CN116964267A

CN116964267A - Glass cloth

Info

Publication number: CN116964267A
Application number: CN202280017470.1A
Authority: CN
Inventors: 服部刚士; 西中大介
Original assignee: Unitika Glass Fiber Co Ltd; Unitika Ltd
Current assignee: Unitika Glass Fiber Co Ltd; Unitika Ltd
Priority date: 2021-03-24
Filing date: 2022-02-24
Publication date: 2023-10-27
Also published as: WO2022202079A1; TW202244343A; KR20230159386A; JPWO2022202079A1

Abstract

The purpose of the present invention is to provide a glass cloth having a residual curvature 2HB/B of 0.5 (cm) which is the ratio of bending hysteresis 2HB in the weft direction to bending stress B in the weft direction ^‑1 ) Hereinafter, the ratio of the shear hysteresis 2HG (gf/cm) in the weft direction to the shear stress G (gf/cm/deg) in the weft direction, i.e., the residual shear strain rate 2HG/G, was 1.4 (deg) ^‑1 ) The following is given. A glass cloth comprising a warp yarn and a weft yarn, wherein at least a part of the surface of the glass long fiber comprises (A) a polyoxyalkylene bisphenol A ether and (B) a silane coupling agent having an acryl or methacryl, the warp yarn density and the weft yarn density of the glass cloth are 70 pieces/25 mm or more, and the carbon content of the glass cloth is 0.4 to 1.5 mass%.

Description

Glass cloth

Technical Field

The present invention relates to glass cloths and prepregs.

Background

A laminated board such as a printed wiring board includes an insulating layer and a conductor layer formed thereon. As the insulating layer, a glass fiber reinforced resin reinforced with a glass fiber base material such as glass cloth is generally used.

In recent years, miniaturization and higher performance of electronic components have been demanded remarkably, and further miniaturization is demanded also for laminated boards. In order to meet such demands, thin printed wiring boards and multilayer printed wiring boards have been developed, and thin glass cloths have been developed as glass fibers used for these.

For example, patent document 1 describes a glass cloth that can suppress the occurrence of pinholes in a prepreg using the glass cloth and that can maintain excellent appearance quality of the prepreg by reducing the occurrence of fuzzing of the glass cloth even if the average number of layers is less than 3.00. Specifically, patent document 1 describes a glass cloth comprising warp yarns and weft yarns in which long glass fibers having diameters in the range of 3.0 to 4.2 μm are bundled in the range of 14 to 55, the warp yarns and weft yarns having a weaving density in the range of 86 to 140 pieces/25 mm, and having a thickness in the range of 7.5 to 12.0 μm and a thickness of 1m each, as a structure of the glass cloth ² The average number of layers expressed by a value obtained by dividing the thickness of the glass cloth by the average value of the diameter of the glass long fibers of the warp yarn and the diameter of the glass long fibers of the weft yarn (thickness of the glass cloth/{ (diameter of the glass long fibers of the warp yarn + diameter of the glass long fibers of the weft yarn)/2 }) in the range of 6.0 to 10.0g is 2.00 or more and less, and the average number of layers expressed by the average value of the open fineness of the warp yarn (yarn width of warp yarn/(diameter of the glass long fibers of the warp yarn × number of glass long fibers of the warp yarn)) and the open fineness of the weft yarn (yarn width of the weft yarn/(diameter of the glass long fibers of the weft yarn × number of glass long fibers of the weft yarn }) The average open fineness shown in (open fineness of warp yarn x open fineness of weft yarn) 1/2 is in the range of 1.000 to 1.300, and the yarn width ratio shown as the ratio of the yarn width of the warp yarn to the yarn width of the weft yarn (yarn width of warp yarn/yarn width of weft yarn) is in the range of 0.720 to 0.960.

On the other hand, in order to improve the impregnation and adhesion of the prepreg and the matrix resin of the printed wiring board obtained from the prepreg to the glass cloth, the glass cloth is surface-treated with a silane coupling agent. As a glass cloth subjected to such surface treatment, there is known a surface-treated glass fiber cloth comprising a glass fiber cloth and a treating agent containing a silane compound and a water-soluble polyurethane, which is attached to the glass fiber cloth (for example, refer to patent document 2). According to the surface-treated glass fiber fabric, it is considered that even when the thickness is reduced, the mesh misalignment is less likely to occur, and the surface-treated glass fiber fabric has sufficient rigidity, and a method for producing the same can be provided.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2018-21274

Patent document 2: japanese patent laid-open No. 2006-342445

Disclosure of Invention

Technical problem to be solved by the invention

In recent years, in order to cope with the demand for miniaturization of electronic devices and the demand for higher mounting of printed wiring boards for higher functionality, the thickness of prepregs and printed wiring boards has been further developed. In order to thin prepregs and printed wiring boards, a thin glass cloth is required. In addition, glass fibers used for prepregs and printed wiring boards are required to have a low dielectric constant due to, for example, a rapid increase in demand for high-speed transmission processing of large-capacity data.

In order to form a glass cloth having a small thickness, it is necessary to weave the glass cloth with warp yarns and weft yarns containing glass fibers having smaller fiber diameters, and to flatten the warp yarns and weft yarns by a fiber opening process.

For reducing the dielectric constant of the glass fiber, a low dielectric constant glass (for example, NE glass, L glass, trade name LU glass manufactured by UNITIKA corporation, etc.) is used as a glass material constituting the glass fiber.

Glass cloths using glass cloths having a small thickness or glass having a low dielectric constant have a problem that they have a lower tensile strength and are easily broken as compared with glass cloths using general-purpose E glass having a relatively large thickness.

Here, glass cloths used in prepregs and printed wiring boards are surface-treated with a surface treatment agent containing a silane coupling agent. The surface treatment step is performed in the final step of the glass cloth. The surface treatment is performed by immersing a glass cloth continuous in the warp direction in a surface treatment agent containing a silane coupling agent or the like, adjusting the amount of the surface treatment agent attached by a nip roller, and drying. The dried glass cloth is wound to form a glass cloth roll, and the glass cloth roll is wound back to impregnate the matrix resin to form a prepreg.

As a result of the studies by the present inventors, it has been found that, when a glass cloth having a relatively low tensile strength such as a glass cloth using a thin glass cloth or a glass cloth having a low dielectric constant is produced by using the techniques of patent documents 1 and 2, if the warp direction tension of the glass cloth load is made relatively low in the surface treatment step as a final step in order to prevent breakage or the like of the glass cloth, warp stripes (stripes extending in the longitudinal direction of warp yarns of the glass cloth) are likely to occur on the wound glass cloth. Specifically, it is known that: by reducing the warp-direction tension, bending and waving occur in the weft direction (width direction) of the glass cloth in the surface treatment step, and if the glass cloth passes through the pinch roller in a state where the bending and waving occur, the glass cloth is folded in the width direction, whereby warp stripes occur. If warp streaks occur in the surface treatment step as a final step, the warp streaks are directly carried into the prepreg production step, and there is a possibility that the quality of the prepreg is affected.

Further, as a result of the study by the present inventors, it has been found that, when glass cloths having relatively low tensile strength, such as glass cloths made of thin glass cloths or glass having a low dielectric constant, are produced by using the techniques of patent documents 1 and 2, a part of the glass cloths may be inclined (the weft yarn does not become right angle to the warp yarn) during winding, and stress is concentrated in the inclined part, so that oblique wrinkles (wrinkles extending in a direction non-parallel to the longitudinal direction of the warp yarn and non-parallel to the longitudinal direction of the weft yarn) may be generated during winding. This phenomenon does not generally occur, for example, when a glass cloth having a relatively thick E-glass material is used. If oblique wrinkles are generated during winding in the surface treatment step as a final step, the oblique wrinkles are directly carried into the prepreg manufacturing step, and there is a possibility that the quality of the prepreg may be affected.

The inventors of the present invention have further studied and found that, in order to suppress the warp streaks, it is important to set "residual curvature 2HB/B, which is the ratio of bending hysteresis 2HB in the weft direction to bending stress B in the weft direction" obtained by using a pure bending tester, which is one type of texture measuring instrument under the conditions described below, to 0.5 (cm) ^-1 ) The following is given. The residual curvature 2HB/B is a value calculated from the bending hysteresis (2 HB) and the bending rigidity (B) obtained from the hysteresis curve in the bending characteristics measured by the pure bending tester, and the energy loss in the course from bending deformation to recovery deformation is captured by the residual strain amount, and the recovery force is quantified by the value of 2 HB/B. That is, the residual curvature 2HB/B can be understood as a residual strain in the process from bending deformation to recovery deformation, and the smaller the residual strain, the higher the recovery force. The inventors of the present invention found that the residual curvature 2HB/B was 0.5 (cm) ^-1 ) In the following, bending, waving, and the like are less likely to occur in the glass cloth manufacturing process, and the occurrence of warp stripes can be easily prevented when passing through the pinch roller in the process.

Further, the present inventors have studied and found that, in order to suppress the above-mentioned oblique wrinkles, it is important to determine "a residual shear strain rate 2HG/G" which is a ratio of a shear hysteresis 2HG (gf/cm) in the weft direction to a shear stress G (gf/cm/deg) in the weft direction "obtained by using a tensile shear tester, which is one kind of texture measuring instrument, under the conditions described below"Set to 1.4 (deg ^-1 ) The following is given. The residual shear strain rate 2HG/G is a value calculated from the shear hysteresis (2 HG) and the shear stress (G) obtained from the hysteresis curve in the shear characteristics measured by the tensile shear tester, and the recovery force is quantified by capturing the energy loss from the shear deformation to the recovery deformation by the residual strain amount and by the value of 2 HG/G. That is, this value can be understood as being captured as residual strain in the process from shear deformation to recovery deformation, and the smaller the residual strain is, the higher the recovery force is. The inventors of the present invention found that by setting the residual shear strain rate to 1.4 (deg ^-1 ) In the following, the strain inherent in the glass cloth is easily relaxed in the surface treatment step, and the occurrence of diagonal wrinkles is easily prevented during winding.

