TW202244343A - glass cloth - Google Patents

Abstract

The purpose of the present invention is to provide a glass cloth in which a residual curvature 2HB/B, which is the ratio of the weft-direction curve hysteresis 2HB to the weft-direction bending stress B, is 0.5 (cm-1) or less, and the residual shear distortion 2HG/G, which is the ratio of the weft-direction shear hysteresis 2HG (gf/cm) to the weft-direction shear stress G (gf/cm/deg), is 1.4 (deg -1) or less. Provided is a glass cloth in which glass yarn composed of a plurality of long glass fibers is configured as warp and weft, wherein at least a part of the surface of the long glass fibers includes (A) a polyoxyalkylene bisphenol A ether and (B) a silane coupling agent having an acrylic group or a methacrylic group, the warp density and weft density of the glass cloth are each at least 70 per 25 mm, and the amount of carbon in the glass cloth is 0.4-1.5 mass%.

Description

glass cloth

The present invention relates to glass cloth and prepreg.

A laminated board such as a printed wiring board is provided with an insulating layer and a conductive layer formed thereon. The insulating layer is usually made of glass fiber-reinforced resin that has been reinforced with glass fibers such as glass cloth.

In recent years, the demand for miniaturization and high performance of electronic components has become prominent, and further miniaturization is also required for laminated boards. Then, in response to the demand, thin printed wiring boards or multilayer printed wiring boards have been developed, and thin glass cloths have been developed as glass fibers for these.

For example, Patent Document 1 describes a glass cloth that suppresses the occurrence of pinholes in a prepreg using glass cloth even if the average number of layers is less than 3.00, and maintains the prepreg because the glass cloth rarely fluffs. The excellent appearance quality of the immersion body. Specifically, Patent Document 1 describes a glass cloth. In terms of the composition of the aforementioned glass cloth, it is composed of warp yarns and weft yarns. The range of 55 yarns is bundled, the weaving density of the warp and weft yarns falls in the range of 86~140 yarns/25mm, and it has a thickness in the range of 7.5~12.0µm and a mass in the range of 6.0~10.0g per 1m ² , and the The average number of layers of glass cloth falls within the range of more than 2.00 and less than 3.00. The average number of layers is the value obtained by dividing the thickness of the glass cloth by the average value of the diameter of the long glass fibers of the warp and the diameter of the long glass fibers of the weft (thickness of glass cloth /{(long glass fiber diameter of the warp + long glass fiber diameter of the weft)/2}) to represent; the average opening degree falls in the range of 1.000~1.300, and the average opening degree is based on the opening degree of the warp yarn (warp yarn width /(The diameter of the glass long fibers constituting the warp x the number of glass long fibers constituting the warp)) and the opening degree of the aforementioned weft yarn (weft yarn width/(the diameter of the glass long fibers constituting the weft x the number of glass long fibers constituting the weft)) The geometric mean ((the opening degree of the warp yarn × the opening degree of the weft yarn) 1/2); the yarn width ratio falls in the range of 0.720~0.960, and the yarn width ratio is the ratio of the width of the warp yarn relative to the width of the weft yarn Ratio (warp yarn width/weft yarn width) to express.

On the other hand, in order to improve the wettability and adhesion of the matrix resin in the prepreg and the printed wiring board obtained from the prepreg to the glass cloth, the glass cloth will be surface-treated with a silane coupling agent. As the surface-treated glass cloth, a surface-treated glass fiber fabric is known, which includes a glass fiber fabric and a treatment agent attached to the glass fiber fabric. The treatment agent contains a silane compound and a water-soluble polyurethane (see, for example, Patent Document 2). According to this surface-treated glass fiber fabric, it is possible to provide a surface-treated glass fiber fabric and a method for producing the same, which rarely generates yarn slipping and has sufficient rigidity even when the thickness is reduced. prior art literature patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2018-21274 Patent Document 2: Japanese Patent Laid-Open No. 2006-342445

The problem to be solved by the invention In recent years, in order to respond to the demand for miniaturization of electronic equipment and the need for high-mountability of printed wiring boards for the purpose of high performance, the thinning of prepregs and printed wiring boards has been further promoted. In order to reduce the thickness of prepregs and printed wiring boards, thin glass cloth is required. In addition, due to the rapid increase in the demand for high-speed transmission and processing of large-capacity data, there is a situation in which a lower dielectric constant is required for glass fibers used in prepregs and printed wiring boards.

In order to form thin glass cloth, warp and weft yarns composed of glass fibers with small fiber diameters must be used for weaving, and the warp yarns and weft yarns must be flattened by fiber opening treatment.

In order to lower the dielectric constant of the glass fiber, low dielectric constant glass (for example, NE glass, L glass, LU glass manufactured by Unitika Co., Ltd., etc.) can be used as the glass material constituting the glass fiber.

Compared with the thicker glass cloth using widely used E glass, thin glass cloth or glass cloth using low dielectric constant glass has the problem of low tensile strength and easy breakage.

Here, the glass cloth used for the prepreg and the printed wiring board is surface-treated with a surface treatment agent containing a silane coupling agent. This surface treatment step is carried out in the final step of the glass cloth. The surface treatment is carried out by soaking the continuous glass cloth in the warp direction into the surface treatment agent including silane coupling agent, adjusting the adhesion amount of the surface treatment agent with nip rollers, and drying it. The dried glass cloth will be rolled up to make a glass cloth roll, and the glass cloth roll will be rolled back and soaked with matrix resin to make a prepreg.

Moreover, the inventors of this case have learned after research that there is the following problem: When using the technology of Patent Documents 1 and 2 to manufacture such as thin glass cloth or glass cloth with low dielectric constant glass, etc., the tensile strength is low. In the case of glass cloth, if the tension in the warp direction of the glass cloth load is set low in the surface treatment step of the final step in order to prevent the glass cloth from breaking, etc., warp streaks ( Streaks extending along the length of the warp of glass cloth). Specifically, it is known that due to the reduction of the tension in the warp direction, deflection or undulation occurs in the weft direction (width direction) of the glass cloth in the surface treatment step, and if the deflection or undulation occurs directly through the nip roll, then Glass cloth bends and overlaps across the width, thus causing warp streaks. If warp streaks are generated in the surface treatment step of the final step, the warp streaks will be directly brought into the prepreg manufacturing step, which may affect the grade of the prepreg.

Also, the inventors of the present case have learned after research that the following situations exist: when using the technology of Patent Documents 1 and 2 to manufacture, for example, glass cloth with thin thickness or glass cloth with low dielectric constant glass, etc., which have low tensile strength In the case of glass cloth, a part of the glass cloth will be oblique during winding (the weft yarn is not at a right angle to the warp yarn), and the stress is concentrated on the oblique part, resulting in oblique wrinkles during winding (along the non-parallel to the length of the warp yarn). direction and not parallel to the direction of the weft length direction of the crease). For example, the use of thicker glass cloth with E glass material usually does not cause this phenomenon. Moreover, if oblique wrinkles are generated during the coiling of the surface treatment step in the final step, the oblique wrinkles will be directly brought into the prepreg manufacturing step, which may affect the grade of the prepreg.

After further study, the inventors of the present case found out that in order to suppress the aforementioned warp streaks, the important method is to set the "ratio of the bending hysteresis 2HB in the weft direction to the bending stress B in the weft direction, that is, the residual curvature 2HB/B" as 0.5 (cm ^-1 ) or less, the residual curvature is calculated by using a pure bending tester, which is one of the property measuring instruments, under the conditions described later. The residual curvature 2HB/B is calculated from the bending hysteresis (2HB) and the bending rigidity (B). The bending hysteresis (2HB) and the bending rigidity (B) are obtained from the hysteresis curve in the bending characteristics measured by a pure bending tester. Calculated, the energy loss in the process from bending deformation to recovery deformation can be grasped by the amount of residual strain, and the restoring force can be quantified by the value of 2HB/B. That is, the residual curvature 2HB/B can be understood as the residual strain during the process from bending deformation to recovery deformation, and the smaller the residual strain, the higher the restoring force. The inventors of the present invention found that by setting the residual curvature 2HB/B to 0.5 (cm ^-1 ) or less, warping or waviness is less likely to occur in the glass cloth manufacturing process, and it is possible to easily prevent the occurrence of warping when passing through nip rolls in the process. Streaks.

In addition, the inventors of the present case have studied and learned that: in order to suppress the above-mentioned oblique creases, the important method is to make "the shear hysteresis 2HG (gf/cm) in the weft direction relative to the shear stress G (gf/cm) in the weft direction /deg), that is, the residual shear strain rate 2HG/G" is 1.4 (deg ^-1 ) or less. Cut the test machine to calculate. The residual shear strain rate 2HG/G is calculated from the shear hysteresis (2HG) and the shear stress (G), and the shear hysteresis (2HG) and the shear stress (G) are measured using a tensile shear tester. The hysteresis curve in the shear characteristic is calculated, the energy loss in the process from shear deformation to recovery deformation can be grasped by the residual strain, and the recovery force can be quantified by the value of 2HG/G. In other words, this value can be understood as the residual strain during the process from shear deformation to recovery deformation, and the smaller the residual strain, the higher the restoring force. The inventors of the present invention found that by setting the residual shear strain rate to 1.4 (deg ^-1 ) or less, the strain existing in the glass cloth can be easily relaxed during the cloth conveyance in the surface treatment step, and it is easy to prevent the oblique direction at the time of winding. wrinkles.

