Surface-treated glass cloth, prepreg, and printed wiring board

Abstract

The present invention provides a surface-treated glass cloth, a prepreg, and a printed wiring board. High insulation reliability can be obtained on the printed wiring board, and wrinkles are not easily generated during the manufacture of the prepreg. The surface-treated glass cloth has a surface treatment layer on the surface, and the surface treatment layer contains a first silane coupling agent having at least one methacryloyl group and a second silane coupling agent represented by the following general formula (1), X(R) 3‑n SiY n …(1). (In the formula, X is an alkyl group having 1 to 4 carbon atoms, R represents each independently one group selected from the group consisting of methyl, ethyl, and phenyl, Y represents each independently an alkoxy group having 1 to 6 carbon atoms, and n is an integer of 1 or more and 3 or less).

Description

Technical Field

[0001] The present invention relates to a surface-treated glass cloth, a prepreg, and a printed wiring board. Background Art

[0002] Conventionally, as a glass cloth used in a printed wiring board, there is known a glass cloth having a surface treatment layer on the surface of which there is a silane coupling agent having at least one methacryloyl group such as 3-methacryloxypropyltrimethoxysilane (γ-methacryloxypropyltrimethoxysilane) (for example, see Patent Document 1).

[0003] According to the surface-treated glass cloth described in Patent Document 1, the whitening distance indicating the degree of interfacial peeling between the glass and the resin on the surface treatment layer when made into a printed wiring board is small, and the printed wiring board can obtain high insulation reliability.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent No. 6734422 Gazette Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] However, the surface-treated glass cloth described in Patent Document 1 has a problem that it has a soft feel and is likely to form wrinkles when manufacturing a prepreg. In addition, in recent years, due to the miniaturization and thinning of electronic devices, the glass cloth used in printed wiring boards is also required to be thinner, and wrinkles are likely to occur when manufacturing thinner glass cloth. Therefore, it has become difficult to handle particularly the surface-treated glass cloth having a soft feel.

[0009] An object of the present invention is to provide a surface-treated glass cloth that can obtain high insulation reliability in a printed wiring board and is not likely to form wrinkles when manufacturing a prepreg, a prepreg using the surface-treated glass cloth, and a printed wiring board using the surface-treated glass cloth in order to solve the above problems.

[0010] Means for Solving the Problems

[0011] In order to achieve the above object, the surface-treated glass cloth of the present invention has a surface treatment layer on the surface, and is characterized in that the surface treatment layer contains a first silane coupling agent having at least one methacryloyl group and a second silane coupling agent represented by the following general formula (1).

[0012] X(R) 3-n SiY n …(1)

[0013] (In the formula, X is an alkyl group having 1 to 4 carbon atoms, R represents each independently one group selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, Y represents each independently an alkoxy group having 1 to 6 carbon atoms, and n is an integer of 1 or more and 3 or less.)

[0014] The surface-treated glass cloth of the present invention can obtain high insulation reliability in a printed wiring board by having a surface treatment layer containing the above-mentioned first silane coupling agent and the above-mentioned second silane coupling agent on the surface, and moreover, the feel becomes hard, so that wrinkles are not easily generated during the production of prepregs.

[0015] The hydrolysis rate of the above-mentioned second silane coupling agent is fast and the reactivity of silanol is high, so the adsorptivity to the glass cloth increases and the feel of the glass cloth can be made hard. In addition, since the alkyl chain of the above-mentioned second silane coupling agent is short, the molecular weight is small and it does not hinder the reaction between the above-mentioned first silane coupling agent and the resin. Therefore, high insulation reliability can be obtained in a printed wiring board.

[0016] In the surface-treated glass cloth of the present invention, preferably, X in the general formula (1) of the above-mentioned second silane coupling agent is a methyl group or an ethyl group, and more preferably a methyl group.