Accordingly, a main object of the present invention is to provide a glass cloth which solves the above problems, wherein the ratio of bending hysteresis 2HB in the weft direction to bending stress B in the weft direction, i.e., the residual curvature 2HB/B, is 0.5 (cm) ^-1 ) Hereinafter, the ratio of the shear hysteresis 2HG (gf/cm) in the weft direction to the shear stress G (gf/cm/deg) in the weft direction, i.e., the residual shear strain rate 2HG/G, was 1.4 (deg) ^-1 ) The following is given. Another object of the present invention is to provide a glass cloth that suppresses the occurrence of warp stripes and diagonal wrinkles.

Technical scheme for solving technical problems

The present inventors have studied the above problems. In order to reduce the residual curvature 2HB/B, it is necessary to reduce the bending hysteresis 2HB in the weft direction and to improve the bending rigidity B. It has also been found that in order to reduce the bending hysteresis 2HB in the weft direction of the glass cloth, it is important to impart a surface treatment agent comprising (a) a polyoxyalkylene bisphenol a ether and (B) a silane coupling agent having an acryl or methacryl group to the glass cloth in the surface treatment step. Further, it is known that it is effective to increase the adhesion amount of the surface treatment agent in order to increase the bending rigidity B.

In addition, 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 to increase the shear stress G in the weft direction. It is known that: in order to reduce the shear hysteresis 2HG in the weft direction of the glass cloth, it is important that a surface treatment agent comprising (a) a polyoxyalkylene bisphenol a ether and (B) a silane coupling agent having an acryl or methacryl group is given to the glass cloth in the surface treatment step. Further, it is known that in order to increase the shearing stress G in the weft direction, it is important to increase the friction force associated with the movement of the interlacing point associated with the shearing deformation by setting the warp density and the weft density of the glass cloth to a specific value or more.

The inventors of the present invention have found that, in a glass cloth comprising a glass yarn comprising a plurality of glass filaments as warp yarns and weft yarns, at least a part of the surface of the glass filaments contains (A) 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 glass cloth are set to 70 pieces/25 mm or more, and the carbon content of the glass cloth is set to 0.4 to 1.5 mass%, whereby the residual curvature 2HB/B is 0.5 (cm ^-1 ) Hereinafter, the residual shear strain rate 2HG/G was 1.4 (deg ^-1 ) Hereinafter, the occurrence of warp stripes and diagonal wrinkles can be suppressed.

The present invention has been completed based on the findings and repeated intensive studies.

That is, the present invention provides the following embodiments.

The glass cloth according to item 1 is a glass cloth comprising a warp yarn and a weft yarn of glass yarn comprising a plurality of glass filaments,

at least a part of the surface of the long glass fiber filler comprises (A) polyoxyalkylene bisphenol A ether and (B) a silane coupling agent having an acryl or methacryl group,

the warp yarn density and the weft yarn density of the glass cloth are above 70/25 mm,

the carbon content of the glass cloth is 0.4-1.5 mass%.

The glass cloth according to item 1, wherein the tensile strength in the warp direction is 20 to 120N/25mm.

Item 3. The glass cloth according to item 1 or 2, wherein the glass cloth has a thickness of 5 to 30. Mu.m.

The glass cloth according to any one of items 1 to 3, wherein the glass cloth is a long glass cloth roll formed by winding glass cloth around a roll core.

A prepreg according to item 5, which comprises the glass cloth according to any one of items 1 to 4 and a thermosetting resin contained in a state of being impregnated in the glass cloth.

Effects of the invention

According to the glass cloth of the present invention, by performing surface treatment with a specific surface treatment agent and setting the weaving density and carbon amount of the glass cloth to specific ranges, it is possible to satisfy a residual curvature 2HB/B of 0.5 (cm ^-1 ) The residual shear strain rate 2HG/G was 1.4 (deg) ^-1 ) In the following, the occurrence of warp stripes and diagonal wrinkles can be effectively suppressed.

Drawings

FIG. 1 (a) is a schematic diagram showing the measurement of residual curvature 2HB/B using a pure bending machine, and FIG. 1 (B) is an example of a bending hysteresis curve obtained using a pure bending machine.

FIG. 2 (a) is a schematic diagram showing the measurement of the residual shear strain rate 2HG/G by using a tensile shear tester, and FIG. 2 (b) is an example of a shear hysteresis curve obtained by using a tensile shear tester.

Detailed Description

1. Glass cloth

The glass cloth of the present invention is a glass cloth comprising a warp yarn and a weft yarn, wherein at least a part of the surface of the glass filaments comprises (A) a polyoxyalkylene bisphenol A ether and (B) a silane coupling agent having an acryl or methacryl, the glass cloth has a weave density of 70 pieces/25 mm or more, and the glass cloth has a carbon content of 0.4 to 1.5 mass%. The glass cloth of the present invention will be described in detail below.

[ glass yarn constituting glass cloth ]

The glass cloth of the present invention uses glass yarns comprising a plurality of glass long fibers 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, and LU glass, C glass, and AR glass manufactured by UNITKA corporation.

From the viewpoint of versatility, it is preferable to use glass yarns having an E glass composition. The E glass composition contains SiO in an amount of 52 to 56 mass% based on the total amount of glass fibers ₂ B in a range of 5 to 10 mass% ₂ O ₃ Al in a range of 12 to 16 mass% ₂ O ₃ CaO and MgO in a total amount of 20 to 25 mass% and Li in a total amount of 0 to 1 mass% ₂ O、K ₂ O and Na ₂ O composition.

Further, from the viewpoint of further improving the strength of the prepreg and the printed wiring board, it is preferable that the glass yarn contains SiO in a range of 60 to 66 mass% relative to the total amount of glass fibers ₂ Al in a range of 20 to 26 mass% ₂ O ₃ And 10 to 15 mass% of MgO.

Further, from the viewpoint of reducing the dielectric constant and dielectric loss tangent of the prepreg and the printed wiring board, the glass yarn preferably contains SiO in an amount ranging from 45 to 60 mass% relative to the total amount of glass fibers ₂ B in a range of 15 to 35 mass% ₂ O ₃ Al in a range of 10 to 20 mass% ₂ O ₃ And 1 to 15 mass% of CaO, more preferably 45 to 55 mass% of SiO based on the total amount of the glass fibers ₂ B in a range of 20 to 35 mass% ₂ O ₃ Al in a range of 10 to 20 mass% ₂ O ₃ And 3 to 10 mass% of CaO.

In the present invention, the glass composition was measured by ICP emission spectrometry. Specifically, the Si content and the B content can be obtained as follows: the weighed glass cloth sample was dissolved in sodium carbonate, dissolved in dilute nitric acid, and the volume was fixed, and the obtained sample was measured by ICP emission spectrometry. The Fe content can be obtained by dissolving a weighed glass cloth sample in an alkali solution and fixing the volume, and measuring the resultant sample by ICP emission spectrometry. Further, the Al content, ca content and Mg content can be obtained as follows: the weighed glass cloth sample was decomposed by heating with sulfuric acid, nitric acid and hydrogen fluoride, dissolved with dilute nitric acid, and the volume was determined, and the obtained sample was measured by ICP emission spectrometry. As the ICP emission spectrometry device, iCAP6300Duo manufactured by Thermo Fisher corporation can be used.

In the glass cloth of the present invention, the average fiber diameter of the long glass fibers is not particularly limited. The average fiber diameter of the long glass fiber filler is, for example, 2 to 7. Mu.m, preferably 2.5 to 5.5. Mu.m, more preferably 3 to 5. Mu.m, from the viewpoint of more easily exhibiting the effect of the present invention.

In the glass cloth of the present invention, the number of the long glass fibers constituting the glass yarn is not particularly limited. For example, from 20 to 200, preferably from 20 to 100, more preferably from 20 to 50 or from 30 to 50, from the viewpoint of more easily exhibiting the effect of the present invention.

The average fiber diameter and the number of the long glass fibers were measured and calculated as follows. That is, 2 pieces of glass cloth to be measured were prepared, one of which was used for warp observation and the other was used for weft observation, and each of the glass cloths was cut into 30cm square glass cloths, and the glass cloths were embedded in an epoxy-based cold-setting resin and cured. Next, glass cloth embedded in an epoxy-based cold-setting resin was ground to such an extent that warp and weft were observed, and the observation was performed using SEM (trade name JSM-6390A manufactured by japan electronics corporation) at a magnification of 2000 times and 500 times as many as the average fiber diameter.

(1) Average fiber diameter (μm) of glass yarn

30 warp yarns and weft yarns were randomly selected, and the cross sections of the long fibers contained in the 30 glass yarns were observed, the diameters were measured, and the average values were calculated as the average fiber diameters of the long glass fibers of the warp yarns and the weft yarns.

(2) Root number (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 an average value was calculated as the number of warp yarns and weft yarns.

In the glass cloth of the present invention, the count of the glass yarn is not particularly limited. For example, from 0.5 to 25tex, from the viewpoint of more easily exhibiting the effect of the present invention, it is preferably from 0.5 to 12tex, more preferably from 0.5 to 5tex, and even more preferably from 0.8 to 3.2tex. In the present invention, the count of the glass yarn is a value measured and calculated according to the method defined in "7.1 count" of the general test method for glass fibers "in JIS R3420 2013, japan industrial standard.