Therefore, the main subject of the present invention is to solve the above problems and provide a glass cloth with a residual curvature 2HB/B of 0.5 (cm ^-1 ) or less and a residual shear strain rate 2HG/G of 1.4 (deg ^-1 ) below, the above-mentioned residual curvature 2HB/B is the ratio of the bending hysteresis 2HB in the weft direction to the bending stress B in the weft direction, and the above-mentioned residual shear strain rate 2HG/G is the shear hysteresis 2HG (gf/cm) in the weft direction relative to The ratio of the shear stress G (gf/cm/deg) in the weft direction. Also, another object of the present invention is to provide a glass cloth in which warp streaks and oblique wrinkles are suppressed. means to solve problems

The inventors of this case have conducted research on the above-mentioned problems. In order to reduce the residual curvature 2HB/B, it is necessary to reduce the bending hysteresis 2HB in the weft direction while increasing the bending rigidity B. And it is known that in order to reduce the bending hysteresis 2HB of the weft direction of the glass cloth, an important method is to impart a surface treatment agent to the glass cloth in the surface treatment step. The surface treatment agent includes: (A) polyoxyalkylene bisphenol A ether, and (B) a silane coupling agent having an acryl group or a methacryl group. It is also known that increasing the adhesion amount of the surface treatment agent can effectively improve the bending rigidity B.

Also, in order to reduce the residual shear strain rate in the weft direction, it is necessary to reduce the shear hysteresis 2HG in the weft direction and increase the shear stress G in the weft direction. In order to reduce the shear hysteresis 2HG in the weft direction of the glass cloth, it is known that an important method is to impart a surface treatment agent to the glass cloth in the surface treatment step. The surface treatment agent includes: (A) polyoxyalkylene bisphenol A ether, and (B) a silane coupling agent having an acryl group or a methacryl group. It is also known that in order to increase the shear stress G in the weft direction, it is important to set the warp density and weft density of the glass cloth to a certain value or more to increase the friction caused by the movement of the interweaving point accompanying shear deformation. .

Furthermore, the inventors of the present invention have found that, in a glass cloth composed of glass yarns composed of a plurality of long glass fibers as warps and wefts, at least a part of the surface of the long glass fibers contains: (A) polyoxyalkylene Bisphenol A ether, and (B) silane coupling agent with acryl or methacryl group, and the warp yarn density and weft yarn density of the glass cloth are set to 70 yarns/25mm or more, and the carbon content of the glass cloth is set 0.4~1.5% by mass, the residual curvature 2HB/B will be 0.5(cm ^-1 ) or less and the residual shear strain rate 2HG/G will be 1.4(deg ^-1 ) or less, which can suppress the generation of warp streaks and Diagonal wrinkles.

The present invention is an invention completed through repeated painstaking studies based on the above-mentioned knowledge and insights.

That is, the present invention provides the inventions of the aspects disclosed below. Item 1. A glass cloth composed of glass yarns composed of a plurality of long glass fibers as warp yarns and weft yarns; At least a part of the surface of the aforementioned long glass fiber comprises: (A) polyoxyalkylene bisphenol A ether, and (B) a silane coupling agent having an acryl or methacryl group; The warp yarn density and weft yarn density of the aforementioned glass cloth are 70 threads/25mm or more; In addition, the carbon content of the aforementioned glass cloth is 0.4-1.5% by mass. Item 2. The glass cloth as in Item 1, the tensile strength in the warp direction is 20~120N/25mm. Item 3. The glass cloth as described in item 1 or 2, the thickness of which is 5~30µm. Item 4. The glass cloth according to any one of Items 1 to 3, which is a rolled long glass cloth obtained by winding the glass cloth around a core. Item 5. A prepreg comprising: the glass cloth according to any one of items 1 to 4, and a thermosetting resin contained in a state soaked into the glass cloth. Invention effect

According to the glass cloth of the present invention, by using a specific surface treatment agent for surface treatment, and setting the weaving density and carbon content of the glass cloth within a specific range, the residual curvature 2HB/B can be satisfied below 0.5 (cm ^-1 ) and The residual shear strain rate 2HG/G is not more than 1.4 (deg ^-1 ), which effectively suppresses the generation of meridional streaks and oblique wrinkles.

1. Glass cloth The glass cloth of the present invention is composed of glass yarns composed of a plurality of long glass fibers as warp and weft, and at least a part of the surface of the long glass fibers includes: (A) polyoxyalkylene bisphenol A ether, and ( B) A silane coupling agent having an acryl group or a methacryl group, the weaving density of the aforementioned glass cloth is 70 strands/25mm or more, and the carbon content of the aforementioned glass cloth is 0.4-1.5% by mass. Hereinafter, the glass cloth of the present invention will be described in detail.

[Glass yarn constituting glass cloth] In the glass cloth of the present invention, glass yarns composed of a plurality of long glass fibers are used as warp yarns and weft yarns.

In the glass cloth of the present invention, the glass material constituting the long glass fibers is not particularly limited. Examples thereof include E glass, T glass, S glass, UT glass, D glass, NE glass, L glass, LU glass manufactured by Unitika Co., Ltd., C glass, or AR glass.

From the point of view of wide applicability, it is advisable to use glass yarn composed of E glass. The aforementioned E glass composition includes the following composition: SiO ₂ in the range of 52 to 56 mass %, B ₂ O ₃ in the range of 5 to 10 mass %, and Al in the range of 12 to 16 mass % relative to the total amount of glass fibers ₂ O ₃ , CaO and MgO in the range of 20 to 25% by mass in total, and Li ₂ O, K ₂ O, and Na ₂ O in the range of 0 to 1% by mass in total.

Also, from the viewpoint of further improving the strength of the prepreg and the printed wiring board, the glass yarn is preferably composed of a glass material having a composition including SiO ₂ , 20 Al ₂ O ₃ in the range of ~26% by mass and MgO in the range of 10-15% by mass.

In addition, from the viewpoint of reducing the dielectric constant and dielectric tangent of the prepreg and the printed wiring board, the glass yarn is preferably composed of a glass material containing SiO in the range of 45 to 60% by mass relative to the total amount of glass fibers. _2. B ₂ O ₃ in the range of 15 to 35% by mass, Al ₂ O ₃ in the range of 10 to 20% by mass, and CaO in the range of 1 to 15% by mass; it is preferably composed of the following glass materials: relative to The total amount of glass fibers is SiO ₂ in the range of 45 to 55% by mass, B ₂ O ₃ in the range of 20 to 35% by mass, Al ₂ O ₃ in the range of 10 to 20% by mass, and 3 to 10% by mass CaO.

In addition, in the present invention, the glass composition is measured by ICP emission spectrometry. Specifically, the Si content and B content are obtained by dissolving the weighed glass cloth sample with sodium carbonate, dissolving it in dilute nitric acid and constant volume, and then measuring the obtained sample by ICP emission spectrometry. In addition, the Fe content was obtained by dissolving the weighed glass cloth sample by alkali dissolution method and constant volume, and then measuring the obtained sample by ICP emission spectrometry. Moreover, the Al content, Ca content, and Mg content are determined by heating and decomposing the weighed glass cloth sample with sulfuric acid, nitric acid, and hydrofluoric acid, then dissolving in dilute nitric acid and constant volume, and then the obtained sample is measured by ICP Obtained by emission spectroscopic analysis. In addition, as an ICP emission spectrometer, iCAP6300Duo manufactured by Thermo Fisher Scientific Inc. can be used.

In the glass cloth of the present invention, the average fiber diameter of the glass long fibers is not particularly limited. The average fiber diameter of the glass long fibers can be, for example, 2-7 µm. From the viewpoint of making the effects of the present invention more easily exhibited, it is preferably 2.5-5.5 µm, more preferably 3-5 µm.

In addition, in the glass cloth of the present invention, the number of long glass fibers constituting the glass yarn is not particularly limited. For example, 20-200 roots can be mentioned. From the viewpoint of making the effects of the present invention more easily exhibited, 20-100 roots are preferable, more preferably 20-50 roots or 30-50 roots.

The average fiber diameter and number of long glass fibers were measured and calculated as follows. That is, two pieces of glass cloth to be measured are cut into 30 cm squares, one of them is used for warp yarn observation, and the other is used for weft yarn observation, and each of these is embedded in epoxy-based cold embedding resin. Let it harden. Next, after grinding the glass cloth embedded in the epoxy-based cold embedding resin to the extent that the warp or weft can be observed, use SEM (trade name JSM-6390A manufactured by Japan Electronics Co., Ltd.) to observe the average at a magnification of 2000 times Fiber diameter, the number of fibers observed at a magnification of 500 times. (1) Average fiber diameter of glass yarn (µm) 30 warp and weft yarns were randomly selected, and the cross-sections of the long fibers contained in the 30 glass yarns were observed and the diameters were measured, and the average value was calculated as the average fiber diameter of the glass long fibers of the warp and weft yarns. (2) Number of roots (root) 30 warp yarns and weft yarns were randomly selected, the number of long fibers contained in each of the 30 glass yarns was measured, and the average value was calculated as the number of warp yarns and weft yarns.

In addition, in the glass cloth of the present invention, the number of glass yarns is not particularly limited. For example, it can be 0.5~25 tex. From the point of view of making the effect of the present invention more easily exerted, it is preferably 0.5~12 tex, more preferably 0.5~5 tex, more preferably 0.8~3.2 tex. In addition, in the present invention, the number of the glass yarn is a value measured and calculated according to the method stipulated in "No. 7.1" of the Japanese Industrial Standard JIS R 3420 2013 "General Test Methods for Glass Fibers".

[Density and Weaving Structure of Glass Cloth] The warp yarn density and weft yarn density of the glass cloth of the present invention are more than 70 yarns/25mm. Thereby, the shear stress G in the weft direction of the glass cloth can be increased, and it is easy to satisfy the residual shear strain rate 2HG/G of 1.4 (deg ^-1 ) or less. From the same point of view, the warp yarn density and weft yarn density should be more than 85 yarns/25mm. The upper limit of the warp yarn density and the weft yarn density is not particularly limited. From the viewpoint of lowering the quality of the glass cloth, it is preferably 130 yarns/25mm or less, more preferably 120 yarns/25mm or less. Specifically, the warp yarn density and weft yarn density can be 70-130 yarns/25mm, and preferably 85-120 yarns/25mm. In addition, in the present invention, warp density and weft density are values measured and calculated according to the method specified in "7.9 Density (Weaving Density)" of JIS R 3420 2013 "General Test Methods for Glass Fibers" in Japanese Industrial Standards.