[0017] In addition, in the surface-treated glass cloth of the present invention, preferably, the total content of the first silane coupling agent and the second silane coupling agent is in the range of 0.03 to 1.50% by mass of the total mass of the surface-treated glass cloth, and the ratio of the content of the second silane coupling agent to the content of the first silane coupling agent (content of the second silane coupling agent / content of the first silane coupling agent) is in the range of 0.01 to 0.25, and more preferably the ratio of the content of the second silane coupling agent to the content of the first silane coupling agent is in the range of 0.03 to 0.17.

[0018] The total content of the first silane coupling agent and the second silane coupling agent of the surface-treated glass cloth of the present invention is in the range of 0.03 to 1.50% by mass of the total mass of the surface-treated glass cloth, and the ratio of the content of the second silane coupling agent to the content of the first silane coupling agent (content of the second silane coupling agent / content of the first silane coupling agent) is in the range of 0.01 to 0.25. Thus, the effects of high insulation reliability in a printed wiring board and hardening the feel of the glass cloth can be obtained in a balanced manner.

[0019] In the surface-treated glass cloth of the present invention, when the total content of the first silane coupling agent and the second silane coupling agent is less than 0.03% by mass of the total mass of the surface-treated glass cloth, the adhesion amount of the silane coupling agent is small, so the interfacial adhesiveness with the resin deteriorates, and high insulation reliability cannot be obtained. In addition, when the total content of the first silane coupling agent and the second silane coupling agent exceeds 1.05% by mass of the total mass of the surface-treated glass cloth, it is necessary to increase the concentration of the silane coupling agent in the glass treatment agent aqueous solution, and the stability of the glass treatment agent aqueous solution deteriorates, so it is difficult to carry out long-term stable continuous production.

[0020] In addition, in the surface-treated glass cloth of the present invention, when the ratio of the content of the second silane coupling agent to the content of the first silane coupling agent (content of the second silane coupling agent / content of the first silane coupling agent) is less than 0.01, the effect of hardening the feel cannot be obtained, and when the above ratio exceeds 0.25, dehydration condensation of the second silane coupling agent is likely to occur, resulting in difficulty in long-term stable continuous production.

[0021] In addition, in the surface-treated glass cloth of the present invention, preferably, the surface treatment layer does not contain a surfactant. In the surface-treated glass cloth of the present invention, since the surface treatment layer does not contain a surfactant, the impregnation property is improved, and high insulation reliability can be obtained in a printed wiring board.

[0022] In addition, the thickness of the surface-treated glass cloth of the present invention is preferably in the range of 5 to 25 μm. The surface-treated glass cloth of the present invention can also obtain the effects of the present invention when the thickness exceeds 25 μm, but by setting the thickness in the range of 5 to 25 μm, high insulation reliability of the printed wiring board and the effect of hardening the feel of the glass cloth can be obtained evenly. In addition, it is technically difficult to manufacture the surface-treated glass cloth of the present invention with a thickness less than 5 μm.

[0023] In addition, the prepreg of the present invention is characterized by containing the surface-treated glass cloth of the present invention, and the printed wiring board of the present invention is characterized by containing the surface-treated glass cloth of the present invention. Detailed Description of the Invention

[0024] Next, the embodiments of the present invention will be described in further detail.

[0025] The surface-treated glass cloth of the present embodiment has a surface treatment layer on the surface, and the surface treatment layer contains a first silane coupling agent having at least one methacryloyl group and a second silane coupling agent represented by the following general formula (1).

[0026] X(R) 3-n SiY n …(1)

[0027] (In the formula, X is an alkyl group having 1 to 4 carbon atoms, R represents each independently one group selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, Y represents each independently an alkoxy group having 1 to 6 carbon atoms, and n is an integer of 1 or more and 3 or less.)

[0028] In the surface-treated glass cloth of the present embodiment, in the general formula (1), X of the second silane coupling agent is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0029] The surface-treated glass cloth of the present embodiment can be manufactured, for example, by the following method.