[ Density and weave of glass cloth ]

The warp yarn density and the weft yarn density of the glass cloth of the invention are above 70/25 mm. Thereby, the shear stress G in the weft direction of the glass cloth can be increased, and the residual shear strain rate 2HG/G can be easily satisfied with 1.4 (deg) ^-1 ) The following is given. From the same point of view, the warp yarn density and the weft yarn density are preferably 85/25 mm or more. The upper limit values of the warp yarn density and the weft yarn density are not particularly limited, but are preferably 130 yarns/25 mm or less, more preferably 120 yarns/25 mm or less, from the viewpoint of making the glass cloth lower in quality. The warp yarn density and weft yarn density are specifically 70 to 130 yarns/25 mm, preferably 85 to 120 yarns/25 mm. In the present invention, the warp yarn density and the weft yarn density are measured and calculated according to the method defined in "7.9 density (knitting density)" of JIS R3420 2013 "glass fiber general test method".

In the production of the glass cloth, the warp yarn is produced in a state of being tensioned more than the weft yarn. Accordingly, the weft yarn of the glass cloth is produced in a state of weak tension, and thus the yarn width is larger than the warp yarn when viewed from the glass cloth plane direction. Accordingly, in the present invention, the weft yarn may be defined as a glass yarn having a larger variation in yarn width when viewed in the plane direction among the warp yarn and the weft yarn.

The weave of the glass cloth is not particularly limited, and examples thereof include plain weave, satin weave, twill weave, basket weave, rib weave, and the like. Among them, a plain weave is preferable.

[ surface treatment of glass cloth ]

The glass cloth of the present invention comprises (A) a polyoxyalkylene bisphenol A ether and (B) a silane coupling agent having an acryl or methacryl group on at least a part of the surface of a long glass fiber filler. By including these, the bending hysteresis 2HB in the weft direction of the glass cloth can be reduced to a residual curvature 2HB/B of 0.5 (cm ^-1 ) The following is given. In addition, by including these, the shear hysteresis 2HG in the weft direction of the glass cloth can be reduced so that the residual shear strain rate 2HG/G is 1.4 (deg ^-1 ) The following is given.

The polyoxyalkylene bisphenol A ether refers to a compound represented by the following general formula (1).

[ chemical 1]

In the general formula (1), R ¹ And R is ² The same or different, represents an alkylene group. The number of carbon atoms of the alkylene group is, for example, 2 to 4, preferably 2 or 3, more preferably 2. In the general formula (1), n ¹ And n ² Represents the average molar number of addition of the alkylene oxide. As n ¹ And n ² For example, it is preferably 2 to 50, more preferably 4 to 30, and still more preferably 6 to 20.n is n ¹ And n ² The values may be different or substantially the same. As one embodiment of the polyoxyalkylene bisphenol A ether, R in the general formula (1) is given ¹ And R is ² Is the same alkylene group, and n ¹ And n ² Polyoxyalkylene bisphenol A ether of approximately 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 molar number of addition of alkylene oxides in the polyoxyalkylene bisphenol A ether used in the present invention is, for example, 2 to 40, preferably 4 to 30, more preferably 6 to 20. The average molar number of addition of the alkylene oxides in the polyoxyalkylene bisphenol A ether herein means an average value of the total number of alkylene oxides contained in 2 polyoxyalkylene chains constituting the polyoxyalkylene bisphenol A ether.

The silane coupling agent having an acryl group or methacryl group includes compounds represented by the following general formula (2).

[ chemical 2]

CH ₂ ＝CR ³ -CO-OR ⁴ -SiR ⁵ _m (OR ⁶ ) _3-m (2)

In the general formula (2), R ² 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. As R ⁴ The alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and still more preferably an alkylene group having 3 carbon atoms. R is R ⁴ The alkylene group may be linear or branched, and is preferably branched. In the general formula (2), R ⁵ And R is ⁶ Each independently represents an alkyl group having 1 to 5 carbon atoms. As R ⁵ And R is ⁶ Examples thereof include alkyl groups having 1 to 3 carbon atoms, more preferably alkyl groups having 1 or 2 carbon atoms, and still more preferably methyl groups. In the general formula (2), m represents an integer of 0 to 2. M is preferably 0 or 1, and more preferably 0.

As the silane coupling agent having an acryl group or a methacryl group, specifically, there can be exemplified: 3-Acryloyloxypropyl trimethoxysilane (in the general formula (2), R ³ H, R of a shape of H, R ⁴ is-C ₃ H ₆ -, m is 0, R ⁶ is-CH ₃ 3-methacryloxypropyl trimethoxysilane (in the general formula (2), R) ³ is-CH ₃ 、R ⁴ is-C ₃ H ₆ -, m is 0, R ⁶ is-CH ₃ 3-acryloxypropyl methyldimethoxysilane (in the general formula (2), R) ³ H, R of a shape of H, R ⁴ is-C ₃ H ₆ -, m is 1, R ⁵ And R is ⁶ is-CH ₃ 3-methacryloxypropyl methyl dimethoxy silane (in the general formula (2), R) ³ is-CH ₃ 、R ⁴ is-C ₃ H ₆ -, m is 1, R ⁵ And R is ⁶ is-CH ₃ A compound of (2),3-Acryloyloxypropyl triethoxysilane (in the general formula (2), R ³ H, R of a shape of H, R ⁴ is-C ₃ H ₆ -, m is 0, R ⁶ is-C ₂ H ₅ 3-methacryloxypropyl triethoxysilane (in the general formula (2), R ³ is-CH ₃ 、R ⁴ is-C ₃ H ₆ -, m is 0, R ⁶ is-C ₂ H ₅ A compound of (c) and the like. Among them, 3-acryloxypropyl trimethoxysilane and 3-methacryloxypropyl trimethoxysilane are preferred.

In the glass cloth of the present invention, the ratio of (a) the polyoxyalkylene bisphenol a ether to (B) the silane coupling agent having an acryl or methacryl group is, for example, 1 to 1000 parts by mass, preferably 10 to 500 parts by mass, more preferably 50 to 400 parts by mass, based on 100 parts by mass of the total amount of (a) the polyoxyalkylene bisphenol a ether, and (B) the silane coupling agent having an acryl or methacryl group.

In the glass cloth of the present invention, the mass ratio of the polyoxyalkylene bisphenol a ether (a) to the total amount of the components adhering to the surface of the long glass fiber filler is, for example, 10 to 90 parts by mass, preferably 10 to 80 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 15 to 45 parts by mass.

In the glass cloth of the present invention, the mass ratio of the silane coupling agent having an acryl or methacryl group (B) to 100 parts by mass of the total amount of the components adhering to the surface of the long glass fiber filler is, for example, 10 to 90 parts by mass, preferably 20 to 80 parts by mass.

In the glass cloth of the present invention, at least a part of the surface of the long glass fiber filler may contain a silane coupling agent other than (B) the silane coupling agent having an acryl or methacryl group. Examples of the silane coupling agent other than the silane coupling agent having an acryl or methacryl group (B) include a silane coupling agent having an amino group, a silane coupling agent having a vinyl group, a silane coupling agent having a phenyl group, a silane coupling agent having a glycidoxy group, a silane coupling agent having an isocyanate group, a silane coupling agent having a mercapto group, a silane coupling agent having a styryl group, a silane coupling agent having an ureido group, and the like. In particular, the combination of (B) a silane coupling agent having an acryl group or a methacryl group and a silane coupling agent having an amino group or a vinyl group is preferable in that the adhesion to a matrix resin is more easily improved when a prepreg is produced.

Examples of the silane coupling agent having an organic functional group containing an amino group include a compound represented by the following general formula (3) and a salt thereof.

[ chemical 3]

X-SiR ⁷ _p (OR ⁸ ) _3-p (3)

In the general formula (3), X represents an organic functional group having 1 or more amino groups. In the general formula (3), p represents an integer of 0 to 2. As p, preferably 0 or 1, more preferably 0. In the general formula (3), R ⁷ And R is ⁸ Each independently represents an alkyl group having 1 to 5 carbon atoms. As R ⁷ And R is ⁸ Examples thereof include alkyl groups having 1 to 3 carbon atoms, and more preferably alkyl groups having 1 or 2 carbon atoms.

Specific examples of the silane coupling agent having an amino group include monomeric compounds such as N- β - (N-vinylbenzylaminoethyl) - γ -aminopropyl trimethoxysilane and its hydrochloride, N- β - (N-vinylbenzylaminoethyl) - γ -aminopropyl triethoxysilane and its hydrochloride, N- β - (N-benzylaminoethyl) - γ -aminopropyl trimethoxysilane and its hydrochloride, N- β - (N-benzylaminoethyl) - γ -aminopropyl triethoxysilane and its hydrochloride, γ - (2-aminoethyl) aminopropyl trimethoxysilane, γ - (2-aminoethyl) aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, γ - (2-aminoethyl) aminopropyl triethoxysilane, and mixtures thereof. Of these, N-beta- (N-vinylbenzylaminoethyl) -gamma-aminopropyl trimethoxysilane and its hydrochloride, N-beta- (N-vinylbenzylaminoethyl) -gamma-aminopropyl triethoxysilane and its hydrochloride, N-beta- (N-benzylaminoethyl) -gamma-aminopropyl trimethoxysilane and its hydrochloride, N-beta- (N-benzylaminoethyl) -gamma-aminopropyl triethoxysilane and its hydrochloride are more preferable.

The silane coupling agent having a vinyl group or a styryl group includes a compound 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 1 or more vinyl groups or styryl groups. In the general formula (4), R ⁹ The alkyl group having 1 to 8 carbon atoms is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl. In general formula (4), OR ¹⁰ The alkoxy group having 1 to 8 carbon atoms which may have a substituent is preferably methoxy, ethoxy or methoxyethoxy. In the general formula (4), q is an integer of 0 to 2, preferably 0.

Specific examples of the silane coupling agent having a vinyl group or a styryl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, styryltrimethoxysilane, and the like.