In addition, the glass cloth is produced in a state where a stronger tension is applied to the warp yarn than to the weft yarn during production. As a result, the weft yarns of the glass cloth are produced under a weak tension state, so the line width variation when viewed from the glass cloth plane direction becomes larger than the line width variance of the warp yarns. Therefore, in the present invention, the weft yarn can also be defined as a glass yarn having a large variation in line width when viewed from a planar direction among the warp yarn and the weft yarn.

The weave of the glass cloth is not particularly limited, and examples include plain weave, satin weave, twill weave, basket weave, muscular weave, and the like. Among them, plain weave is preferred.

[Surface treatment of glass cloth] The glass cloth of the present invention contains at least a part of the surface of the long glass fiber: (A) polyoxyalkylene bisphenol A ether, and (B) having acryl or methacryl Silane coupling agent. By including these, the bending hysteresis 2HB in the weft direction of the glass cloth can be reduced, and the residual curvature 2HB/B can be made 0.5 (cm ⁻¹ ) or less. Also, by including these, the shear hysteresis 2HG in the weft direction of the glass cloth can be reduced, and the residual shear strain rate 2HG/G can be made 1.4 (deg ^-1 ) or less.

The polyoxyalkylene bisphenol A ether is a compound represented by the following general formula (1). [chemical formula 1]

In the general formula (1), R ¹ and R ² may be the same or different, and represent an alkylene group. The number of carbon atoms in the alkylene group can be, for example, 2 to 4, preferably 2 or 3, more preferably 2. In the general formula (1), n ¹ and n ² represent the average added moles of alkylene oxide. n ¹ and n ² can be, for example, 2-50, preferably 4-30, more preferably 6-20. n ¹ and n ² may be different numerical values, or substantially the same numerical value. As an aspect of the polyoxyalkylene bisphenol A ether, in the general formula (1), R ¹ and R ² are the same alkylene group, and n ¹ and n ² are substantially the same value.

The polyoxyalkylene bisphenol A ether used in the present invention is preferably polyoxyethylene bisphenol A ether or polyoxypropylene bisphenol A ether. Among them, polyoxyethylene bisphenol A ether is more preferable from the viewpoint of excellent lubricity and easier reduction of fuzzing of the glass cloth. The average added mole number of alkylene oxide in the polyoxyalkylene bisphenol A ether used in the present invention can be, for example, 2-40, preferably 4-30, more preferably 6-20. Here, the average added mole number of alkylene oxide in polyoxyalkylene bisphenol A ether is the alkylene oxide contained in the two polyalkylene oxide chains constituting polyoxyalkylene bisphenol A ether. The average of the total.

Examples of the silane coupling agent having an acryl group or a methacryl group include compounds represented by the following general formula (2). [Chemical formula 2] CH ₂ =CR ³ -CO-OR ⁴ -SiR ⁵ _m (OR ⁶ ) _3-m (2)

In the general formula (2), R ³ represents a hydrogen atom or a methyl group. In the general formula (2), R ⁴ is an alkylene group having 1 to 6 carbon atoms. R ⁴ is preferably an alkylene group with 1 to 4 carbon atoms, more preferably an alkylene group with 2 to 4 carbon atoms, more preferably an alkylene group with 3 carbon atoms. The alkylene group of R ⁴ may be either linear or branched, preferably branched. In the general formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 5 carbon atoms. R ⁵ and R ⁶ are preferably alkyl groups having 1 to 3 carbon atoms, more preferably alkyl groups having 1 or 2 carbon atoms, and more preferably methyl groups. In general formula (2), m represents the integer of 0-2. m is preferably 0 or 1, more preferably 0.

A silane coupling agent having an acryl group or a methacryl group, specifically the following can be exemplified: 3-acryloxypropyl trimethoxysilane (in general formula (2), R ³ is H, R ⁴ -C ₃ H ₆ -, m is 0, R ⁶ is -CH ₃ compound), 3-methacryloxypropyltrimethoxysilane (in general formula (2), R ³ is -CH ₃ , R ⁴ is -C ₃ H ₆ -, m is 0, R ⁶ is a compound of -CH ₃ ), 3-acryloxypropylmethyldimethoxysilane (in general formula (2), R ³ is H, R ⁴ is -C ₃ H ₆ -, m is 1, R ⁵ and R ⁶ are -CH ₃ compounds), 3-methacryloxypropylmethyldimethoxysilane (general formula (2), R ³ is -CH ₃ , R ⁴ is -C ₃ H ₆ -, m is 1, R ⁵ and R ⁶ are -CH ₃ compounds), 3-acryloxypropyl triethoxy Silane (in general formula (2), R ³ is H, R ⁴ is -C ₃ H ₆ -, m is 0, R ⁶ is a compound of -C ₂ H ₅ ), 3-methacryloxypropane Triethoxysilane (in the general formula (2), R ³ is -CH ₃ , R ⁴ is -C ₃ H ₆ -, m is 0, R ⁶ is a compound of -C ₂ H ₅ ). Among them, 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane are preferable.

In the glass cloth of the present invention, the ratio of (A) polyoxyalkylene bisphenol A ether to (B) silane coupling agent having acryl or methacryl group can be exemplified as: (A) polyoxyalkylene The total amount of alkyl bisphenol A ether is 100 parts by mass per 100 parts by mass. (B) The total amount of silane coupling agent having acryl or methacryl group is 1-1000 parts by mass, preferably 10-500 parts by mass. More preferably, it is 50-400 mass parts.

Also, in the glass cloth of the present invention, the mass ratio of (A) polyoxyalkylene bisphenol A ether can be, for example, 10 to 90 parts by mass in the total amount of components attached to the surface of the glass long fibers per 100 parts by mass, It is preferably 10 to 80 parts by mass, more preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass.

Also, in the glass cloth of the present invention, in every 100 parts by mass of the total amount of components attached to the surface of the glass long fibers, the mass ratio of (B) a silane coupling agent having an acryl group or a methacryl group can be, for example, 10 ~90 parts by mass, preferably 20~80 parts by mass.

In the glass cloth of the present invention, at least a part of the surface of the long glass fibers may contain (B) a silane coupling agent other than the silane coupling agent having an acryl group or a methacryl group. (B) Silane coupling agents other than silane coupling agents with acryl or methacryl groups include the following: silane coupling agents with amino groups, silane coupling agents with vinyl groups, and silanes with phenyl groups Coupling agent, silane coupling agent with glycidyl group, silane coupling agent with isocyanate group, silane coupling agent with mercapto group, silane coupling agent with styryl group, silane coupling agent with urea group. Combined use of (B) silane coupling agent with acryl or methacryl group and silane coupling agent with amino or vinyl group can improve the adhesion to matrix resin when making prepreg Especially ideal.

Examples of the silane coupling agent having an organic functional group including an amino group include compounds represented by the following general formula (3) and salts thereof. [Chemical formula 3] X-SiR ⁷ _p (OR ⁸ ) _3-p (3)

In general formula (3), X represents an organic functional group having one or more amino groups. In general formula (3), p represents an integer of 0 to 2. p is preferably 0 or 1, more preferably 0. In the general formula (3), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 5 carbon atoms. R ⁷ and R ⁸ are preferably alkyl groups having 1 to 3 carbon atoms, more preferably alkyl groups having 1 or 2 carbon atoms.

Specific examples of silane coupling agents with amino groups include: N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane and its hydrochloride, N-β-(N- Vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane and its hydrochloride, N-β-(N-benzylaminoethyl)-γ-aminopropyltrimethoxysilane and its hydrochloride Hydrochloride, N-β-(N-benzylaminoethyl)-γ-aminopropyltriethoxysilane and its hydrochloride, γ-(2-aminoethyl)aminopropyltrimethoxysilane , γ-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane and other monomer compounds or a mixture thereof. Among them, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyl trimethoxysilane and its hydrochloride, N-β-(N-vinylbenzyl N-β-(N-benzylaminoethyl)-γ-aminopropyltrimethoxysilane and its hydrochloride , N-β-(N-benzylaminoethyl)-γ-aminopropyltriethoxysilane and its hydrochloride.

Examples of the silane coupling agent having a vinyl group or a styrene group include compounds represented by the following general formula (4). [Chemical formula 4] Y-SiR ⁹ _q (OR ¹⁰ ) _3-q (4)

In the general formula (4), Y represents an organic functional group containing one or more vinyl groups or styryl groups. In the general formula (4), ^R9 is an alkyl group with 1 to 8 carbon atoms, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl or tertiary butyl. Also, in the general formula (4), OR ¹⁰ is an alkoxy group having 1 to 8 carbon atoms which may have a substituent, and is preferably a methoxy group, an ethoxy group or a methoxyethoxy group. In the general formula (4), q is an integer of 0 to 2 and is preferably 0.

Specific examples of silane coupling agents having vinyl or styryl groups include: vinyl trimethoxysilane, vinyl triethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, styryl trimethoxysilane Oxysilane etc.

In the glass cloth of the present invention, in every 100 parts by mass of the total amount of components attached to the surface of the glass long fibers, the mass ratio of the total amount of silane coupling agent can be, for example, 10-90 parts by mass, preferably 40-90 parts by mass. It is preferably 45 to 85 parts by mass. Here, the total amount of silane coupling agents is the total mass of (B) silane coupling agents having acryl or methacryl groups and other silane coupling agents included as required.

Also, in the glass cloth of the present invention, in every 100 parts by mass of the total amount of silane coupling agent attached to the surface of the glass long fiber, (B) the mass ratio of the silane coupling agent having an acryl group or a methacryl group can be exemplified For example, 10-100 parts by mass, preferably 30-100 parts by mass, more preferably 50-100 parts by mass. Here, the total amount of silane coupling agents is the total mass of (B) silane coupling agents having acryl or methacryl groups and other silane coupling agents included as required.

In addition, in the glass cloth of the present invention, at least a part of the surface of the long glass fibers may contain a softening agent, an antistatic agent, or a surfactant as required. Softeners, antistatic agents, and surfactants can be properly selected according to the type of surface treatment agent used.