[0030] First, a specified glass batch (glass raw material) is melted and fibrillated to obtain glass filaments. The glass composition constituting the above glass filaments is not particularly limited, and the composition of E glass, T glass, NE glass, L glass, etc. is preferred. From the viewpoints of low dielectric constant and low dielectric loss tangent, the glass composition of the above glass filaments is more preferably NE glass or L glass. Specifically, the following composition is more preferably adopted: containing, relative to the total amount: SiO2 in the range of 48.0 to 62.0% by mass; B2O3 in the range of 17.0 to 26.0% by mass; Al2O3 in the range of 9.0 to 18.0% by mass; MgO in the range of 0 to 6.0% by mass; CaO in the range of 0.1 to 9.0% by mass; Na2O, K2O, and Li2O in a total range of 0 to 0.5% by mass; TiO2 in the range of 0 to 5.0% by mass; SrO in the range of 0 to 6.0% by mass; P2O5 in the range of 0 to 6.0% by mass; F2 and Cl2 in a total range of 0 to 3.0% by mass.

[0031] Here, for the measurement of the content of each component of the composition of the above glass, ICP emission spectroscopic analysis equipment can be used to measure Li as a light element, and wavelength dispersive X-ray fluorescence analysis equipment can be used to measure other elements.

[0032] The following method can be used as the measurement method. When there is an organic substance attached to the surface of the glass cloth, or when the glass cloth is mainly included as a reinforcing material in an organic substance (resin), for example, after removing the organic substance by heating in a muffle furnace at 300 to 600 °C for about 2 to 24 hours, etc., the glass cloth is cut into an appropriate size and then placed in a platinum crucible. It is held at a temperature of 1550 °C in an electric furnace for 6 hours and melted while stirring to obtain a homogeneous molten glass. Then, after pouring the obtained molten glass onto a carbon plate to make glass chips, it is crushed and powdered. After heating and decomposing the glass powder with an acid, ICP emission spectrometry is used to quantitatively analyze Li as a light element. After molding the glass powder into a disc shape with a press, wavelength dispersive X-ray fluorescence spectrometry is used to quantitatively analyze other elements. After converting these quantitative analysis results into oxides, the content and total amount of each component are calculated, and based on these values, the content (% by mass) of each of the above components can be obtained.

[0033] The filament diameter of the above-mentioned glass filaments is not particularly limited, but in the application of printed wiring boards, the filament diameter is preferably 10 μm or less, more preferably 8 μm or less, and particularly preferably in the range of 3 to 5 μm.

[0034] The above-mentioned glass filaments are bundled into a glass fiber yarn with 25 to 500, and preferably 40 to 300 filaments by a method known per se. It should be noted that the following method is called spinning: melting and fibrillating a glass batch to obtain glass filaments, and then bundling multiple glass filaments into a glass fiber yarn.

[0035] The filament diameter of the above-mentioned glass filaments is the average value of the following measured values: when measuring the diameter of the glass filaments constituting the warp or weft of the glass cloth, the measured values obtained by using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, trade name: S-3400N, magnification: 3000 times) for 50 cross-sections of the warp or 50 cross-sections of the weft of the glass cloth. In addition, the number of the above-mentioned glass filaments is the average value of the following measured values: when measuring the number of the glass filaments constituting the warp or weft of the glass cloth, the measured values obtained by using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, trade name: S-3400N, magnification: 500 times) for 50 cross-sections of the warp or 50 cross-sections of the weft of the glass cloth.

[0036] The count of the above-mentioned glass fiber yarn is preferably 0.8 to 135 tex, more preferably 1 to 25 tex. It should be noted that the count (tex) of the glass fiber yarn corresponds to the mass (unit: g) of every 1000 m of glass fiber.