In the glass cloth of the present invention, the mass ratio of the total amount of the silane coupling agent to 100 parts by mass of the total amount of the components adhering to the surface of the long glass fiber filler is, for example, 10 to 90 parts by mass, preferably 40 to 90 parts by mass, and more preferably 45 to 85 parts by mass. The total amount of the silane coupling agent means the total mass of (B) the silane coupling agent having an acryl or methacryl group and other silane coupling agents contained as needed.

In the glass cloth of the present invention, the mass ratio of the silane coupling agent having an acryl or methacryl group (B) to 100 parts by mass of the total amount of the silane coupling agents attached to the surface of the long glass fiber filler is, for example, 10 to 100 parts by mass, preferably 30 to 100 parts by mass, and more preferably 50 to 100 parts by mass. The total amount of the silane coupling agent means the total mass of (B) the silane coupling agent having an acryl or methacryl group and other silane coupling agents contained as needed.

In the glass cloth of the present invention, a softening agent, an antistatic agent, and a surfactant may be contained as necessary in at least a part of the surface of the long glass fiber filler. The softening agent, antistatic agent, and surfactant may be appropriately 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 mass%. The carbon amount is an index of the adhesion amount of a surface treatment agent comprising (a) a polyoxyalkylene bisphenol a ether and (B) a silane coupling agent having an acryl group or a methacryl group. By setting the carbon content to the above range, the bending rigidity B can be effectively improved, and the residual curvature 2HB/B can be made 0.5 (cm ^-1 ) The following is given. The carbon content is more preferably 0.5 to 1.2 mass%, and still more preferably 0.6 to 1.1 mass%, from the viewpoint of easier improvement of adhesion to the matrix resin when the prepreg is produced. In the present invention, the carbon amount is a value measured according to the following procedure. First, using a total carbon measurement device, the glass cloth was burned and reduced at a reaction temperature of 850 ℃ and a reduction temperature of 600 ℃ under an oxygen cycle, and total organic carbon separated by porous polymer bead packed column chromatography was quantified using a Thermal Conductivity Detector (TCD). Next, the carbon amount of the glass cloth was calculated from a standard curve prepared using elemental quantitative standard specimen acetanilide as a standard specimen.

In the glass cloth of the present invention, the weight loss on ignition is not particularly limited, and examples thereof include: 0.2 to 1.5% by mass, preferably 0.5 to 1.5% by mass, more preferably 1.0 to 1.4% by mass, and even more preferably 1.05 to 1.3% by mass. In the present invention, the loss on ignition is in accordance with Japanese Industrial Standard JIS R3420: 2013 "glass fiber general test method" in "7.3.2 loss on ignition".

The quality of the glass cloth of the present invention is not particularly limited, and examples thereof include: 5-50 g/m ² Preferably 5 to 30g/m ² More preferably 5 to 20g/m ² . In the present invention, the mass of the glass cloth is in accordance with japanese industrial standard JIS R3420:2013 "mass (mass) of cloth and mat of 7.2" of glass fiber general test method ".

The thickness (μm) of the glass cloth of the present invention is not particularly limited, and examples thereof include 5 to 50. Mu.m, preferably 5 to 30. Mu.m, and more preferably 9 to 25. Mu.m. In the present invention, the thickness of the glass cloth is measured by using an electronic micrometer having a minimum display value of 0.001mm according to JIS R3420 of Japanese Industrial Standard: 2013 "thickness of 7.10.1 cloth of glass fiber general test method" by the B method.

In the glass cloth of the present invention, the tensile strength in the warp direction is 20 to 120N/25mm, preferably 25 to 110N/25mm, more preferably 30 to 100N/25mm. The tensile strength is a value obtained by: according to Japanese Industrial Standard JIS R3420:2013 "case of glass fiber general test method" the method specified in "7.4.2 cloth" was used, the length of the test piece was set to 25cm, the width of the test piece (width before yarn was unwound from both ends) was set to 30mm, the holding interval was set to 15cm, the width of the test piece (width after yarn was unwound from both ends) was set to 25mm, the constant-speed stretching speed was set to 200mm/min, and the warp direction of the glass cloth was measured 5 times, respectively, and the average value was set to the warp-direction tensile strength (N/25 mm) of the glass cloth.

In the production of glass cloth, the degreasing treatment of the bundling agent and paste required for weaving warp and weft is performed. This deoiling treatment is called a heat washing treatment. The tensile strength of the glass cloth subjected to the heat-cleaning treatment is reduced to about half or less as compared with that before the heat-cleaning treatment. The preferable range of the tensile strength is 20 to 120N/25mm, which means that the tensile strength of the glass cloth subjected to the heat-cleaning treatment is significantly different from that of the glass cloth not subjected to the heat-cleaning treatment.

In the glass cloth comprising a glass yarn comprising a plurality of glass filaments as warp yarns and weft yarns, at least a part of the surface of the glass filaments comprises (A) a polyoxyalkylene bisphenol A ether and (B) a silane coupling agent having an acryl or methacryl, the glass cloth has a weave density of 70 pieces/25 mm or more, and the glass cloth has a carbon content of 0.4 to 1.5 mass%, based on which the glass cloth can be fully usedFoot residual curvature 2HB/B is 0.5cm ^-1 The residual shear strain rate 2HG/G was 1.4 (deg) ^-1 ) The following is given. A more preferable range of the residual curvature 2HB/B provided in the glass cloth of the present invention is 0.1cm ^-1 Above and 0.5cm ^-1 Hereinafter, more preferably 0.2cm ^-1 Above and 0.45cm ^-1 The following is given. Further, the residual shear strain rate 2HG/G of the glass cloth of the present invention is preferably in the range of 0.1deg ^-1 Above and 1.4deg ^-1 Hereinafter, more preferably 0.5deg ^-1 Above and 1.2deg ^-1 Hereinafter, it is more preferably 0.7deg ^-1 Above and 1.1deg ^-1 The following is given.

In the present invention, the residual curvature 2HB/B of the glass cloth is a value measured by using a KES-FB2 pure bending tester manufactured by Kato Tech Co. The method for measuring the residual curvature 2HB/B of the glass cloth will be described below with reference to FIG. 1. The left diagram of fig. 1 (a) is a schematic diagram of a state in which a glass cloth is bent into an arc shape using a pure bending tester, and the right diagram of fig. 1 (a) is a diagram schematically showing a bending moment (M) generated in a state in which a glass cloth is bent into an arc shape using a pure bending tester. FIG. 1 (b) shows an example of a bending hysteresis curve obtained by using a pure bending tester. First, two samples were prepared, each of which was obtained by cutting a glass cloth into a 20cm×20cm piece, and the two pieces were stacked so that warp and weft were in the same direction, and the two pieces were used as test samples. In the case where the warp yarn and the weft yarn in the glass cloth cannot be immediately distinguished from each other, as described above, it is determined that the one having the larger variation in yarn width when viewed in the plane direction corresponds to the weft yarn. The test sample was fixed with a distance between chucks of 1 cm. When the test sample is fixed, the test sample is uniformly wound around the chuck from both ends in the longitudinal direction of the weft yarn (i.e., the direction in which the weft yarn continues). Next, as shown in fig. 1 (a), the weft yarn was cut at a constant speed (deformation speed (0.5) ^-1 /sec)) is curved in an arc shape until the curvature k= +2.5cm is reached ^-1 The weft yarn is then laid down at a uniform speed (deformation speed (0.5 ^-1 /sec)) is curved in an arc shape to the opposite side until the maximum curvature becomes-2.5 cm ^-1 After the recovery, a bending test was performed to measure a bending moment generated with a change in curvature (fig. 1 (a))). The bending test was performed in 1 cycle, and a bending hysteresis curve (vertical axis: bending moment, horizontal axis: curvature) shown in fig. 1 b was obtained as a bending characteristic value. From the bending hysteresis curve, the bending rigidity B (gf cm) per unit length was obtained ² /cm) and a hysteresis width 2HB (gf cm/cm). The assay was performed at 23℃in a 50% RH environment. In the present invention, the bending rigidity B per unit length is defined as the bending rigidity k= +0.5cm ^-1 To +1.5cm ^-1 The average inclination of the differential values of the bending moment (M) measured therebetween, the width of hysteresis 2HB as the curvature K= +1.0cm ^-1 The width of the hysteresis (see fig. 1 b) is calculated. The present measurement can be performed, for example, using the KES-FB SYSTEM (Ver.7.18 WJ) data measurement program, and the KES-FB CALC (Ver.7.07J) data calculation program is used to calculate B and 2HB. The above measurement was performed 5 times using 10 different glass cloth samples, and the ratio of bending hysteresis 2HB in the weft direction to bending stress B in the weft direction, that is, the average value of residual shear strain rate 2HB/B was obtained.