[Physical Properties of Glass Cloth, etc.] The carbon content of the glass cloth of the present invention is 0.4 to 1.5% by mass. The amount of carbon is an indicator of the adhesion of the surface treatment agent. The surface treatment agent is composed of: (A) polyoxyalkylene bisphenol A ether, and (B) silane coupling with acryl or methacryl dosers. By setting the amount of carbon within the above-mentioned range, the bending rigidity B can be effectively improved, and the residual curvature 2HB/B can be made 0.5 (cm ⁻¹ ) or less. From the standpoint of making it easier to improve the adhesion to the matrix resin when forming a prepreg, the aforementioned carbon content is preferably 0.5-1.2% by mass, more preferably 0.6-1.1% by mass. In the present invention, the amount of carbon is a value measured by the following procedure. First, using a total carbon measuring device, the glass cloth is burned and reduced under the oxygen cycle at a reaction temperature of 850°C and a reduction temperature of 600°C, and the thermal conductivity detector (TCD) is used to quantify the porous polymer bead-filled column layer. Analysis and separation of total organic carbon. Next, the carbon content of the glass cloth was calculated from the calibration curve prepared using the element quantification standard sample acetaminophen as the standard sample.

In the glass cloth of the present invention, the loss on ignition is not particularly limited, and may be, for example, 0.2-1.5 mass%, preferably 0.5-1.5 mass%, more preferably 1.0-1.4 mass%, more preferably 1.05-1.3 mass%. In the present invention, the loss on ignition is a value measured in accordance with the method specified in "7.3.2 Loss on ignition" of Japanese Industrial Standard JIS R 3420:2013 "General Test Methods for Glass Fibers".

The mass of the glass cloth of the present invention is not particularly limited, for example, 5-50 g/m ² , preferably 5-30 g/m ² , more preferably 5-20 g/m ² . In the present invention, the quality of glass cloth is the value measured according to the method specified in "7.2 Quality of cloth and mat (mass)" of Japanese Industrial Standard JIS R 3420:2013 "General Test Methods for Glass Fiber".

The thickness (µm) of the glass cloth of the present invention is not particularly limited, and may be, for example, 5-50 µm, preferably 5-30 µm, more preferably 9-25 µm. In the present invention, the thickness of the glass cloth is determined by using an electronic micrometer with a minimum display value of 0.001 mm, which is specified in "7.10.1 Cloth Thickness" of the Japanese Industrial Standard JIS R 3420:2013 "General Test Methods for Glass Fibers" The value measured by method B.

In the glass cloth of the present invention, the tensile strength in the warp direction can be 20-120N/25mm, preferably 25-110N/25mm, more preferably 30-100N/25mm. In addition, the above-mentioned tensile strength is a value calculated by using constant velocity according to the method stipulated in "7.4.2 In the case of cloth" in Japanese Industrial Standard JIS R 3420:2013 "General Test Methods for Glass Fibers". In the elongation type tensile testing machine, the length of the test piece is set to 25 cm, the width of the test piece (the width before the yarn is removed from the The width after the yarn) is set to 25mm, the constant speed stretching speed is set to 200mm/min, and the warp direction of the glass cloth is measured 5 times, and the average value is regarded as the tensile strength of the warp direction of the glass cloth (N/25mm) .

In addition, when manufacturing glass cloth, deoiling of sizing agents and pastes required for weaving warp and weft yarns is carried out. This deoiling treatment is called thermal cleaning treatment. The tensile strength of the glass cloth after the heat cleaning treatment is reduced to less than half of that before the heat cleaning treatment. Moreover, the ideal range of 20~120N/25mm for the aforementioned tensile strength means that the tensile strength of the glass cloth after heat cleaning treatment is very different from that of glass cloth without heat cleaning treatment.

Regarding the glass cloth of the present invention, in the glass cloth composed of glass yarns composed of a plurality of long glass fibers as warp and weft yarns, at least a part of the surface of the long glass fibers contains: (A) polyoxyalkylene bismuth Phenol A ether, and (B) a silane coupling agent having an acryl or methacryl group, the weaving density of the aforementioned glass cloth is 70 strands/25 mm or more, and the carbon content of the aforementioned glass cloth is 0.4-1.5% by mass, Based on the above, the residual curvature 2HB/B is 0.5 cm ⁻¹ or less and the residual shear strain rate 2HG/G is 1.4 (deg ⁻¹ ) or less. The more desirable range of the residual curvature 2HB/B possessed by the glass cloth of the present invention is 0.1 cm ^-1 to 0.5 cm ^-1 , more preferably 0.2 cm ^-1 to 0.45 cm ^-1 . Furthermore, the more desirable range of the residual shear strain rate 2HG/G possessed by the glass cloth of the present invention is preferably not less than 0.1 deg ^-1 and not more than 1.4 deg ^-1 , more preferably not less than 0.5 deg ^-1 and not more than 1.2 deg ^-1 , more preferably not less than 0.7deg ^-1 and not more than 1.1deg ^-1 .

In the present invention, the residual curvature 2HB/B of the glass cloth is a value measured using a KES-FB2 pure bending tester manufactured by KATO TECH CO., LTD. Hereinafter, the method of measuring the residual curvature 2HB/B of the glass cloth will be described with reference to FIG. 1 . The left picture of Figure 1(a) is a schematic diagram of the state where the glass cloth is bent into an arc shape by a pure bending test machine, and the right picture of Figure 1(a) is a schematic diagram showing that the glass cloth is bent into an arc shape by a pure bending test machine A graph of the bending moment (M) generated in the state. Figure 1(b) is an example of a bending hysteresis curve obtained using a pure bending tester. First, two pieces of glass cloth cut into 20 cm x 20 cm were prepared, and these two pieces were stacked so that the respective warp and weft yarns were in the same direction to prepare a test sample. In addition, when the warp and weft in the glass cloth cannot be clearly distinguished immediately, it is only necessary to determine that the yarn width variation when viewed from the plane direction is equivalent to the weft as described above. The test sample was fixed so that the distance between the jigs might become 1 cm. When fixing, the two ends of the weft yarn of the test sample in the length direction (that is, the direction in which the weft yarn is continuous) are equally wrapped around the fixture. Next, as shown in Figure 1(a), bend into an arc shape at a constant speed (deformation speed (0.5-1/sec)) until the weft yarn becomes curvature K=+2.5cm ^{-1 ,} and then bend at a constant speed (deformation speed) (0.5 ^-1 /sec)) bend to the opposite side into an arc shape until the weft reaches the maximum curvature -2.5cm ^-1 and then return to the original shape, thereby performing a bending test and measuring the bending moment generated together with the curvature change (Fig. 1(a)). The bending test was set as one cycle, and the bending hysteresis curve (vertical axis: bending moment, horizontal axis: curvature) as shown in Fig. 1(b) was obtained as the bending characteristic value. From this bending hysteresis curve, the bending rigidity B (gf·cm ² /cm) and the hysteresis width 2HB (gf·cm/cm) per unit length were calculated. This measurement is performed under the environment of 23°C and 50%RH. In addition, in the present invention, the bending rigidity B per unit length is calculated by the average slope of the differential value of the bending moment (M) measured between the curvature K=+0.5cm ^-1 to +1.5cm ^-1 , hysteresis Width 2HB is calculated by the hysteresis width of curvature K=+1.0cm ^-1 (refer to Fig. 1(b)). This measurement can be performed, for example, using the KES-FB SYSTEM (Ver.7.18WJ) data measurement program, and B and 2HB can be calculated using the KES-FB CALC (Ver.7.07J) data calculation program. Use 10 different glass cloth samples to carry out the above-mentioned measurement 5 times, and calculate the average value of the residual shear strain rate 2HB/B. The residual shear strain rate 2HB/B is the bending hysteresis 2HB in the weft direction relative to the weft yarn The ratio of the bending stress B in the direction.

In addition, in the present invention, the residual shear strain rate 2HG/G of the glass cloth is a value measured using a KES-FB1 tensile shear tester manufactured by KATO TECH CO., LTD. Hereinafter, the method of measuring the residual shear strain rate 2HG/G of the glass cloth will be described with reference to FIG. 2 . Figure 2(a) is a schematic diagram of the state where the glass cloth is sheared and deformed by a tensile shear tester until the shear angle is φ, and Figure 2(b) is a shear hysteresis curve obtained by using a tensile shear tester An example of an example. First, two pieces of glass cloth cut into 20 cm x 20 cm were prepared, and these two pieces were stacked so that the respective warp and weft yarns were in the same direction to prepare a test sample. In addition, when the warp and weft in the glass cloth cannot be clearly distinguished immediately, it is only necessary to determine that the yarn width variation when viewed from the plane direction is equivalent to the weft as described above. The test sample was fixed so that the distance between the jigs might become 5 cm. When fixing, the two ends of the weft yarn of the test sample in the length direction (that is, the direction in which the weft yarn is continuous) are equally wrapped around the fixture. Next, as shown in Figure 2, under the state of applying a forced load (W) of 10gf/cm in the longitudinal direction of the weft yarn (that is, the direction in which the weft yarn is continuous), the glass cloth is moved to the warp yarn at a constant speed (0.00834°/sec). The length direction of the warp yarn (that is, the direction in which the warp is continuous) is deformed until the shear angle φ=+8°, and then deformed in the opposite direction until the shear angle φ=-8°, and then returns to the original shape. Measurement and shear The shear force generated together with the change of the cutting angle (refer to Figure 2(a)). The shear test was set as one cycle, and the shear hysteresis curve (vertical axis: shear force, horizontal axis: shear angle) as shown in Figure 2(b) was obtained as the shear characteristic value. From this shear hysteresis curve, the shear stress G (gf/cm/deg) and the hysteresis width 2HG (gf/cm) in the weft direction were calculated. This measurement is performed under the environment of 23°C and 50%RH. In addition, the shear stress G per unit length is calculated by the average slope of the differential value of the shear force (Fs) measured at the shear angle φ=+0.5 to +2.5, and the hysteresis width 2HG is calculated by the shear angle The hysteresis width of φ=+0.5 (refer to Fig. 2(b)) is calculated. This measurement can be performed, for example, using the KES-FB SYSTEM (Ver.7.18WJ) data measurement program, and G and 2HG can be calculated using the KES-FB CALC (Ver.7.07J) data calculation program. Use 10 pieces of different glass cloth samples to carry out the above-mentioned measurement 5 times, and calculate the average value of the residual shear strain rate 2HG/G, which is the shear hysteresis 2HG in the weft direction (gf /cm) to the ratio of the shear stress G (gf/cm/deg) in the weft direction.