[0037] Next, a glass cloth is obtained by weaving the above-mentioned glass fiber as a warp or a weft. The above weaving method is not particularly limited, and examples thereof include a plain weave method, a satin weave method, and a twill weave method, and a plain weave method is preferably used. The fabric density of the above glass fiber yarn during the above weaving is not particularly limited, and for example, it is preferably in the range of 10 to 150 threads / 25 mm, and more preferably in the range of 40 to 100 threads / 25 mm.

[0038] The fabric density of the above glass fiber yarn can be obtained by the following method: According to JIS R3420, using a fabric dissecting microscope, the number of warp or weft yarns within 25 mm in the warp direction or the weft direction is counted.

[0039] When performing the above weaving, a sizing agent is used in the bundling of the above glass filaments, the warping of the warp yarns, etc. As the above sizing agent, for example, a sizing agent having a film-forming agent component of a starch-based or PVA (polyvinyl alcohol)-based can be cited. The above sizing agent may contain an oil agent, a softening agent, etc.

[0040] The adhesion amount of the above sizing agent in the above glass cloth is preferably 0.1 to 3 parts by mass, and more preferably 0.5 to 1.5 parts by mass, relative to 100 parts by mass of the above glass fiber yarn. It should be noted that the range of the adhesion amount of the above sizing agent and the adhesion amount of the sizing agent in the case where no special designation is made represent the average adhesion amount of the sizing agent relative to the warp or weft yarn.

[0041] From the viewpoint of the base material use of a printed wiring board, the mass per unit area of the above glass cloth obtained by the above weaving is preferably 110 g / m 2 Hereinafter. On the other hand, from the viewpoint of weavability, the mass per unit area of the glass cloth is preferably 8 g / m 2 or more.

[0042] The mass of the above glass cloth is the average value of the following values: Using a scale according to JIS R 3420, the masses of 3 pieces of glass cloth cut into a size of 200 mm × 200 mm are measured, and the values obtained by converting them into the mass per square meter (1 m 2 ) are obtained.

[0043] Next, the above glass cloth is subjected to fibrillating treatment. As the fibrillating treatment, for example, the following can be cited: fibrillating using water flow pressure; fibrillating using high-frequency vibration with a liquid as a medium; fibrillating using the pressure of a fluid with surface pressure; fibrillating using roller pressing, etc. In the above fibrillating treatment, when fibrillating using water flow pressure or fibrillating using high-frequency vibration with a liquid as a medium is adopted, it is possible to reduce the deviation of the yarn width after the fibrillating treatment of the warp and weft yarns, so these two fibrillating treatments are preferred. In addition, in the above fibrillating treatment, multiple fibrillating treatment methods can also be used in combination.

[0044] Next, the glass cloth subjected to the above fibrillating treatment is subjected to degreasing treatment. This degreasing treatment can be carried out, for example, in the following manner: the above glass cloth is placed in a heating furnace at an atmosphere temperature in the range of 350°C to 450°C for a time range of 40 to 80 hours to thermally decompose the spinning bundling agent and weaving bundling agent attached to the glass cloth.

[0045] Next, the glass cloth subjected to the above degreasing treatment is immersed in an aqueous solution of a surface treatment agent. After removing the excess water, it is heated and dried at a temperature in the range of 80 to 180°C, for example, at 110°C, for a time range of 1 to 30 minutes, for example, 5 minutes, whereby the surface-treated glass cloth of the present embodiment can be obtained.

[0046] The following aqueous solution can be used as the above aqueous solution of the surface treatment agent: relative to the total amount of the aqueous solution of the surface treatment agent, it contains 0.1 to 2.0% by mass range of a first silane coupling agent having at least one methacryloyl group and a second silane coupling agent represented by the following general formula (1) in terms of solid content, and contains 0.5 to 2.0% by mass range of a weak acid (for example, acetic acid, citric acid, propionic acid, etc.) as a pH regulator.

[0047] X(R) 3-n SiY n …(1)

[0048] (In the formula, X is an alkyl group having 1 to 4 carbon atoms, R represents each independently one group selected from the group consisting of methyl, ethyl, and phenyl, Y represents each independently an alkoxy group having 1 to 6 carbon atoms, and n is an integer of 1 or more and 3 or less.)