In the present invention, the residual shear strain rate 2HG/G of the glass cloth is a value measured by using a KES-FB1 tensile shear tester manufactured by Kato Tech Co. Hereinafter, a method for measuring the residual shear strain rate 2HG/G of the glass cloth will be described with reference to FIG. 2. FIG. 2 (a) is a drawing of glass cloth to a shearing angle by a tensile shear testerFig. 2 (b) is an example of a shear hysteresis curve obtained by using a tensile shear tester. First, two samples were prepared, each of which was obtained by cutting a glass cloth into a 20cm×20cm piece, and the two pieces were stacked so that warp and weft were in the same direction, and the two pieces were used as test samples. In the case where the warp yarn and the weft yarn in the glass cloth cannot be immediately distinguished from each other, as described above, it is determined that the one having the larger variation in yarn width when viewed in the plane direction corresponds to the weft yarn. The test sample was fixed with a distance between chucks of 5 cm. When the test sample is fixed, the test sample is uniformly wound around the chuck from both ends in the longitudinal direction of the weft yarn (i.e., the direction in which the weft yarn continues). Then, as shown in FIG. 2As shown, the warp yarn was deformed in the longitudinal direction (i.e., the direction in which the warp yarn continued) to a shearing angle at a constant speed (0.00834 °/sec) under a forced load (W) of 10gf/cm in the longitudinal direction (i.e., the direction in which the warp yarn continued) of the weft yarn >Then deformed in the opposite direction to a shearing angle +.>After that, the sheet is restored again, and the shearing force generated together with the change in the shearing angle is measured (see fig. 2 (a)). The shear test was performed in 1 cycle, and a shear hysteresis curve (vertical axis: shear force, horizontal axis: shear angle) shown in fig. 2 (b) was obtained as a shear characteristic value. From the shear hysteresis curve, the shear stress G (gf/cm/deg) in the weft direction and the hysteresis width 2HG (gf/cm) were obtained. The assay was performed at 23℃in a 50% RH environment. The shear stress G per unit length is defined as +.> Average gradient of differential value of shear force (Fs) measured between +2.5, width of hysteresis 2HG as shear angleThe width of the lag at the time (see fig. 2 b). The present measurement can be performed, for example, using the KES-FB SYSTEM (Ver.7.18 WJ) data measurement program, and G and 2HG are calculated using the KES-FB CALC (Ver.7.07J) data calculation program. The above measurement was performed 5 times using 10 different glass cloth samples, and the average value of the residual shear strain rate 2HG/G, which is the ratio of the shear hysteresis 2HG (gf/cm) in the weft direction to the shear stress G (gf/cm/deg) in the weft direction, was obtained.

[ method for producing glass cloth ]

Next, an example of a method for producing a glass cloth according to the present invention will be described. First, a glass cloth is woven with glass yarns including a plurality of glass filaments as warp yarns and weft yarns. The knitting method may be any conventionally known method, and examples thereof include a step of applying a warping step and a sizing step to warp yarns, and then driving weft yarns using a jet loom (e.g., an air jet loom, a water jet loom, etc.), a Sulzer loom, a rapier loom (rapier loom), etc.

Then, a fiber opening treatment and/or a heat cleaning treatment may be performed as needed. Examples of the method of the opening treatment include an opening treatment of the obtained glass cloth by the pressure of water flow, an opening treatment by high-frequency vibration with water (for example, deaerated water, ion-exchanged water, deionized water, electrolytic cationic water, or electrolytic anionic water) as a medium, and a processing treatment under pressure by a roll. The opening treatment may be performed simultaneously with the knitting or after the knitting. The fiber-opening treatment may be performed before or after the heat-washing treatment or simultaneously with the heat-washing treatment, or may be performed simultaneously with or after the surface treatment described later. As a method for adjusting the opening degree of the warp and weft, a known method can be used, and a method for adjusting the warp tension can be mentioned; a method of opening a fiber while adjusting and balancing the tension in the warp direction and the weft direction by using a Pinch expander (Pinch expander), a bending rubber roller, a rotary slide roller, a Miravo roller, or a tenter; or a method of combining them, and the like.

When a substance (for example, a bundling agent or the like) that inhibits adhesion and impregnation of a matrix resin when a prepreg or a printed wiring board is produced is attached to the woven glass cloth, the substance is preferably removed by, for example, a heat-washing treatment or the like. The heat-cleaning treatment may be omitted for glass cloth woven from glass yarns to which a surface treatment agent described later is applied to the paste for 1 time and 2 times. The temperature conditions for the heat-washing treatment include preferably 350℃or higher, more preferably 350 to 500℃and still more preferably 380 to 450 ℃. The time for the heat-washing treatment may be appropriately set according to the temperature conditions used, and for example, when the glass cloth is formed into a roll product (a product in which the glass cloth is wound around a winding core), the heat-washing treatment is performed in the state of the roll product, and may be performed for 20 to 60 hours, preferably 24 to 48 hours, and more preferably 24 to 36 hours.

Then, in the method for producing a glass cloth according to the present invention, the prepared glass cloth is subjected to a surface treatment. As the surface treatment, first, a treating agent is prepared.

The prepared treating agent contains a component and a solvent which adhere to the surface of the long glass fiber filler, specifically, a treating agent containing (a) a polyoxyalkylene bisphenol a ether and/or (B) a silane coupling agent having an acryl or methacryl group, and a solvent. The type of the solvent is not particularly limited, and examples thereof include water.

The content of the polyoxyalkylene bisphenol A ether (A) in the treating agent is not particularly limited, and examples thereof include 1 to 30g/L, preferably 2 to 20g/L, and more preferably 3 to 15g/L. The content of the silane coupling agent having an acryl or methacryl group in the treating agent (B) is not particularly limited, and examples thereof include 3 to 40g/L, preferably 5 to 35g/L, and more preferably 10 to 30g/L.

The mass ratio of the polyoxyalkylene bisphenol a ether (a) in the mass of the total nonvolatile components contained in the treating agent is not particularly limited, and may be, for example, 10 to 90 mass%, preferably 20 to 80 mass%, more preferably 10 to 50 mass%, and even more preferably 15 to 45 mass%. The proportion of the mass of the silane coupling agent having an acryl or methacryl group (B) in the mass of the total nonvolatile components contained in the treating agent is not particularly limited, and may be, for example, 10 to 90 mass%, and preferably 20 to 80 mass%. The proportion of the total silane coupling agent in the mass of the total nonvolatile components contained in the treating agent is not particularly limited, and may be, for example, 10 to 90 mass%, preferably 40 to 90 mass%, and more preferably 45 to 85 mass%. The proportion of the total mass of the silane coupling agents having an acryl group or a methacryl group relative to 100 parts by mass of the total silane coupling agents contained in the treating agent is not particularly limited, and may be, for example, 10 to 100 parts by mass, preferably 30 to 100 parts by mass, and more preferably 50 to 100 parts by mass. In the present invention, the term "nonvolatile component" means an absolute dry component when a constant amount is obtained by removing a solvent or the like by heat treatment at 110 ℃ under normal pressure, and is a component that remains after finally adhering to the surface of the long glass fiber filler in the glass cloth of the present invention.

The surface of the glass cloth can be treated by applying the treating agent to the glass cloth by a method of dipping, coating or spraying the prepared treating agent on the glass cloth, or the like, and then drying the glass cloth. In the surface treatment step, the prepared glass cloth may be subjected to surface treatment by applying and drying the glass cloth as a treatment agent in which the (a) and (B) are mixed, or the glass cloth may be subjected to surface treatment by applying and drying the (a) and (B) as respective treatment agents in 2 stages.

[ shape and use of glass cloth ]

In one embodiment of the glass cloth of the present invention, a long roll-shaped glass cloth in which a glass cloth is wound around a winding core is provided. In the case where the glass cloth of the present invention is a rolled glass cloth, the length and width of the glass cloth are not particularly limited, and examples thereof include 10 to 4000m, preferably 50 to 3000m, more preferably 100 to 2000m, and examples thereof include 10 to 200cm, preferably 30 to 150cm, more preferably 50 to 130cm.

The glass cloth of the present invention is suitable for use as a fibrous substrate for prepregs. In particular, the glass cloth of the present invention is particularly suitable for use as a fibrous substrate for prepregs for printed wiring boards. The prepreg using the glass cloth of the present invention will be described later.

2. Prepreg material

The prepreg of the present invention comprises the glass cloth and a thermosetting resin contained in a state of being impregnated in the glass cloth.

The thermosetting resin is not particularly limited as long as it is a resin cured by heat, and examples thereof include phenol resins, epoxy resins, non-halogen epoxy resins, cyanate resins, maleimide resins, bismaleimide resins, modified bismaleimide resins, isocyanate resins, benzocyclobutene resins, vinyl resins, bismaleimide triazine resins, phenol resins, thermosetting polyphenylene ether resins, and the like. The thermosetting resin may be used alone or in combination of 2 or more.

The prepreg of the present invention may contain an inorganic filler. Examples of the inorganic filler include silica types such as natural silica, fused silica, amorphous silica, and hollow silica; boehmite (b); molybdenum compounds such as molybdenum oxide and zinc molybdate; glass fillers such as alumina, talc, calcined talc, mica, glass short fibers, and spherical glass (glass fillers having E glass, T glass, UT glass, S glass, D glass, NE glass, L glass, and LU glass as glass materials).

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

Examples

Hereinafter, examples and comparative examples are shown and the present invention is described in detail. The invention is not limited to the examples.

1. Measurement and evaluation method

1-1 average fiber diameter and number of glass filaments

The average fiber diameter of the glass filaments and the number of the glass filaments constituting the glass yarn were measured as follows. That is, 2 pieces of glass cloth obtained by cutting the glass cloth into 30cm square glass cloth were prepared, one was used for warp observation and the other was used for weft observation, and each of them was embedded in an epoxy-based cold-setting resin (trade name epoxy Specix-40 manufactured by Struers Co., ltd.) and cured. Next, the glass cloth embedded in the epoxy resin was ground to such an extent that warp and weft could be observed, and the average fiber diameter was observed at a magnification of 2000 times and the number was observed at a magnification of 500 times by using a Scanning Electron Microscope (SEM) (trade name JSM-6390A manufactured by japan electronics corporation).

(1) Average fiber diameter (μm) of glass long fiber

30 warp yarns and weft yarns were randomly selected, and the diameters of the long glass fibers included in the 30 glass yarns were measured by observing the cross sections of the long glass fibers, and the average values were calculated as the average fiber diameters of the long glass fibers of the warp yarns and the weft yarns.

(2) Number of glass long fiber (root)

30 warp yarns and weft yarns were randomly selected, and the total number of long glass fibers contained in each of the 30 glass yarns was measured to calculate an average value as the number of long glass fibers in the warp yarns and weft yarns.