[Manufacturing method of glass cloth] Next, an example of the manufacturing method of the glass cloth of this invention is demonstrated. First, weave glass cloth, which uses glass yarns composed of multiple glass long fibers as warp and weft yarns. As long as the weaving method is conventionally known, any method may be used, for example, the warp is subjected to a warping step and a sizing step, and a jet loom (such as an air jet loom, a water jet loom, etc.), Sulzer (Sulzer) loom, rapier (Rapier) loom, etc. to input weft yarn.

Then, fiber opening treatment and/or thermal cleaning treatment may be performed as required. The method of fiber-opening treatment can be, for example: fiber-opening treatment on the obtained glass cloth by water flow pressure, using water (such as degassed water, ion-exchanged water, deionized water, electrolyzed cationic water or electrolyzed anion water, etc.) Such as fiber opening treatment by high-frequency vibration as a medium, processing using pressure by rollers, etc. The fiber opening treatment can be performed simultaneously with weaving or after weaving. In addition, the fiber opening treatment may be performed before, after, or simultaneously with the heat cleaning treatment, or may be performed simultaneously with or after the surface treatment described later. Also, the method of adjusting the degree of fiber opening of the warp and weft can be known methods, such as the following: the method of adjusting the tension of the warp; A method of adjusting and imparting a tension balance between the warp direction and the weft direction by means of a rotary roller, a miravo roll, or a tenter frame, and simultaneously performing fiber opening; or a combination of these methods.

When the woven glass cloth is attached with a substance (such as a sizing agent, etc.) that will hinder the adhesion or wettability of the matrix resin when it is made into a prepreg or a printed wiring board, it is advisable to remove the substance by such as heat cleaning treatment, etc. . In addition, heat cleaning treatment can also be omitted for glass cloth woven with glass yarn to which the surface treatment agent described later is applied to the primary and secondary pastes. The temperature condition of thermal cleaning treatment should be above 350°C, more preferably 350~500°C, more preferably 380~450°C. Also, as for the heat cleaning treatment time, it can be appropriately set according to the temperature conditions adopted. For example, when the glass cloth is made into a roll product (the product after the glass cloth is wound on the core) and the roll product is directly processed During thermal cleaning treatment, the thermal cleaning treatment time is preferably 20-60 hours, more preferably 24-48 hours, more preferably 24-36 hours.

And, in the manufacturing method of the glass cloth of this invention, the surface treatment is performed to the prepared glass cloth. As surface treatment, first prepare a treatment agent.

The prepared treatment agent includes components and solvents intended to be attached to the surface of the long glass fibers, and specifically includes the following treatment agent: (A) polyoxyalkylene bisphenol A ether group and/or (B) has Acryl or methacryl silane coupling agent and solvent. The type of solvent is not particularly limited, and examples include water.

The content of (A) polyoxyalkylene bisphenol A ether in the treatment agent is not particularly limited, for example, 1-30 g/L, preferably 2-20 g/L, more preferably 3-15 g/L. Also, the content of (B) silane coupling agent with acryl or methacryl in the treatment agent is not particularly limited, for example, 3-40 g/L, preferably 5-35 g/L, more preferably 10 ~30g/L.

The mass ratio of (A) polyoxyalkylene bisphenol A ether in the mass of the total non-volatile components contained in the treatment agent is not particularly limited, for example, 10-90% by mass, and preferably 20-80% by mass, More preferably, it is 10-50 mass %, More preferably, it is 15-45 mass %. The mass ratio of (B) silane coupling agent with acryl or methacryl group in the mass of the total non-volatile components contained in the treatment agent is not particularly limited, for example, it can be 10-90% by mass, and preferably 20% by mass. ~80% by mass. Also, the mass ratio of the total silane coupling agent in the mass of the total non-volatile components contained in the treatment agent is not particularly limited, for example, 10-90% by mass, preferably 40-90% by mass, more preferably 45-85% by mass quality%. Also, the ratio of the total mass of the silane coupling agent having an acryl group or a methacryl group to a total of 100 parts by mass of the total silane coupling agent contained in the treatment agent is not particularly limited, for example, 10 to 100 parts by mass, It is preferably 30 to 100 parts by mass, more preferably 50 to 100 parts by mass. In addition, in the present invention, "non-volatile components" refer to the absolute dry components when heat treatment is carried out at 110°C under normal pressure to remove the solvent etc. The remaining components attached to the surface of the glass long fiber.

The glass cloth can be surface-treated by applying the treating agent to the glass cloth by soaking, coating, or spraying the prepared treating agent on the glass cloth and then drying it. In the surface treatment step, the surface treatment can be carried out by making the above-mentioned (A) and (B) into a mixed treatment agent and then applying it to the glass cloth prepared above and drying it, or by making the above-mentioned (A) Surface treatment is carried out by applying and drying the treating agent differently from the above (B) in two stages.

[Form and application of glass cloth] In one embodiment of the glass cloth of the present invention, the glass cloth is provided in the form of a roll-shaped long glass cloth wound around a core. When the glass cloth of the present invention is a rolled glass cloth, the length and width of the glass cloth are not particularly limited, for example, the length is 10-4000m, preferably 50-3000m, more preferably 100-2000m, and the width can be 10 ~200cm, preferably 30~150cm, more preferably 50~130cm.

The glass cloth of the present invention is suitable for use as a fiber substrate of a prepreg. Especially, the glass cloth of this invention is especially suitable as a fiber base material of the prepreg for printed wiring boards. A prepreg using the glass cloth of the present invention will be described later.

2. Prepreg The prepreg of this invention contains the said glass cloth, and the thermosetting resin contained in the state impregnated in the said glass cloth.

The thermosetting resin is not particularly limited as long as it is a resin that can be cured by heat, and examples include the following: phenolic resin, epoxy resin, non-halogen epoxy resin, cyanate resin, maleic acid resin, etc. Imine resins, bismaleimide resins, modified bismaleimide resins, isocyanate resins, benzenecyclobutene resins, vinyl resins, bismaleimide trisulphate resins, phenolic resins, thermosetting types Polyphenylene ether resin. A thermosetting resin may be used individually by 1 type, and may use 2 or more types together.

In addition, the prepreg of the present invention may contain an inorganic filler. Examples of inorganic fillers include the following: natural silica, fused silica, amorphous silica, hollow silica and other silicas; boehmite; molybdenum compounds such as molybdenum oxide or zinc molybdate; Alumina, talc, calcined talc, mica, short glass fiber, spherical glass and other glass fillers (E glass or T glass, UT glass, S glass, D glass, NE glass, L glass, LU glass, etc. glass filler).

The prepreg of the present invention is suitably used as a constituent material of a printed wiring board. Example

Hereinafter, an Example and a comparative example are shown and this invention is demonstrated in detail. However, the present invention is not limited to the Examples.

1. Measurement and evaluation methods 1-1. Average fiber diameter and number of glass long fibers The average fiber diameter of the glass long fibers and the number of glass long fibers constituting the glass yarn were measured as follows. That is, prepare two pieces of glass cloth obtained by cutting them into 30 cm squares, one of them is used for warp yarn observation, and the other is used for weft yarn observation, and these are respectively embedded in epoxy-based cold embedding resin (Struers Co., Ltd. Made in epoxy resin SpeciFix-40) and let it harden. Next, after grinding the glass cloth embedded in the epoxy-based cold embedding resin to the extent that the warp or weft can be observed, using a scanning electron microscope (SEM) (trade name JSM-6390A manufactured by JEOL Ltd.) The average fiber diameter was observed at a magnification of 2000 times, and the number of fibers was observed at a magnification of 500 times to perform measurement. (1) Average fiber diameter of glass long fibers (µm) 30 warp and weft yarns were randomly selected, and the cross-sections of the long fibers contained in the 30 glass yarns were observed and the diameters were measured, and the average value was calculated as the average fiber diameter of the glass long fibers of the warp and weft yarns. (2) Number of glass long fibers (roots) Randomly select 30 warp yarns and weft yarns respectively, measure the total number of long fibers contained in each of the 30 glass yarns, and calculate the average value as the number of glass long fibers in the warp yarns and weft yarns.

1-2. Weaving density of glass cloth The weaving density of the glass cloth is measured according to the method stipulated in "7.9 Density (Weaving Density)" of the Japanese Industrial Standard JIS R 3420: 2013 "General Test Methods for Glass Fiber". Specifically, the position at least 50 mm away from the edge of the glass cloth and the cloth edge is the measurement object, the measurement interval is set at 10 mm to 200 mm, and the number of all yarns within the set measurement interval is measured. Set the above as one measurement, move to other positions that do not contain the previously measured yarn, and measure the number of all filaments in the measurement interval in the same way, and then measure twice. After every 3 measurements, calculate the number of roots per 25mm according to the following formula, and calculate the average value of the 3 measurements. [mathematical formula 1] Mi=(ni/ai)×25 Mi: the number of yarns per 25mm ni: the number of yarns measured ai: the correct distance for measurement (mm)

1-3. Glass yarn number The glass yarn number of the glass cloth is measured according to the method stipulated in "No. 7.1" of the Japanese Industrial Standard JIS R 3420 2013 "General Test Methods for Glass Fiber". Specifically, first, 500 m of glass yarn was taken from a winding device and made into a test piece. Place the test piece flat in the furnace and burn it at 625°C for 25 minutes, then place it in a desiccator to cool, and then measure the mass of the test piece. Then calculate the number according to the following formula. [mathematical formula 2] t=(m/500)×1000 t: number m: mass of test piece (g)

1-4. Quality of glass cloth The quality of glass cloth is measured according to the method stipulated in "7.2 Quality of cloth and mat (mass)" of Japanese Industrial Standard JIS R 3420: 2013 "General Test Methods for Glass Fiber". Specifically, a square test piece with an area of 100 cm ² is taken from a place more than 50 mm away from the selvedge of the glass cloth, and the mass of the test piece is measured after drying the test piece at 105°C for 1 hour, and the weight per 1 m ² is calculated according to the following formula of quality. [Mathematical formula 3] ρA=(ms/100)×10 ⁴ ρA: mass per 1m ² (g/m ² ) ms: mass of test piece (g)

1-5. Glass cloth thickness The thickness of the glass cloth is measured according to the method B stipulated in "7.10.1 Thickness of the cloth" of the Japanese Industrial Standard JIS R 3420:2013 "General Test Methods for Glass Fiber". Specifically, an electronic micrometer with a minimum display value of 0.001 mm is used to measure the thickness at a point 50 mm or more inward from both ends and the selvedge.