[0049] As the above silane coupling agent having at least one methacryloyl group, for example, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, etc. can be cited.

[0050] In addition, examples of the second silane coupling agent represented by the above general formula (1) include, for example: methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane. Preferably, in the above second silane coupling agent, X in the above general formula (1) is methyl or ethyl. Examples of such a second silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. More preferably, in the above second silane coupling agent, X in the above general formula (1) is methyl. Examples of such a second silane coupling agent include methyltrimethoxysilane and methyltriethoxysilane, and most preferably it is methyltrimethoxysilane.

[0051] In the surface-treated glass cloth of the present embodiment, the total content of the first silane coupling agent and the second silane coupling agent is preferably in the range of 0.03 to 1.50% by mass, more preferably in the range of 0.05 to 1.20% by mass, further preferably in the range of 0.1 to 1.0% by mass, particularly preferably in the range of 0.2 to 0.8% by mass, especially preferably in the range of 0.3 to 0.7% by mass, and most preferably in the range of 0.4 to 0.6% by mass, relative to the total amount of the surface-treated glass cloth.

[0052] In addition, in the surface-treated glass cloth of the present embodiment, the ratio of the content of the second silane coupling agent to the content of the first silane coupling agent (content of the second silane coupling agent / content of the first silane coupling agent) is preferably in the range of 0.01 to 0.25, more preferably in the range of 0.03 to 0.20, further preferably in the range of 0.03 to 0.17, and most preferably in the range of 0.10 to 0.17.

[0053] As a result, the surface-treated glass cloth of the present embodiment having a surface treatment layer can be obtained, and the surface of the surface treatment layer contains the first silane coupling agent having at least one methacryloyl group and the second silane coupling agent represented by the above general formula (1).

[0054] In addition, the surface-treated glass cloth of the present embodiment preferably has a surface treatment layer that does not contain a surfactant, and the thickness is preferably in the range of 5 to 60 μm, more preferably in the range of 5 to 40 μm, and further preferably in the range of 5 to 25 μm.

[0055] Here, as the thickness of the surface-treated glass cloth, the average value of the following measured values can be adopted: According to JIS R3420, the measured values of the thickness at 15 locations in the surface-treated glass cloth are measured using a micrometer.

[0056] Next, examples, comparative examples, and reference examples of the present invention are shown.

[0057] (Example 1)

[0058] In this example, a glass cloth with a gauze specification #1017 under the IPC 4412 standard for weaving (glass composition: NE glass, yarn used: BC3000 (filament diameter 4.0 μm, yarn weight 1.5 tex), warp fabric density: 95 threads / 25 mm, weft fabric density: 95 threads / 25 mm, mass per unit area: 11.4 g / m 2 ) was fibrillated by applying a water flow pressure of high-pressure water flow at 40 °C with a pressure of 2 MPa to the glass cloth, and degreasing treatment was performed by heating at a temperature of 400 - 450 °C for 60 hours. Then, the degreased glass cloth was immersed in an aqueous solution of a glass treatment agent, and after removing the excess water, it was heated and dried at 110 °C for 5 minutes to obtain the surface-treated glass cloth of this example.

[0059] The above-mentioned aqueous solution of the glass treatment agent was prepared as follows: 3-methacryloxypropyltrimethoxysilane (manufactured by Dow Toray Co., Ltd.) as the first silane coupling agent at 1.0 mass%, methyltrimethoxysilane (manufactured by Momentive Performance Materials Japan LLC) as the second silane coupling agent at 0.15 mass%, acetic acid was mixed with water to be 0.5 mass%, and stirred with a magnetic stirrer for 1 hour.