1-2 weaving Density of glass cloth

The weaving density of the glass cloth is in accordance with japanese industrial standard JIS R3420: 2013 "glass fiber general test method" was measured by a method specified in "7.9 density (braid density)". Specifically, the positions 50mm or more from the ends and sides of the glass cloth are set to 10mm or more and 200mm or less in the measurement interval, and the total yarn count within the set measurement interval is measured. This was taken as 1 measurement, moved to another position not containing the yarn measured before, and the total yarn count within the measurement interval was measured 2 more times by the same method. For each 3 measurements, the number of yarns per 25mm was determined according to the following formula, and the average of 3 measurements was calculated.

[ number 1]

Mi＝(ni/ai)×25

Mi: number of yarns per 25mm

ni: number of measured yarn

ai: the correct distance (mm) to measure

1-3 count of glass yarn

The count of glass yarn in the glass cloth was measured according to the method specified in "7.1 count" of "glass fiber general test method" of JIS R3420 2013, japan industrial standard. Specifically, first, 500m glass yarn was collected from a yarn winding device, and a test piece was produced. The test piece was placed flat and in a muffle furnace, burned at 625 ℃ for 25 minutes, and then cooled in a dryer to determine the mass of the test piece. The count was calculated according to the following formula.

[ number 2]

t＝(m/500)×1000

t: count number

m: quality of test piece (g)

1-4 quality of glass cloth

The quality of the glass cloth was in accordance with Japanese Industrial Standard JIS R3420: 2013 "mass (mass) of cloth and mat of 7.2" glass fiber general test method ". Specifically, the area of the glass cloth collected from a position 50mm or more from the edge of the glass cloth was 100cm ² After drying the test piece at 105℃for 1 hour, the mass of the test piece was measured and calculated for each 1m according to the following formula ² Is a mass of (3).

[ number 3]

ρA＝(ms/100)×10 ⁴

ρa: every 1m ² Mass (g/m) ² )

ms: quality of test piece (g)

1-5 thickness of glass cloth

The thickness of the glass cloth is in accordance with Japanese Industrial Standard JIS R3420: 2013 "thickness of 7.10.1 cloth" of glass fiber general test method "was measured by the method B specified in the specification. Specifically, the thickness of the portion located 50mm or more inward from both ends and the edge was measured using an electronic micrometer having a minimum display value of 0.001 mm.

1-6, loss on ignition of glass cloth

The weight loss on ignition of the glass cloth was determined in accordance with Japanese Industrial Standard JIS R3420: 2013 "glass fiber general test method" the method specified in "7.3.2 loss on ignition" was used for measurement. Specifically, 100cm is cut from the inner part of the distance angle or end 10mm or more ² The above test piece was put into a dryer at 105℃and dried for 30 minutes. After drying, the test piece was transferred to a dryer, cooled to room temperature, and the mass was measured. The drying, cooling and measurement were repeated until the mass became constant, and the mass of the dried test piece was obtained. Next, the dried test piece was placed in a muffle furnace adjusted to 625℃and heated for 10 minutes or more. After the test piece was taken out of the muffle furnace, it was transferred to a dryer and cooled, and the mass of the test piece was measured. Repeating the heating, cooling and measuring until the mass becomesThe mass of the dried and heated test piece was determined at a constant level. The loss on ignition (%) was calculated as follows.

[ number 4]

H ₂ ＝(m ₁ -m ₂ )/m ₁ ×100

H ₂ : loss on ignition (%)

m ₁ : quality (g) of dried test piece

m ₂ : quality (g) of dried and heated test piece

1-7 tensile Strength of glass cloth

Tensile strength of glass cloth is in accordance with Japanese Industrial Standard JIS R3420: 2013 "case of a glass fiber general test method" was defined in "7.4.2 cloth", using a constant-speed elongation tensile tester (manufactured by Intersco corporation), the test piece length was set to 25cm, the width of the test piece (width before unwinding the yarn from both ends) was set to 30mm, the holding interval was set to 15cm, the width of the test piece (width after unwinding the yarn from both ends) was set to 25mm, the constant-speed stretching speed was set to 200mm/min, and the 5-time breaking strength was measured for the warp direction of the glass cloth, and the average value of the measured values was taken as the tensile strength (N/25 mm) of the glass cloth.

1-8 carbon content of glass cloth

The glass cloth was burned and reduced at a reaction temperature of 850℃and a reduction temperature of 600℃under an oxygen cycle using a total carbon measuring apparatus (Sumika Chemical Analysis Service, ltd. SUMIGRAPH (registered trademark) NCH-22F), and the total organic carbon obtained by the porous polymer bead packed column chromatography was quantified by a Thermal Conductivity Detector (TCD). The carbon content of the glass cloth was calculated from a standard curve prepared using elemental quantitative standard specimen acetanilide as a standard specimen.

1-9 variation in yarn widths of warp and weft yarns

The yarn width unevenness was obtained by cutting a glass cloth into 20cm×20cm pieces, arbitrarily selecting 1 glass yarn constituting warp yarn when viewed in a plane direction by an optical microscope or the like, measuring yarn widths of 3 portions 1cm in a longitudinal direction of the glass yarn from one end, repeatedly measuring the yarn widths at 19 total positions from the positions at 1cm intervals in the longitudinal direction of the glass yarn, and obtaining a coefficient of variation CV (=standard deviation/average) of the yarn widths at 19 positions. The measurement was performed on 3 glass yarns constituting warp yarns, and the average value of CV values of the 3 warp yarns was obtained. The CV value of the yarn width of the glass yarn constituting the weft yarn was also obtained by the same method. The larger the CV value, the larger the yarn width unevenness was determined.

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 bending tester. Specifically, two samples were prepared, each of which was obtained by cutting a glass cloth into 20cm×20cm pieces, and the two pieces were stacked so that the warp and weft were in the same direction, and the two pieces were used as test samples. The test sample was fixed with a distance between chucks of 1 cm. When the test sample is fixed, the test sample is uniformly wound around the chuck from both ends in the longitudinal direction of the weft yarn. Next, as shown in fig. 1 (a), the weft yarn was cut at a constant speed (deformation speed (0.5) ^-1 /sec)) is curved in an arc shape until the curvature k= +2.5cm is reached ^-1 The weft yarn is then laid down at a uniform speed (deformation speed (0.5 ^-1 /sec)) is curved in an arc shape to the opposite side until the maximum curvature becomes-2.5 cm ^-1 After that, a bending test was performed to measure a bending moment generated together with a change in curvature (fig. 1 (a)). The bending test was conducted in 1 cycle, and the bending hysteresis curve shown in FIG. 1 (B) was obtained as a bending characteristic value, and the bending rigidity B (gf cm) per unit length was obtained ² /cm) and a hysteresis width 2HB (gf cm/cm). The assay was performed at 23℃in a 50% RH environment. In the present invention, B is a value obtained by blending a material having a curvature of k= +0.5cm ^-1 To +1.5cm ^-1 The average inclination of the differential values of the bending moment (M) measured therebetween is 2HB as the curvature K= +1.0cm ^- The width of the hysteresis in 1 (see fig. 1 (b)). In this experiment, measurements were made using the KES-FB SYSTEM (Ver.7.18 WJ) data measurement program, and B and 2HB were calculated using the KES-FB CALC (Ver.7.07J) data calculation program. The residual shear was determined by performing 5 above determinations using 10 different glass cloth samplesAverage strain rate 2 HB/B.

1-11 residual shear Strain Rate 2HG/G

The residual shear strain rate 2HG/G was measured using a KES-FB1 manufactured by Kato Tech Co., ltd. Specifically, two samples were prepared, each of which was obtained by cutting a glass cloth into a 20cm×20cm piece, and the two pieces were overlapped so that warp and weft were in the same direction, and the two pieces were used as test samples. The test sample was fixed with a distance between chucks of 5 cm. When the test sample is fixed, the test sample is uniformly wound around the chuck from both ends in the longitudinal direction of the weft yarn. Next, as shown in fig. 2, the warp yarn was deformed at a constant velocity (0.00834 °/sec) to a shearing angle in the longitudinal direction of the warp yarn (i.e., the direction in which the warp yarn continued) in a state where a force load (W) of 10gf/cm was applied to the longitudinal direction of the weft yarn (i.e., the direction in which the weft yarn continued) Then deformed in the opposite direction to a shearing angle +.>After that, the sheet is restored again, and the shearing force generated together with the change in the shearing angle is measured (see fig. 2 (a)). The shear test was performed at 1 cycle, and a shear hysteresis curve shown in FIG. 2 (b) was obtained as a shear characteristic value, and the shear stress G (gf/cm/deg) in the weft direction and the hysteresis width 2HG (gf/cm) were obtained. The assay was performed at 23℃in a 50% RH environment. G is +.>The average inclination of the differential values of the shear forces (Fs) measured between +2.5, 2HG, is taken as the shear angle +.>The width of the lag at the time (see fig. 2 b). In this assay, the measurements were performed using the KES-FB SYSTEM (Ver.7.18 WJ) data measurement program and the G and 2HG were calculated using the KES-FB CALC (Ver.7.07J) data calculation program. Using 10 different glass cloth patternsThe above measurement was performed 5 times, and the average value of the residual shear strain rate 2HG/G was obtained.

1-12 evaluation of the level of warp stripes of glass cloth

The obtained glass cloth was visually inspected randomly for 1000m length, the number of warp stripes was observed, the number of warp stripes per 100m length was calculated, and the evaluation was performed according to the following criteria. The warp direction stripes were counted for stripes having a length of 100cm or more.

A: the number of warp stripes was 0.0/100 m.

B: the number of warp stripes is 0.1-0.5/100 m.