1-6. Loss on ignition of glass cloth The loss on ignition of glass cloth is measured in accordance with the method specified in "7.3.2 Loss on ignition" of Japanese Industrial Standard JIS R 3420: 2013 "General Test Methods for Glass Fiber". Specifically, a test piece of more than 100 cm ² is cut out from the corner or edge to the inside of more than 10 mm, and it is placed in a dryer at 105°C for 30 minutes to dry. After drying, move the test piece to a desiccator and let it cool down to room temperature, then measure the mass. Repeat drying, cooling and measurement until the mass is fixed, and obtain the mass of the test piece after drying. Next, put the dried test piece into a set furnace adjusted to 625° C. and heat for more than 10 minutes. After the test piece is taken out from the set furnace, it is moved to a desiccator for cooling, and then the mass of the test piece is measured. Heating, cooling, and measurement are repeated until the mass is fixed, and the mass of the test piece after drying and heating is obtained. Then calculate the loss on ignition (%) according to the following formula. [Mathematical formula 4] H ₂ =(m ₁ -m ₂ )/m ₁ ×100 H ₂ : loss on ignition (%) m ₁ : mass of test piece after drying (g) m ₂ : test after drying and heating Tablet mass (g)

1-7. Tensile strength of glass cloth The tensile strength of glass cloth is based on the method stipulated in "7.4.2 When it is cloth" of Japanese Industrial Standard JIS R 3420: 2013 "General Test Methods for Glass Fiber", using a constant velocity extension type tensile tester (INTESCO co. ., Ltd.), the length of the test piece was set to 25 cm, the width of the test piece (the width before the yarn was removed from both ends) was set to 30 mm, the clamping interval was set to 15 cm, the width of the test piece (the The width after the yarn) is set to 25mm, the constant speed stretching speed is set to 200mm/min, the breaking strength is measured 5 times in the warp direction of the glass cloth, and the average value of the measured values is regarded as the tensile strength of the glass cloth (N/25mm ).

1-8. Carbon content of glass cloth Using a total carbon measuring device (SUMIGRAPH (registered trademark) NCH-22F manufactured by Sumika Chemical Analysis Service, Ltd.), the glass cloth was burned and reduced under an oxygen cycle at a reaction temperature of 850°C and a reduction temperature of 600°C, and the heat conduction The TCD quantifies the total organic carbon that has been separated by chromatography on a column packed with porous polymer beads. The carbon content of the glass cloth is calculated from the calibration curve prepared by using the element quantitative standard sample acetaminophen as the standard sample.

1-9. The yarn width of warp yarn and weft yarn varies Yarn Width Variation: Cut the glass cloth into 20cm×20cm, observe it from the plane direction with an optical microscope, and randomly select one glass yarn that constitutes the warp yarn, and measure 1cm from the edge end to the length direction of the glass yarn for each of the three yarns. The yarn width of the glass yarn is measured every 1cm from this point to the length direction of the glass yarn, and the remaining 18 measurements are repeated. After measuring the yarn width of 19 places in total, the coefficient of variation CV value of the yarn width of the 19 places is calculated ( = standard deviation/mean). This measurement was performed for three glass yarns constituting the warp, and the average value of the CV values of the three warp yarns was obtained. Also, the CV value of the yarn width of the glass yarn constituting the weft yarn was obtained in the same manner. The larger the CV value, the larger the variation in yarn width is judged.

1-10. Residual curvature 2HB/B The residual curvature 2HB/B was measured using a KES-FB2 pure bending tester manufactured by KATO TECH CO., LTD. as a tester for bending measurement. Specifically, two pieces of glass cloth cut into 20 cm x 20 cm were prepared, and these two pieces were stacked so that the respective warp and weft yarns were in the same direction to prepare a test sample. The test sample was fixed so that the distance between the jigs might become 1 cm. When fixing, the two ends of the length direction of the weft yarn of the test sample are equally wrapped around the fixture. Next, as shown in Figure 1(a), bend into an arc shape at a constant speed (deformation speed (0.5-1/sec)) until the weft yarn becomes curvature K=+2.5cm ^{-1 ,} and then bend at a constant speed (deformation speed) (0.5 ^-1 /sec)) bends to the opposite side into an arc shape until the weft yarn reaches the maximum curvature -2.5cm ^-1 and then returns to the original shape, so as to conduct a bending test and measure the bending moment generated together with the curvature change ( Figure 1(a)). The bending test is set as one cycle, and the bending hysteresis curve shown in Figure 1(b) is obtained as the bending characteristic value, and the bending rigidity B (gf·cm ² /cm) and hysteresis width 2HB (gf·cm 2 /cm) per unit length are obtained. cm/cm). This measurement is performed under the environment of 23°C and 50%RH. In addition, in the present invention, B is calculated by the average slope of the differential value of the bending moment (M) measured between the curvature K=+0.5cm ^-1 to +1.5cm ^-1 , and 2HB is calculated by the curvature K=+ The hysteresis width of 1.0cm ^-1 (refer to Fig. 1(b)) was calculated. In this test, the KES-FB SYSTEM (Ver.7.18WJ) data measurement program was used for measurement, and the KES-FB CALC (Ver.7.07J) data calculation program was used to calculate B and 2HB. The above-mentioned measurement was implemented 5 times using 10 different glass cloth samples, and the average value of the residual shear strain rate 2HB/B was calculated|required.

1-11. Residual shear strain rate 2HG/G The residual shear strain rate 2HG/G was measured using KES-FB1 manufactured by KATO TECH CO., LTD. as a tensile shear tester. Specifically, two pieces of glass cloth cut into 20 cm x 20 cm were prepared, and these two pieces were stacked so that the respective warp and weft yarns were in the same direction to prepare a test sample. The test sample was fixed so that the distance between the jigs might become 5 cm. When fixing, the two ends of the length direction of the weft yarn of the test sample are equally wrapped around the fixture. Next, as shown in Figure 2, under the state of applying a forced load (W) of 10gf/cm in the longitudinal direction of the weft yarn (that is, the direction in which the weft yarn is continuous), the glass cloth is moved to the warp yarn at a constant speed (0.00834°/sec). The length direction of the warp (that is, the continuous direction of the warp) is deformed to the shear angle φ=+8°, and then deformed in the opposite direction to the shear angle φ=-8°, and then returns to the original shape. The shear force generated with the change of the shear angle (refer to Figure 2(a)). The shear test is set as one cycle, and the shear hysteresis curve shown in Figure 2(b) is obtained as the shear characteristic value, and the shear stress G (gf/cm/deg) and hysteresis width 2HG ( gf/cm). This measurement is performed under the environment of 23°C and 50%RH. In addition, G is calculated by the average slope of the differential value of the shear force (Fs) measured between the shear angle φ=+0.5 and +2.5, and 2HG is calculated by the hysteresis width of the shear angle φ=+0.5 (refer to Figure 2(b)) calculated. In this measurement, the KES-FB SYSTEM (Ver.7.18WJ) data measurement program was used for measurement, and the KES-FB CALC (Ver.7.07J) data calculation program was used to calculate G and 2HG. The above-mentioned measurement was implemented 5 times using 10 different glass cloth samples, and the average value of the residual shear strain rate 2HG/G was calculated|required.

1-12. Evaluate the degree of warp streaks on glass cloth Random visual inspection of the length of 1000m of the obtained glass cloth, observing the number of warp striations, calculating the number of warp striations per 100m length, and evaluating according to the following criteria. In addition, warp streaks count the number of those with a length of 100 cm or more. A: The number of warp streaks is 0.0/100m. B: The number of warp streaks is 0.1~0.5/100m. C: The number of warp streaks exceeds 0.6/100m.

1-13. Evaluate whether there are oblique wrinkles on the glass cloth The length of 1000m of the obtained glass cloth was randomly inspected visually, the number of oblique wrinkles was observed, and the presence or absence of oblique wrinkles was evaluated. In addition, oblique wrinkles count the number of those with a length of 10 cm or more. A: The number of oblique wrinkles was not observed. B: The number of oblique wrinkles observed.

2. Fabrication of glass cloth Example 1 The warp and weft yarns are made of glass yarns with an average fiber diameter of 4.0 µm and 100 long glass fibers. The long glass fibers are made of low dielectric constant/low dielectric Made of tangential glass material, the composition of the glass material includes: SiO ₂ : 51% by mass, Al ₂ O ₃ : 13% by mass, CaO: 8% by mass, B ₂ O ₃ : 23% by mass and the rest 5% by mass. Weaving glass yarn with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 75/25mm and a weft density of 76/25mm (long glass cloth wound on a core) . Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, prepare the treatment agent of recipe 1 as the surface treatment agent. The composition ratio of the non-volatile components of the treatment agent is listed in Table 1. (prescription 1) N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride (trade name Sila-Ace (registered trademark) S-350 manufactured by JNC Co., Ltd., non-volatile component 30%): 9.0g/L 3-methacryloxypropyltrimethoxysilane (trade name Sila-Ace (registered trademark) S-710 manufactured by JNC Co., Ltd., non-volatile content 98%): 13.5g/L Polyoxyethylene bisphenol A ether (trade name GF690 manufactured by Yoshimura Oil Chemical Co., Ltd., non-volatile content 70%): 5.2g/L Remainder: pure water

Apply a tension of 150N/m to the glass cloth after thermal cleaning treatment in the length direction of the warp yarn (the direction in which the warp yarn is continuous), and soak it in the treatment agent of prescription 1 at the same time, and use a clamping pressure of 35N/ ^cm2 The nip rolls are twisted and dried at a temperature of 120°C. Then, after performing the fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 1, twist it with the nip roll of 35N/ ^cm2 , and dry it at a temperature of 120°C, thereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 96N/25mm, the residual curvature 2HB/B in the weft direction is 0.41 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 0.99 (deg ^-1 ), the loss on ignition was 1.16% by mass, and the carbon content was 0.72% by mass.