[0060] The obtained surface-treated glass cloth was cut into 350 mm × 400 mm, and the obtained surface-treated glass cloth sheet was immersed in a polyphenylene ether resin varnish and pre-dried at 150 °C for 10 minutes to obtain a prepreg. The above-mentioned polyphenylene ether resin varnish was composed of 450 parts by mass of low molecular weight polyphenylene ether (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name: OPE-2St), 100 parts by mass of triallyl isocyanurate (manufactured by Evonik Japan Co., Ltd., trade name: TAICROS), 4 parts by mass of α,α'-bis(tert-butylperoxy)diisopropylbenzene (manufactured by NOF Corporation, trade name: Perbutyl P), and 250 parts by mass of toluene (manufactured by Fujifilm Wako Pure Chemical Corporation).

[0061] Next, 4 pieces of the above prepregs were laminated, and fiber membranes were overlapped on the top and bottom, and heated and pressed for a specified time using a vacuum hot press (manufactured by Kitakawa Seiki Co., Ltd.) to obtain a laminate with a plate thickness of about 0.2 mm.

[0062] Next, the laminate obtained in this example was cut into 7 cm × 4 cm, and slits with a length of 2 cm were cut longitudinally and transversely using a diamond cutter to make test pieces. An aqueous solution of NaOH (manufactured by FUJIFILM Wako Pure Chemical Corporation) adjusted to 1 mol / L was added to a beaker and heated to a temperature of 60°C. After immersing the above test pieces in this aqueous solution for 24 hours, a digital microscope (manufactured by KEYENCE CORPORATION) was used to measure the whitening distance of the interface peeling between the resin and the glass in the warp direction and the weft direction at a magnification of 100 times. During the measurement, 24 points were measured in both the warp direction and the weft direction, and the average value was calculated and used as the whitening distance. The whitening distance caused by this peeling is correlated with the insulation reliability of the printed wiring board. The shorter the whitening distance, the higher the insulation reliability.

[0063] Next, the surface-treated glass cloth obtained in this example was cut into 90 mm × 30 mm to be used as a glass cloth piece for feel measurement. The feel was measured according to the rigid-flexible test by the sliding method based on JIS L 1096. One end of the short side of the glass cloth piece for feel measurement was fixed to a horizontal platform with a long side direction of 30 mm, and the other part was set as a free end and placed on a moving platform whose upper surface was flush with the horizontal platform. The moving platform was lowered based on the upper surface of the horizontal platform, and the moving distance of the top center of the free end from the moving platform was measured. The above moving distance was measured using 5 glass cloth pieces for feel measurement, and the average value was calculated. The moving distance of this moving platform is correlated with the feel of the glass cloth. The shorter the moving distance, the harder the feel of the glass cloth.

[0064] Next, the surface-treated glass cloth obtained in this example was cut into 60 mm × 40 mm to make an impregnation property evaluation test piece. The impregnation property evaluation test piece was immersed in benzyl alcohol, and the time from just after immersion to when benzyl alcohol completely penetrated into the glass cloth piece for impregnation property evaluation was measured in the weft direction. The measurement was performed using 5 glass cloth pieces for impregnation property evaluation, and the average value was calculated. The measurement results of the whitening distance, feel, and impregnation property are shown in Table 1. It should be noted that in Table 1, 3-methacryloxypropyltrimethoxysilane is abbreviated as "methacrylic acid silane", and methyltrimethoxysilane is abbreviated as "methyl silane".

[0065] (Example 2)

[0066] In this example, except that the amount of methyltrimethoxysilane (manufactured by Momentive Performance Materials Japan LLC), which is the second silane coupling agent contained in the glass treatment agent aqueous solution, was set to 0.05% by mass, the surface-treated glass cloth, prepreg, and laminate were obtained in exactly the same manner as in Example 1.

[0067] Next, except for using the surface-treated glass cloth and laminate obtained in this example, the whitening distance, feel, and impregnability were measured in exactly the same manner as in Example 1. The measurement results are shown in Table 1.

