parts by mass with respect to 100 parts by mass of the glass fiber thread.

Next, an alkali whitening test was performed in exactly the same manner as in Example 1 except that the surface- treated glass cloth obtained in this comparative example was used, and the whitening distance was measured. Table 2 shows the results.

[Comparative Example 4]
In this comparative example, the same procedure as in Comparative Example 3 was performed except that an aqueous surface treatment agent solution containing N-β-(N-vinylbenzylamino)ethyl-aminopropylmethoxysilane was used as the silane coupling agent . A surface-treated glass cloth was obtained. The amount of the silane coupling agent attached to the glass cloth was 0.21 parts by mass with respect to 100 parts by mass of the glass fiber thread.

Next, an alkali whitening test was performed in exactly the same manner as in Example 1 except that the surface- treated glass cloth obtained in this comparative example was used, and the whitening distance was measured. Table 2 shows the results.

From Table 1, it can be seen that the surface-treated glass cloths of Examples 1 to 4 obtained by surface- treating glass cloths woven using glass fibers having a composition in which the B ₂ O ₃ content is 15% by mass or more: , The surface treatment layer contains a silane coupling agent having a methacrylic group and does not contain a surfactant, so that the whitening distance and the ratio of the surfactant-free whitening distance to the surfactant-containing whitening distance are It is clear that it is small and can improve insulation reliability.

Further, according to the surface-treated glass cloth of Example 1 in which silica fine particles are attached to the surface of the glass filaments constituting the glass cloth, the surface-treated layer contains a silane coupling agent having a methacrylic group, and a surfactant is not contained, the whitening distance is smaller than the surface-treated glass cloths of Examples 2 to 4 in which silica fine particles are not attached to the glass filament surface, and the insulation reliability can be further improved. is clear.

Further, according to the surface-treated glass cloth of Example 2 in which the composition of the glass constituting the glass cloth is the glass composition A corresponding to the first aspect, the composition of the glass constituting the glass cloth is the second composition. It is clear that the tensile strength is greater than that of the surface-treated glass cloth of Reference Example 2, which is the glass composition B corresponding to the embodiment.

On the other hand, a surface- treated glass cloth obtained by surface-treating a glass cloth woven using glass fibers having a composition in which the B ₂ O ₃ content is 15% by mass or more, wherein the surface-treated In the surface-treated glass cloths of Comparative Examples 1 and 2, in which the layer contains a silane coupling agent other than a silane coupling agent having a methacrylic group, the whitening distance when the surface-treated layer does not contain a surfactant is It is clear that the effect of improving the insulation reliability due to the surface treatment layer not containing a surfactant can be obtained. is.

Further, in the surface-treated glass cloth of Comparative Example 3 obtained by surface- treating a glass cloth woven using glass fibers having a composition in which the B ₂ O ₃ content is less than 15% by mass, the surface treatment Even if the layer contains a silane coupling agent having a methacrylic group, the whitening distance when the surface treatment layer does not contain a surfactant is larger than when the surface treatment layer contains a surfactant, It is clear that the effect of improving insulation reliability cannot be obtained because the surface treatment layer does not contain a surfactant.

Further, a surface-treated glass cloth obtained by surface-treating a glass cloth woven using glass fibers having a composition in which the B ₂ O ₃ content is less than 15% by mass, wherein the surface -treated layer is In the surface-treated glass cloth of Comparative Example 4 containing a silane coupling agent other than a silane coupling agent having a methacrylic group, the whitening distance when the surface treatment layer does not contain a surfactant is This is equivalent to the case of containing an active agent, and it is clear that the effect of improving insulation reliability cannot be obtained by the surface treatment layer not containing a surfactant.

unsigned.

Claims (8)

A surface-treated glass cloth having a surface-treated layer on its surface,
The glass constituting the glass cloth contains SiO ₂ in the range of 52.0 to 60.0% by mass, B ₂ O ₃ in the range of 15.0 to 26.0% by mass, and 9.0% by mass. Al ₂ O ₃ in the range of ∼18.0 wt%, MgO in the range of 1.0 to 8.0 wt%, CaO in the range of 1.0 to 10.0 wt%, and 0 to 6.0 wt%. a composition comprising _SrO in the range _{of wt} .
The glass cloth has a surface coverage in the range of 75.0-98.5% and a thickness in the range of 8-95 μm,
The surface treatment layer contains a silane coupling agent having a methacrylic group and does not contain a surfactant,
The surface coverage rate is 100 x (25000 (μm) x warp width (μm) x warp weave density (thread/25mm) + 25000 (μm) x weft thread width (μm) x weft weave density (thread / 25 mm) - warp thread width (μm) × warp weave density (thread/25 mm) × weft thread width (μm) x weft thread density (thread/25 mm)) / (25000 (μm) x 25000 (μm) )) , and the resin with which the surface-treated glass cloth is impregnated is a polyphenylene ether resin or a modified polyphenylene ether resin . 2. The surface-treated glass cloth according to claim 1, wherein said glass filaments constituting said glass cloth have silica fine particles attached to their surfaces. 3. The surface-treated glass cloth according to claim 1, wherein said glass cloth has a surface coverage in the range of 85.5 to 98.5%. 4. The surface-treated glass cloth according to claim 3, wherein said glass cloth has a thickness in the range of 8-60 μm. 4. The surface-treated glass cloth according to claim 3, wherein said glass cloth has a thickness in the range of 8-40 μm. 6. The surface-treated glass cloth according to any one of claims 1 to 5, wherein the glass constituting the glass cloth contains SiO ₂ in a range of 52.0 to 60.0% by mass, and 15% by mass. B ₂ O ₃ in the range of 0% by mass or more and less than 20.0% by mass, Al ₂ O ₃ in the range of 9.0 to 18.0% by mass, and 1.0 to 6.0% by mass MgO, CaO in the range of 1.0 to 9.0% by weight, SrO in the range of 0% to less than 0.5% by weight, and TiO ₂ in the range of 1.0 to 6.0% by weight. , and a total of F ₂ and Cl ₂ in the range of 0.1 to 2.5% by mass. 6. The surface-treated glass cloth according to any one of claims 1 to 5, wherein the glass constituting the glass cloth contains SiO ₂ in a range of 52.0 to 60.0% by mass and 20% by mass with respect to the total amount. B ₂ O ₃ in the range from 0 to less than 26.0 wt %, Al ₂ O ₃ in the range from 9.0 to 18.0 wt %, and MgO in the range from 1.0 to 6.0 wt %. , CaO in the range of 1.0 to 9.0 wt.%, SrO in the range of 0.5 to less than 6.0 wt.%, and TiO ₂ in the range of 0 to 6.0 wt. A surface-treated glass cloth characterized by having a composition containing F ₂ and Cl ₂ in the range of 1 to 2.5% by mass. A prepreg comprising the surface-treated glass cloth according to any one of claims 1 to 7.

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