[Example 2] The warp and weft yarns are glass yarns made of 100 long glass fibers with an average fiber diameter of 4.0 µm. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 51% by mass, Al ₂ O ₃ : 13% by mass, CaO: 8% by mass, B ₂ O ₃ : 23% by mass and the rest 5% by mass. The glass yarn was woven on an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 75 threads/25 mm and a weft density of 76 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, prepare the treatment agent of recipe 2 as the surface treatment agent. The composition ratio of the non-volatile components of the treatment agent is listed in Table 1. (prescription 2) 3-methacryloxypropyltrimethoxysilane (trade name Sila-Ace (registered trademark) S710 manufactured by JNC Co., Ltd., non-volatile content 98%): 6.75g/L Vinyltrimethoxysilane (trade name Sila-Ace (registered trademark) S210 manufactured by JNC Co., Ltd., non-volatile content 99%): 6.0g/L Polyoxyethylene bisphenol A ether (trade name GF690 manufactured by Yoshimura Oil Chemical Co., Ltd., non-volatile content 70%): 15.7g/L Polyalkylenepolyamine fatty amide (trade name KSK-2240 manufactured by Lion Specialty Chemicals Co., Ltd., 30% non-volatile content): 5.0g/L Remainder: pure water

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 2 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 2, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, whereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 81N/25mm, the residual curvature 2HB/B in the weft direction is 0.36 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 0.94 (deg ^-1 ), the loss on ignition was 1.25% by mass, and the carbon content was 0.96% by mass.

[Example 3] The warp and weft yarns are made of glass yarns with an average fiber diameter of 4.0 µm and 100 long glass fibers. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 51% by mass, Al ₂ O ₃ : 13% by mass, CaO: 8% by mass, B ₂ O ₃ : 23% by mass and the rest 5% by mass. The glass yarn was woven on an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 75 threads/25 mm and a weft density of 76 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, prepare the treatment agent of prescription 3 as the surface treatment agent. The composition ratio of the non-volatile components of the treatment agent is listed in Table 1. (prescription 3) 3-methacryloxypropyltrimethoxysilane (trade name Sila-Ace (registered trademark) S-710 manufactured by JNC Co., Ltd., non-volatile content 98%): 13.5g/L Polyoxyethylene bisphenol A ether (trade name GF690 manufactured by Yoshimura Oil Chemical Co., Ltd., non-volatile content 70%): 5.2g/L Remainder: pure water

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after thermal cleaning, soak it in the treatment agent of prescription 3 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 3, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, whereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 84N/25mm, the residual curvature 2HB/B in the weft direction is 0.34 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 1.02 (deg ⁻¹ ), the loss on ignition was 1.10% by mass, and the carbon content was 0.65% by mass.

[Example 4] The warp and weft are made of glass yarns with an average fiber diameter of 4.0 µm and 50 long glass fibers. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 49% by mass, Al ₂ O ₃ : 14% by mass, CaO: 6% by mass, B ₂ O ₃ : 28% by mass and the remainder 3% by mass. The glass yarn was woven with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 95 threads/25 mm and a weft density of 95 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, as a surface treatment agent, the treatment agent of the aforementioned recipe 1 was prepared. The composition ratio of the non-volatile components of the treatment agent is listed in Table 1.

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 1 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing the fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 1, twist it with the nip roll of 35N/ ^cm2 , and dry it at a temperature of 120°C, thereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 49N/25mm, the residual curvature 2HB/B in the weft direction is 0.40 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 0.96 (deg ^-1 ), the loss on ignition was 1.13% by mass, and the carbon content was 0.64% by mass.

[Example 5] The warp and weft yarns are made of glass yarns with an average fiber diameter of 4.0 µm and 50 long glass fibers. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 49% by mass, Al ₂ O ₃ : 14% by mass, CaO: 6% by mass, B ₂ O ₃ : 28% by mass and the remainder 3% by mass. The glass yarn was woven with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 95 threads/25 mm and a weft density of 95 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, the treatment agent of the aforementioned prescription 2 was prepared as a surface treatment agent. In addition, the composition ratio of the non-volatile components of the treatment agent is shown in Table 1.

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 2 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 2, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, whereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 50N/25mm, the residual curvature 2HB/B in the weft direction is 0.43 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 0.93 (deg ^-1 ), the loss on ignition was 1.35% by mass, and the carbon content was 1.06% by mass.

[Example 6] The warp and weft yarns use glass yarns made of 50 long glass fibers with an average fiber diameter of 4.0 µm. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 49% by mass, Al ₂ O ₃ : 14% by mass, CaO: 6% by mass, B ₂ O ₃ : 28% by mass and the remainder 3% by mass. The glass yarn was woven with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 95 threads/25 mm and a weft density of 95 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, the treatment agent of the aforementioned prescription 3 was prepared as a surface treatment agent. The composition ratio of the non-volatile components of the treatment agent is shown in Table 2.

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after thermal cleaning, soak it in the treatment agent of prescription 3 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 3, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, thereby Get glass cloth.

In the obtained glass cloth, the yarn width variation of the weft yarn is larger than that of the warp yarn, the tensile strength in the warp direction is 52N/25mm, the residual curvature 2HB/B in the weft direction is 0.41 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 1.07 (deg ^-1 ), the loss on ignition was 1.06% by mass, and the carbon content was 0.70% by mass.

[Example 7] The warp and weft yarns are made of glass yarns with an average fiber diameter of 4.0 µm and 40 long glass fibers. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 50% by mass, Al ₂ O ₃ : 15% by mass, CaO: 5% by mass, B ₂ O ₃ : 27% by mass and the remainder 3% by mass. The glass yarn was woven with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 95 threads/25 mm and a weft density of 95 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, as a surface treatment agent, the treatment agent of the aforementioned recipe 1 was prepared. In addition, the composition ratio of the non-volatile components of the treatment agent is shown in Table 2.

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 1 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing the fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 1, twist it with the nip roll of 35N/ ^cm2 , and dry it at a temperature of 120°C, thereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 36N/25mm, the residual curvature 2HB/B in the weft direction is 0.44 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 0.89 (deg ^-1 ), the loss on ignition was 1.17% by mass, and the carbon content was 0.80% by mass.

[Example 8] The warp and weft are made of glass yarns with an average fiber diameter of 4.0 µm and 40 long glass fibers. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 50% by mass, Al ₂ O ₃ : 15% by mass, CaO: 5% by mass, B ₂ O ₃ : 27% by mass and the remainder 3% by mass. The glass yarn was woven with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 95 threads/25 mm and a weft density of 95 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, the treatment agent of the aforementioned prescription 2 was prepared as a surface treatment agent. The composition ratio of the non-volatile components of the treatment agent is shown in Table 2.

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 2 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 2, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, whereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 36N/25mm, the residual curvature 2HB/B in the weft direction is 0.49 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 0.89 (deg ^-1 ), the loss on ignition was 1.30% by mass, and the carbon content was 0.92% by mass.

[Example 9] The warp and weft yarns are made of glass yarns with an average fiber diameter of 4.0 µm and 40 glass long fibers. The glass long fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 50% by mass, Al ₂ O ₃ : 15% by mass, CaO: 5% by mass, B ₂ O ₃ : 27% by mass and the remainder 3% by mass. The glass yarn was woven with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 95 threads/25 mm and a weft density of 95 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, the treatment agent of the aforementioned prescription 3 was prepared as a surface treatment agent. In addition, the composition ratio of the non-volatile components of the treatment agent is shown in Table 2.

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after thermal cleaning, soak it in the treatment agent of prescription 3 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 3, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, thereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 39N/25mm, the residual curvature 2HB/B in the weft direction is 0.49 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 1.01 (deg ^-1 ), the loss on ignition was 1.18% by mass, and the carbon content was 0.66% by mass.

[Example 10] The warp and weft yarns use glass yarns made of glass long fibers with an average fiber diameter of 3.6 μm and a number of 38. The long glass fibers are made of E glass, and the composition of the E glass includes : SiO ₂ : 54% by mass, Al ₂ O ₃ : 14% by mass, CaO: 23% by mass, MgO: 1% by mass, B ₂ O ₃ : 6% by mass, and the remainder 2% by mass. The glass yarn was woven with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 105 threads/25 mm and a weft density of 110 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, as a surface treatment agent, the treatment agent of the aforementioned recipe 1 was prepared. In addition, the composition ratio of the non-volatile components of the treatment agent is shown in Table 2.

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 1 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing the fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 1, twist it with the nip roll of 35N/ ^cm2 , and dry it at a temperature of 120°C, thereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 51N/25mm, the residual curvature 2HB/B in the weft direction is 0.48 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 1.03 (deg ^-1 ), the loss on ignition was 0.61% by mass, and the carbon content was 0.73% by mass.

[Comparative Example 1] The warp and weft yarns are glass yarns made of 100 long glass fibers with an average fiber diameter of 4.0 µm. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 51% by mass, Al ₂ O ₃ : 13% by mass, CaO: 8% by mass, B ₂ O ₃ : 23% by mass and the rest 5% by mass. The glass yarn was woven on an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 75 threads/25 mm and a weft density of 76 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, prepare the treatment agent of prescription 4 as the surface treatment agent. The composition ratio of the non-volatile components of the treatment agent is shown in Table 3. (prescription 4) N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride (trade name Sila-Ace (registered trademark) S-350 manufactured by JNC Co., Ltd., non-volatile component 30%): 9.0g/L Trimethoxyphenylsilane (trade name Z6124 manufactured by DuPont Toray Specialty Materials K.K., 90% non-volatile content): 14.7g/L Remainder: pure water

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 4 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 4, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, whereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 96N/25mm, the residual curvature 2HB/B in the weft direction is 0.34 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 2.96 (deg ^-1 ), the loss on ignition was 0.99% by mass, and the carbon content was 0.43% by mass.