[0068] (Example 3)

[0069] In this example, except for adding 0.001% by mass of polyoxyethylene alkyl ether (manufactured by Toho Chemical Industry Co., Ltd.) as a surfactant to the aqueous solution of the glass treatment agent, the surface-treated glass cloth, prepreg, and laminate were obtained in exactly the same manner as in Example 2.

[0070] Next, except for using the surface-treated glass cloth and laminate obtained in this example, the whitening distance, feel, and impregnability were measured in exactly the same manner as in Example 1. The measurement results are shown in Table 1.

[0071] (Example 4)

[0072] In this example, except for setting the amount of methyltrimethoxysilane (manufactured by Momentive Performance Materials Japan LLC) as the second silane coupling agent contained in the aqueous solution of the glass treatment agent to 0.19% by mass, the surface-treated glass cloth, prepreg, and laminate were obtained in exactly the same manner as in Example 1.

[0073] Next, except for using the surface-treated glass cloth and laminate obtained in this example, the whitening distance, feel, and impregnability were measured in exactly the same manner as in Example 1. The measurement results are shown in Table 1.

[0074] (Example 5)

[0075] In this example, except for using 0.05% by mass of propyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.) instead of methyltrimethoxysilane (manufactured by Momentive Performance Materials Japan LLC) as the second silane coupling agent contained in the aqueous solution of the glass treatment agent, the surface-treated glass cloth, prepreg, and laminate were obtained in exactly the same manner as in Example 1.

[0076] Next, except for using the surface-treated glass cloth and laminate obtained in this example, the whitening distance, feel, and impregnability were measured in exactly the same manner as in Example 1. The measurement results are shown in Table 1.

[0077] It should be noted that in Table 1, propyltrimethoxysilane is abbreviated as "propyl silane".

[0078] (Example 6)

[0079] In this example, except for using a glass cloth of gauze specification #1078 under IPC 4412 standard (glass composition: NE glass, used yarn: D450 (filament diameter 5.0 μm, yarn weight 10.0 tex), warp fabric density: 53 threads / 25 mm, weft fabric density: 53 threads / 25 mm, mass per unit area: 44.0 g / m 2 ), the surface-treated glass cloth, prepreg, and laminate were prepared in exactly the same manner as in Example 1.

[0080] Next, except for using the surface-treated glass cloth and laminate prepared in this example, the whitening distance, hand feeling, and impregnation property were measured in exactly the same manner as in Example 1. The measurement results are shown in Table 2.

[0081] (Comparative Example 1)

[0082] In this comparative example, except for using 0.05% by mass of hexyltrimethoxysilane (manufactured by Dow Toray Co., Ltd.) instead of methyltrimethoxysilane (manufactured by Momentive Performance Materials Japan LLC) as the second silane coupling agent contained in the aqueous solution of the glass treatment agent, the surface-treated glass cloth, prepreg, and laminate were prepared in exactly the same manner as in Example 1.

[0083] Next, except for using the surface-treated glass cloth and laminate prepared in this comparative example, the whitening distance, hand feeling, and impregnation property were measured in exactly the same manner as in Example 1. The measurement results are shown in Table 2.

[0084] It should be noted that in Table 2, hexyltrimethoxysilane is abbreviated as "hexyl silane".

[0085] (Reference Example 1)

[0086] In this reference example, except for containing only 1.0% by mass of 3-methacryloxypropyltrimethoxysilane (manufactured by Dow Toray Co., Ltd.) as the first silane coupling agent in the aqueous solution of the glass treatment agent and completely not containing the second silane coupling agent, the surface-treated glass cloth, prepreg, and laminate were prepared in exactly the same manner as in Example 1.

[0087] Next, except for using the surface-treated glass cloth and laminate obtained in this reference example, the whitening distance, hand feel, and impregnation property were measured in exactly the same manner as in Example 1. The measurement results are shown in Table 2.