C: the number of warp stripes produced exceeds 0.6/100 m.

1-13 evaluation of the occurrence of oblique wrinkles in glass cloth

The obtained glass cloth was visually inspected randomly for 1000m in length, and the number of diagonal wrinkles was observed to evaluate the presence or absence of diagonal wrinkles. The diagonal wrinkles are wrinkles having a length of 10cm or more.

A: no number of diagonal wrinkles was observed.

B: the number of diagonal wrinkles was observed.

2. Manufacture of glass cloth

Example 1

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :51 mass%, al ₂ O ₃ :13 mass percent of CaO:8 mass%, B ₂ O ₃ :23 mass% and the balance of 5 mass% of a low dielectric constant low dielectric loss tangent glass material, wherein the average fiber diameter was 4.0 μm and the number of the fibers was 100. Glass yarns were woven with an air-jet loom to obtain plain weave glass cloth rolls (a roll-shaped glass cloth in which a long glass cloth was wound around a winding core) having a warp density of 75 pieces/25 mm and a weft density of 76 pieces/25 mm. Next, the obtained glass cloth roll was heated at an atmospheric temperature of 400℃for 30 hours, thereby performing a heat cleaning treatment And (5) managing. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

Next, the treating agent of formula 1 was prepared as a surface treating agent. The composition ratio of the nonvolatile components of the treating agent is shown in table 1.

(formulation 1)

N-beta- (N-vinylbenzyl amino ethyl) -gamma-aminopropyl trimethoxysilane hydrochloride (trade name Sila-Ace (registered trademark) S-350, non-volatile component 30% manufactured by JNC Co., ltd.): 9.0g/L

3-methacryloxypropyl trimethoxysilane (trade name Sila-Ace (registered trademark) S-710, non-volatile 98%) manufactured by JNC Co., ltd.): 13.5g/L

Polyoxyethylene bisphenol A ether (trade name GF690, non-volatile component 70% manufactured by Jicun oil chemical Co., ltd.): 5.2g/L

The balance: pure water

Applying 150N/m tension to the glass cloth subjected to the heat cleaning treatment along the length direction of the warp (the continuous direction of the warp) and immersing the glass cloth in the treating agent of formula 1 at the same time, using 35N/cm ² Is pressed by a nip roll having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 1 at a concentration of 35N/cm ² Is pressed by a clamping roller of the clamping pressure, and is dried at a temperature of 120 ℃, thereby obtaining the glass cloth.

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

Example 2

As warp and weft yarns, glass yarns comprising glass filaments are used, which glass filaments consist of: siO (SiO) ₂ :51 mass%, al ₂ O ₃ :13 mass percent of CaO:8 mass%, B ₂ O ₃ :23 mass% and the balance of 5 mass% of a low dielectric constant low dielectric loss tangent glass material, and the average fiber diameter was4.0 μm, the number of the roots is 100. Glass yarn was woven with an air jet loom to obtain a plain weave glass cloth roll having a warp density of 75 pieces/25 mm and a weft density of 76 pieces/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

Next, the treating agent of formula 2 was prepared as a surface treating agent. The composition ratio of the nonvolatile components of the treating agent is shown in table 1.

(formulation 2)

3-methacryloxypropyl trimethoxysilane (trade name Sila-Ace (registered trademark) S710, manufactured by JNC Co., ltd., nonvolatile 98%): 6.75g/L

Vinyl trimethoxy silane (trade name Sila-Ace (registered trademark) S210, nonvolatile matter 99%) manufactured by JNC corporation: 6.0g/L

Polyoxyethylene bisphenol A ether (trade name GF690, non-volatile component 70% manufactured by Jicun oil chemical Co., ltd.): 15.7g/L

Polyalkylene polyamine fatty acid amide (trade name KSK-2240, non-volatile matter 30% manufactured by Lion Specialty Chemicals Co., ltd.): 5.0g/L

The balance: pure water

Applying 150N/m tension to the glass cloth subjected to the heat cleaning treatment along the length direction of the warp yarn, and immersing the glass cloth in the treating agent of formula 2 at the same time, using 35N/cm ² Is pressed by a nip roller having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 2 at a concentration of 35N/cm ² Is pressed by a clamping roller of the clamping pressure, and is dried at a temperature of 120 ℃, thereby obtaining the glass cloth.

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

Example 3

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :51 mass%, al ₂ O ₃ :13 mass percent of CaO:8 mass%, B ₂ O ₃ :23 mass% and the balance of 5 mass% of a low dielectric constant low dielectric loss tangent glass material, wherein the average fiber diameter was 4.0 μm and the number of the fibers was 100. Glass yarn was woven with an air jet loom to obtain a plain weave glass cloth roll having a warp density of 75 pieces/25 mm and a weft density of 76 pieces/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

Next, the treating agent of formula 3 was prepared as a surface treating agent. The composition ratio of the nonvolatile components of the treating agent is shown in table 1.

(formulation 3)

The balance: pure water

Applying 150N/m tension to the glass cloth subjected to the heat cleaning treatment along the length direction of the warp yarn, and immersing the glass cloth in the treating agent of formula 3 at the same time, using 35N/cm ² Is pressed by a nip roller having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 3 at a concentration of 35N/cm ² Is pressed by a clamping roller of the clamping pressure, and is dried at a temperature of 120 ℃, thereby obtaining the glass cloth.

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

Example 4

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :49 mass% of Al ₂ O ₃ :14 mass%, caO:6 mass%, B ₂ O ₃ :28 mass% and the balance of 3 mass% of a low dielectric constant low dielectric loss tangent glass material, wherein the average fiber diameter was 4.0 μm and the number of the fibers was 50. Glass yarn was woven with an air jet loom to obtain a plain weave glass cloth roll having a warp density of 95/25 mm and a weft density of 95/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

Next, the treating agent of the above formula 1 was prepared as a surface treating agent. The composition ratio of the nonvolatile components of the treating agent is shown in table 1.

Applying 150N/m tension to the glass cloth subjected to the heat cleaning treatment along the length direction of the warp yarn, and immersing the glass cloth in the treating agent of formula 1 at the same time, using 35N/cm ² Is pressed by a nip roller having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 1 at a concentration of 35N/cm ² Is pressed by a clamping roller of the clamping pressure, and is dried at a temperature of 120 ℃, thereby obtaining the glass cloth.

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

Example 5

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :49 mass% of Al ₂ O ₃ :14 mass%, caO:6 mass%, B ₂ O ₃ :28 mass% of low dielectric constant and low dielectric loss with the balance being 3 mass% The loss tangent glass material had an average fiber diameter of 4.0 μm and a number of 50. Glass yarn was woven with an air jet loom to obtain a plain weave glass cloth roll having a warp density of 95/25 mm and a weft density of 95/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

Next, the treating agent of the above formula 2 was prepared as a surface treating agent. The composition ratios of the nonvolatile components of the treatment agents are shown in table 1.

The glass cloth subjected to the heat cleaning treatment was immersed in the treating agent of formula 2 while applying a tension of 150N/m along the longitudinal direction of the warp yarn, and the tension was adjusted to 35N/cm ² Is pressed by a nip roller having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 2 at a concentration of 35N/cm ² Is pressed by a clamping roller of the clamping pressure, and is dried at a temperature of 120 ℃, thereby obtaining the glass cloth.

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

Example 6

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :49 mass% of Al ₂ O ₃ :14 mass%, caO:6 mass%, B ₂ O ₃ :28 mass% and the balance of 3 mass% of a low dielectric constant low dielectric loss tangent glass material, wherein the average fiber diameter was 4.0 μm and the number of the fibers was 50. Glass yarn was woven with an air jet loom to obtain a plain weave glass cloth roll having a warp density of 95/25 mm and a weft density of 95/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. At heatThe glass cloth after the cleaning treatment has no warp stripes and oblique wrinkles.

Next, the treating agent of the above formula 3 was prepared as a surface treating agent. The composition ratio of the nonvolatile components of the treating agent is shown in table 2.

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

Example 7

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :50 mass% of Al ₂ O ₃ :15 mass percent of CaO:5 mass%, B ₂ O ₃ :27 mass% and the balance of 3 mass% of a low dielectric constant low dielectric loss tangent glass material, wherein the average fiber diameter was 4.0 μm and the number of the fibers was 40. Glass yarn was woven with an air jet loom to obtain a plain weave glass cloth roll having a warp density of 95/25 mm and a weft density of 95/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

Next, the treating agent of the above formula 1 was prepared as a surface treating agent. The composition ratios of the nonvolatile components of the treatment agents are shown in table 2.

The glass cloth subjected to the heat cleaning treatment is arranged along the length of the warp yarnApplying 150N/m tension in the direction, soaking in the treating agent of formula 1, and applying 35N/cm tension ² Is pressed by a nip roller having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 1 at a concentration of 35N/cm ² Is pressed by a clamping roller of the clamping pressure, and is dried at a temperature of 120 ℃, thereby obtaining the glass cloth.

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

Example 8

Next, the treating agent of the above formula 2 was prepared as a surface treating agent. The composition ratio of the nonvolatile components of the treating agent is shown in table 2.

Applying 150N/m tension to the glass cloth subjected to the heat cleaning treatment along the length direction of the warp yarn, and immersing the glass cloth in the treating agent of formula 2 at the same time, using 35N/cm ² Is pressed by a nip roller having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 2 at a concentration of 35N/cm ² Is pressed by a clamping roller at a temperature of 120 DEG CDrying, thereby obtaining the glass cloth.

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

Example 9

Next, the treating agent of the above formula 3 was prepared as a surface treating agent. The composition ratios of the nonvolatile components of the treatment agents are shown in table 2.