[Comparative Example 2] The warp and weft yarns are glass yarns made of 100 long glass fibers with an average fiber diameter of 4.0 µm. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 51% by mass, Al ₂ O ₃ : 13% by mass, CaO: 8% by mass, B ₂ O ₃ : 23% by mass and the rest 5% by mass. The glass yarn was woven on an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 75 threads/25 mm and a weft density of 76 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, prepare the treatment agent of recipe 5 as the surface treatment agent. The composition ratio of the non-volatile components of the treatment agent is shown in Table 3. (prescription 5) N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride (trade name Sila-Ace (registered trademark) S-350 manufactured by JNC Co., Ltd., non-volatile component 30%): 9.0g/L Remainder: pure water

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 5 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 5, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, whereby Get glass cloth.

In the obtained glass cloth, the yarn width variation of the weft yarn is larger than that of the warp yarn, the tensile strength in the warp direction is 78N/25mm, the residual curvature 2HB/B in the weft direction is 0.62 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 1.83 (deg ^-1 ), the loss on ignition was 0.63% by mass, and the carbon content was 0.14% by mass.

[Comparative Example 3] The warp and weft yarns are glass yarns made of 100 long glass fibers with an average fiber diameter of 4.0 µm. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 51% by mass, Al ₂ O ₃ : 13% by mass, CaO: 8% by mass, B ₂ O ₃ : 23% by mass and the rest 5% by mass. The glass yarn was woven on an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 75 threads/25 mm and a weft density of 76 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, prepare the treatment agent of recipe 6 as the surface treatment agent. The composition ratio of the non-volatile components of the treatment agent is listed in Table 3. (prescription 6) N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride (trade name Sila-Ace (registered trademark) S-350 manufactured by JNC Co., Ltd., non-volatile component 30%): 3.0g/L Polyoxyethylene bisphenol A ether (trade name GF690 manufactured by Yoshimura Oil Chemical Co., Ltd., non-volatile content 70%): 5.2g/L Remainder: pure water

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 6 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 6, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, thereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 92N/25mm, the residual curvature 2HB/B in the weft direction is 1.42 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 1.09 (deg ^-1 ), the loss on ignition was 0.85% by mass, and the carbon content was 0.24% by mass.

[Comparative Example 4] The warp and weft yarns are glass yarns made of 50 long glass fibers with an average fiber diameter of 4.0 µm. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 49% by mass, Al ₂ O ₃ : 14% by mass, CaO: 6% by mass, B ₂ O ₃ : 28% by mass and the remainder 3% by mass. The glass yarn was woven with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 95 threads/25 mm and a weft density of 95 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, as a surface treatment agent, the treatment agent of the aforementioned prescription 5 was prepared. In addition, the composition ratio of the non-volatile components of the treatment agent is shown in Table 3.

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 5 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 5, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, thereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 53N/25mm, the residual curvature 2HB/B in the weft direction is 0.58 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 1.79 (deg ^-1 ), the loss on ignition was 0.65% by mass, and the carbon content was 0.12% by mass.

[Comparative Example 5] The warp and weft yarns are glass yarns made of 40 long glass fibers with an average fiber diameter of 4.0 µm. The long glass fibers are made of low dielectric constant/low dielectric tangent glass material The composition of the glass material includes: SiO ₂ : 50% by mass, Al ₂ O ₃ : 15% by mass, CaO: 5% by mass, B ₂ O ₃ : 27% by mass and the remainder 3% by mass. The glass yarn was woven with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 95 threads/25 mm and a weft density of 95 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, as a surface treatment agent, the treatment agent of the aforementioned prescription 5 was prepared. The composition ratio of the non-volatile components of the treatment agent is listed in Table 3.

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 5 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 5, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, thereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 30N/25mm, the residual curvature 2HB/B in the weft direction is 0.56 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 1.63 (deg ^-1 ), the loss on ignition was 0.65% by mass, and the carbon content was 0.12% by mass.

[Comparative Example 6] The warp and weft yarns are glass yarns made of 38 long glass fibers with an average fiber diameter of 3.6 μm. The long glass fibers are made of E glass, and the composition of the E glass includes : SiO ₂ : 54% by mass, Al ₂ O ₃ : 14% by mass, CaO: 23% by mass, MgO: 1% by mass, B ₂ O ₃ : 6% by mass, and the remainder 2% by mass. The glass yarn was woven with an air-jet loom to obtain a plain weave glass cloth roll with a warp density of 105 threads/25 mm and a weft density of 110 threads/25 mm. Next, the thermal cleaning process was performed by heating the obtained glass cloth roll material for 30 hours under the condition of an atmospheric temperature of 400 degreeC. No meridional streaks and oblique wrinkles occurred in the glass cloth after thermal cleaning.

Next, as a surface treatment agent, the treatment agent of the aforementioned prescription 5 was prepared. In addition, the composition ratio of the non-volatile components of the treatment agent is shown in Table 3.

Apply a tension of 150N/m in the length direction of the warp to the glass cloth after heat cleaning treatment, soak it in the treatment agent of prescription 5 at the same time, and twist it with a nip roller with a clamping pressure of 35N/ ^cm2 , Dry at a temperature of 120°C. Then, after performing fiber opening treatment by high-pressure spraying, soak again in the treatment agent of prescription 5, and twist it with a nip roller with a nip pressure of 35N/ ^cm2 , and dry it at a temperature of 120°C, thereby Get glass cloth.

In the obtained glass cloth, the yarn width of the weft yarn varies more than that of the warp yarn, the tensile strength in the warp direction is 43N/25mm, the residual curvature 2HB/B in the weft direction is 0.79 (cm ^-1 ), and the residual shear in the weft direction The strain rate 2HG/G was 1.59 (deg ^-1 ), the loss on ignition was 0.23% by mass, and the carbon content was 0.21% by mass.

3. Results For each glass cloth, the following were evaluated: the average fiber diameter and number of long glass fibers contained in the glass yarn used, the weaving density, the number of glass yarn used, the mass, thickness, loss on ignition, tensile strength and carbon amount, residual curvature 2HB/B, residual shear strain rate 2HG/G, generation of warp streaks, and generation of oblique wrinkles. The evaluation results are listed in Table 1, Table 2 and Table 3.

[Table 1]

[Table 2]

[table 3]

The glass cloths of Examples 1 to 10 are glass cloths made of glass yarns composed of a plurality of long glass fibers as warp yarns and weft yarns. At least a part of the surface of the long glass fibers includes: (A) polyoxyalkylene bisphenol A ether, and (B) a silane coupling agent having an acryl group or a methacryl group, the weaving density of the aforementioned glass cloth is 70 pieces/25mm or more, and the carbon content of the aforementioned glass cloth is 0.4~1.5% by mass, so It is a glass cloth having a residual curvature 2HB/B of 0.5 (cm ^-1 ) or less and a residual shear strain rate 2HG/G of 1.4 (deg ^-1 ) or less. Furthermore, the glass cloths of Examples 1 to 10 were those which could suppress the generation of longitudinal wrinkles and oblique wrinkles.

On the other hand, although the glass cloth of Comparative Example 1 has a carbon content of 0.4% by mass or more, it does not include (A) polyoxyalkylene bisphenol A ether, and (B) on at least a part of the surface of the long glass fibers. Silane coupling agents with acryl or methacryl groups have a residual shear strain rate 2HG/G greater than 1.4 (deg ^-1 ). Furthermore, the glass cloth of Comparative Example 1 could not suppress generation of oblique wrinkles.

In addition, in Comparative Examples 2 and 4 to 6, the carbon content of the glass cloth is less than 0.4% by mass, and at least a part of the surface of the long glass fiber does not contain: (A) polyoxyalkylene bisphenol A ether, and (B) having Acryl-based or methacryl-based silane coupling agents are those with residual curvature 2HB/B greater than 0.5 (cm ^-1 ) and residual shear strain rate 2HG/G greater than 1.4 (deg ^-1 ). Moreover, the glass cloths of Comparative Examples 2 and 4 to 6 could not suppress the generation of longitudinal streaks and oblique wrinkles.

The glass cloth of Comparative Example 3 has a carbon content of less than 0.4% by mass and does not include (B) a silane coupling agent having an acryl group or a methacryl group on at least a part of the surface of the long glass fiber, so it is a residual shear strain Rate 2HG/G greater than 1.4 (deg ^-1 ). Moreover, the glass cloth of Comparative Example 3 could not suppress the occurrence of longitudinal streaks.

(none)

In Fig. 1 , (a) shows a schematic diagram when measuring the residual curvature 2HB/B using a pure bending tester, and (b) shows an example of a bending hysteresis curve obtained using a pure bend tester. In FIG. 2 , (a) shows a schematic diagram when the residual shear strain rate 2HG/G is measured using a tensile shear tester, and (b) shows an example of a shear hysteresis curve obtained by using a tensile shear tester.

(none)

Claims (5)

A glass cloth made of glass yarn composed of a plurality of long glass fibers as warp and weft; At least a part of the surface of the aforementioned long glass fiber comprises: (A) polyoxyalkylene bisphenol A ether, and (B) a silane coupling agent having an acryl or methacryl group; The warp yarn density and weft yarn density of the aforementioned glass cloth are 70 threads/25mm or more; In addition, the carbon content of the aforementioned glass cloth is 0.4-1.5% by mass. For example, the glass cloth of claim 1 has a tensile strength of 20~120N/25mm in the warp direction. Such as the glass cloth of claim 1 or 2, its thickness is 5~30µm. The glass cloth of claim 1 or 2 is a roll-shaped strip of glass cloth formed by winding glass cloth on a core. A prepreg comprising: the glass cloth according to any one of claims 1 to 4, and a thermosetting resin contained in a state soaked into the glass cloth.

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