[0088] (Reference Example 2)

[0089] In this reference example, except that the silane coupling agent contained in the aqueous solution of the glass treatment agent was only 1.0 mass% of 3-methacryloxypropyltrimethoxysilane (manufactured by Dow Toray Co., Ltd.) as the first silane coupling agent and did not contain the second silane coupling agent at all, the surface-treated glass cloth, prepreg, and laminate were obtained in exactly the same manner as in Example 6.

[0090] Next, except for using the surface-treated glass cloth and laminate obtained in this reference example, the whitening distance, hand feel, and impregnation property were measured in exactly the same manner as in Example 1. The measurement results are shown in Table 2.

[0091] (Table 1)

[0092]

[0093] (Table 2)

[0094]

[0095] It should be noted that the "whitening distance deterioration rate" in Examples 1 to 5 and Comparative Example 1 in Table 1 and Table 2 represents the increase rate of the whitening distance relative to the whitening distance of Reference Example 1; the "whitening distance deterioration rate" of Example 6 represents the increase rate of the whitening distance relative to the whitening distance of Reference Example 2. The "hand feel improvement rate" in Examples 1 to 5 and Comparative Example 1 in Table 1 and Table 2 represents the reduction rate of the hand feel relative to the hand feel of Reference Example 1; the "hand feel improvement rate" of Example 6 represents the reduction rate of the hand feel relative to the hand feel of Reference Example 2.

[0096] In addition, the "hand feel improvement rate / whitening distance deterioration rate" in Table 1 and Table 2 is an index indicating the height of the insulation reliability in the printed wiring board and the ease of generating wrinkles during the manufacture of the prepreg. The larger the value, the higher the insulation reliability in the printed wiring board and the less likely to generate wrinkles during the manufacture of the prepreg.

[0097] It is obvious from Table 1 and Table 2 that the surface treated glass cloths of Examples 1 to 6 have a larger value of the hand feel improvement rate / whitening distance degradation rate than the surface treated glass cloth of Comparative Example 1, can obtain high insulation reliability in a printed wiring board, and are less likely to wrinkle when manufacturing prepreg. The surface treated glass cloths of Examples 1 to 6 have a surface treated layer on the surface, the surface treated layer containing a first silane coupling agent having at least one methacryloyl group and a second silane coupling agent represented by the general formula (1); Comparative Example 1 has a surface treated layer on the surface, the surface treated layer containing a first silane coupling agent having at least one methacryloyl group but not containing the second silane coupling agent represented by the general formula (1).

Claims

1. A surface-treated glass cloth, characterized in that, The surface-treated glass cloth has a surface treatment layer on its surface. The surface treatment layer contains a first silane coupling agent having at least one methacryloyl group and a second silane coupling agent represented by the following general formula (1). The ratio of the content of the second silane coupling agent to the content of the first silane coupling agent, that is, the content of the second silane coupling agent / the content of the first silane coupling agent, is in the range of 0.03 to 0.

17. The surface treatment layer does not contain a surfactant. The mass per unit area of the surface-treated glass cloth is 8 g / m 2 or more and 110 g / m 2 or less. X(R) 3-n SiY n …(1), In the formula, X is an alkyl group having 1 to 4 carbon atoms, R is each independently one group selected from the group consisting of methyl, ethyl, and phenyl, Y is each independently an alkoxy group having 1 to 6 carbon atoms, and n is an integer of 1 or more and 3 or less.

2. The surface-treated glass cloth according to claim 1, wherein In the general formula (1), X of the second silane coupling agent is methyl or ethyl.

3. The surface-treated glass cloth according to claim 1, wherein In the general formula (1), X of the second silane coupling agent is methyl.

4. The surface-treated glass cloth according to claim 1, characterized in that, The thickness of the surface-treated glass cloth is in the range of 5 to 25 μm.

5. A prepreg, characterized in that, Comprising the surface-treated glass cloth according to any one of claims 1 to 4.

6. A printed wiring board, characterized in that, Comprising the surface-treated glass cloth according to any one of claims 1 to 4.

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