The glass cloth obtained had a larger variation in weft yarn width than the warp yarn, a tensile strength in the warp direction of 39N/25mm, and a residual curvature 2HB/B in the weft direction of 0.49 (cm) ^-1 ) The residual shear strain rate in the weft direction 2HG/G was 1.01 (deg ^-1 ) Loss on ignition of 1.18 massThe carbon content was 0.66 mass%.

Example 10

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :54 mass% of Al ₂ O ₃ :14 mass%, caO:23 mass%, mgO:1 mass%, B ₂ O ₃ :6 mass% and the balance of 2 mass% of E glass, wherein the average fiber diameter is 3.6 μm and the number of the E glass is 38. Glass yarn was woven with an air jet loom to obtain a plain weave glass cloth roll having a warp density of 105/25 mm and a weft density of 110/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

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

Comparative example 1

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :51 mass%, al ₂ O ₃ :13 mass percent of CaO:8 mass%, B ₂ O ₃ :23 mass percent,The balance of 5 mass% of a low dielectric constant low dielectric loss tangent glass material, the average fiber diameter was 4.0 μm, and the number of the fibers was 100. Glass yarn was woven with an air jet loom to obtain a plain weave glass cloth roll having a warp density of 75 pieces/25 mm and a weft density of 76 pieces/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

Next, the treating agent of formula 4 was prepared as a surface treating agent. The composition ratio of the nonvolatile components of the treating agent is shown in Table 3.

(formulation 4)

Trimethoxyphenylsilane (trade name Z6124, non-volatile component 90% manufactured by DuPont Toray Specialty Material Co., ltd.): 14.7g/L

The balance: pure water

Applying 150N/m tension to the glass cloth subjected to the heat cleaning treatment along the length direction of the warp yarn, and immersing the glass cloth in the treating agent of formula 4 at the same time, using 35N/cm ² Is pressed by a nip roller having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 4 at a concentration of 35N/cm ² Is pressed by a clamping roller of the clamping pressure, and is dried at a temperature of 120 ℃, thereby obtaining the glass cloth.

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

Comparative example 2

Next, the treating agent of formula 5 was prepared as a surface treating agent. The composition ratio of the nonvolatile components of the treating agent is shown in Table 3.

(formulation 5)

The balance: pure water

Applying 150N/m tension to the glass cloth subjected to the heat cleaning treatment along the length direction of the warp yarn, and immersing the glass cloth in the treating agent of formula 5 at the same time, using 35N/cm ² Is pressed by a nip roller having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 5 at a concentration of 35N/cm ² Is pressed by a clamping roller of the clamping pressure, and is dried at a temperature of 120 ℃, thereby obtaining the glass cloth.

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

Comparative example 3

Next, the treating agent of formula 6 was prepared as a surface treating agent. The composition ratio of the nonvolatile components of the treating agent is shown in Table 3.

(formulation 6)

N-beta- (N-vinylbenzyl amino ethyl) -gamma-aminopropyl trimethoxysilane hydrochloride (trade name Sila-Ace (registered trademark) S-350, non-volatile component 30% manufactured by JNC Co., ltd.): 3.0g/L

The balance: pure water

Applying 150N/m tension to the glass cloth subjected to the heat cleaning treatment along the length direction of the warp yarn, and immersing the glass cloth in the treating agent of formula 6 at the same time, using 35N/cm ² Is pressed by a nip roller having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 6 at a concentration of 35N/cm ² Is pressed by a clamping roller of the clamping pressure, and is dried at a temperature of 120 ℃, thereby obtaining the glass cloth.

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

Comparative example 4

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :49 qualityAmount of Al ₂ O ₃ :14 mass%, caO:6 mass%, B ₂ O ₃ :28 mass% and the balance of 3 mass% of a low dielectric constant low dielectric loss tangent glass material, wherein the average fiber diameter was 4.0 μm and the number of the fibers was 50. Glass yarn was woven with an air jet loom to obtain a plain weave glass cloth roll having a warp density of 95/25 mm and a weft density of 95/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

Next, the treating agent of the above formula 5 was prepared as a surface treating agent. The composition ratios of the nonvolatile components of the treatment agents are shown in table 3.

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

Comparative example 5

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :50 mass% of Al ₂ O ₃ :15 mass percent of CaO:5 mass%, B ₂ O ₃ :27 mass% and the balance of 3 mass% of a low dielectric constant low dielectric loss tangent glass material, wherein the average fiber diameter was 4.0 μm and the number of the fibers was 40. Weaving glass yarn with air-jet loom to obtain 95 warp yarn density/25 mm and weft yarn densityA glass cloth roll with a plain weave of 95 pieces/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

Next, the treating agent of the above formula 5 was prepared as a surface treating agent. The composition ratio of the nonvolatile components of the treating agent is shown in Table 3.

Applying 150N/m tension to the glass cloth subjected to the heat cleaning treatment along the length direction of the warp yarn, and immersing the glass cloth in the treating agent of formula 5 at the same time, using 35N/cm ² Is pressed by a nip roller having a nip pressure, and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 5 at a concentration of 35N/cm ² Is pressed by a nip roller of the nip pressure of (a) and dried at a temperature of 120 ℃ to thereby obtain a glass cloth.

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

Comparative example 6

As warp and weft yarns, glass yarns comprising glass filaments consisting of: siO (SiO) ₂ :54 mass% of Al ₂ O ₃ :14 mass%, caO:23 mass%, mgO:1 mass%, B ₂ O ₃ :6 mass% and the balance of 2 mass% of E glass, wherein the average fiber diameter is 3.6 μm and the number of the E glass is 38. Glass yarns were woven with an air jet loom to give plain weave glass cloth rolls having a warp density of 105 yarns/25 mm and a weft density of 110 yarns/25 mm. Then, the obtained glass cloth roll was heated at an atmospheric temperature of 400 ℃ for 30 hours, thereby performing a heat cleaning treatment. In the glass cloth after the heat-washing treatment, warp stripes and diagonal wrinkles were not generated.

Applying 150N/m tension to the glass cloth subjected to the heat cleaning treatment along the length direction of the warp yarn, and immersing the glass cloth in the treating agent of formula 5 at the same time, using 35N/cm ² Is pressed by a nip roller of the nip pressure of (2), and is dried at a temperature of 120 ℃. Next, the fiber was opened by high-pressure spraying, and then immersed again in the treating agent of formula 5 at a concentration of 35N/cm ² Is pressed by a nip roller of the nip pressure of (a) and dried at a temperature of 120 ℃ to thereby obtain a glass cloth.

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

3. Results

For each glass cloth, the average fiber diameter and the number of long glass fibers contained in the glass yarn used, the knitting density, the count, the mass, the thickness, the firing weight loss, the tensile strength and the carbon amount of the glass yarn used, the residual curvature 2HB/B, the residual shear strain rate 2HG/G, the generation of warp stripes, and the generation of diagonal wrinkles were evaluated. The evaluation results are shown in tables 1, 2 and 3.

TABLE 1

TABLE 2

TABLE 3

The glass cloths of examples 1 to 10 were made of a plurality of glass clothsGlass cloth comprising glass yarns of glass filaments as warp yarns and weft yarns, wherein at least a part of the surface of the glass filaments comprises (A) a polyoxyalkylene bisphenol A ether and (B) a silane coupling agent having an acryl or methacryl group, the glass cloth has a weave density of 70 pieces/25 mm or more, and the glass cloth has a carbon content of 0.4 to 1.5 mass%, whereby a residual curvature 2HB/B of 0.5 (cm) ^-1 ) The residual shear strain rate 2HG/G was 1.4 (deg) ^-1 ) The following glass cloths. Further, the glass cloths of examples 1 to 10 can suppress the generation of longitudinal wrinkles and diagonal wrinkles.

On the other hand, the glass cloth of comparative example 1, although having a carbon content of 0.4 mass% or more, does not contain (A) a polyoxyalkylene bisphenol A ether and (B) a silane coupling agent having an acryl or methacryl group in at least a part of the surface of the long glass fiber filler, and therefore has a residual shear strain rate 2HG/G exceeding 1.4 (deg) ^-1 ). Moreover, the glass cloth of comparative example 1 cannot suppress the generation of diagonal wrinkles.

In addition, the glass cloths of comparative examples 2 and 4 to 6 have a carbon content of less than 0.4% by mass, and at least a part of the surface of the long glass fiber filler does not contain (A) a polyoxyalkylene bisphenol A ether and (B) a silane coupling agent having an acryl or methacryl group, so that the residual curvature 2HB/B exceeds 0.5 (cm ^-1 ) And a residual shear strain rate 2HG/G exceeding 1.4 (deg ^-1 ). Further, the glass cloths of comparative examples 2 and 4 to 6 did not inhibit the generation of longitudinal streaks and diagonal wrinkles.

The glass cloth of comparative example 3 has a carbon content of less than 0.4 mass% and contains no (B) silane coupling agent having an acryl or methacryl group on at least a part of the surface of the long glass fiber filler, so that the residual shear strain rate 2HG/G exceeds 1.4 (deg ^-1 ). Moreover, the glass cloth of comparative example 3 cannot suppress the generation of longitudinal streaks.

Claims

1. A glass cloth comprising a warp yarn and a weft yarn, wherein the warp yarn comprises a glass yarn comprising a plurality of glass filaments,

the carbon content of the glass cloth is 0.4-1.5 mass%.

2. The glass cloth according to claim 1, wherein the tensile strength in the warp direction is 20 to 120N/25mm.

3. The glass cloth according to claim 1 or 2, wherein the glass cloth has a thickness of 5 to 30 μm.

4. The glass cloth according to any one of claims 1 to 3, wherein the glass cloth is a long glass cloth roll in which a glass cloth is wound around a roll core.

5. A prepreg comprising the glass cloth according to any one of claims 1 to 4 and a thermosetting resin impregnated in the glass cloth.