CN111379063A - Method for producing glass cloth and glass yarn - Google Patents
Method for producing glass cloth and glass yarn Download PDFInfo
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- CN111379063A CN111379063A CN201911344834.3A CN201911344834A CN111379063A CN 111379063 A CN111379063 A CN 111379063A CN 201911344834 A CN201911344834 A CN 201911344834A CN 111379063 A CN111379063 A CN 111379063A
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
- D03D15/267—Glass
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D1/00—Woven fabrics designed to make specified articles
- D03D1/0082—Fabrics for printed circuit boards
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
- D10B2101/06—Glass
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Abstract
The present invention relates to a method for producing glass cloth and glass yarn. [ problem ] to]The purpose is to provide: a method for producing a low dielectric glass cloth having uniform quality, and a glass yarn suitable for producing a low dielectric glass cloth. [ solution ]]A method for manufacturing glass cloth, which is formed by weaving glass yarns formed by a plurality of glass filaments as warp yarns and weft yarnsThe density of the glass yarn to be the weft yarn is 2.2g/cm3Above and below 2.5g/cm3The dispersion of the yarn width (yarn width dispersion coefficient) of the glass yarn to be the weft yarn is 0.003 to 0.013, and/or the variation coefficient A of the yarn width distribution of the glass yarn to be the weft yarn, which represents the dispersion of the yarn width distribution, is 0.0002 to 0.0015.
Description
Technical Field
The present invention relates to a method for producing glass cloth and glass yarn.
Background
In recent years, data communication and/or signal processing have been carried out at high speed with a large capacity while the information communication society has been developed, and the reduction of the dielectric constant of a printed circuit board used for electronic equipment has been remarkably carried out. Therefore, among glass cloths constituting printed wiring boards, a large number of low dielectric glass cloths have also been proposed.
For example, in the low dielectric glass cloth disclosed in patent document 1, a large amount of B is added to a glass composition of E glass cloth which has been generally used in the past2O3While adjusting SiO2And the like, to achieve a low dielectric constant.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-292567
Disclosure of Invention
Problems to be solved by the invention
The present inventors have conducted studies and, as a result, have found that: low dielectric glass cloth produced using such low dielectric glass yarn has large fluctuations in performance and quality as compared with E glass cloth which has been conventionally used. Such fluctuations in the performance and quality of the glass cloth also affect the quality of prepregs, laminates for printed wiring boards, and the like obtained using the glass cloth.
The present invention has been made in view of the above problems, and an object thereof is to provide: a method for producing a low dielectric glass cloth having uniform quality, and a glass yarn suitable for producing a low dielectric glass cloth.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have completed the present invention by solving the above-described problems by setting the yarn width of the glass yarn, the fluctuation range of the yarn width, and the uniformity of the fluctuation range of the yarn width to specific ranges.
Namely, the present invention is as follows.
[1]
A method for manufacturing glass cloth, which is formed by weaving glass yarns formed by a plurality of glass filaments as warp yarns and weft yarns,
the density of the glass yarn to be the weft yarn is 2.2g/cm3Above and below 2.5g/cm3，
The glass yarn to be the weft has a yarn width dispersion coefficient of 0.003 to 0.013 inclusive for expressing the dispersion of the yarn width,
the glass yarn to be the weft has a yarn width distribution variation coefficient A of 0.0002 to 0.0015, which represents a distribution dispersion of the yarn width.
The yarn width dispersion coefficient is a value obtained by dividing the standard deviation of the yarn width (yarn width standard deviation a) by the average diameter of the glass filaments
The coefficient of variation a of yarn width distribution is a value obtained by dividing the standard deviation of yarn width B (standard deviation of yarn width distribution) by the diameter of the glass filaments constituting the weft yarn when the standard deviation of yarn width per 0.5m length (standard deviation of yarn width B) is obtained
[2]
The method for producing a glass cloth according to item [1], wherein,
the density of the glass yarn is more than 2.2g/cm3And less than 2.5g/cm3，
The yarn width dispersion coefficient is more than 0.003 and less than 0.010,
and/or the coefficient of variation A of the yarn width distribution exceeds 0.0003 and is less than 0.0012.
[3]
The method for producing a glass cloth according to item [1], wherein,
the yarn width dispersion coefficient is 0.005 or more and 0.013 or less,
the coefficient of variation A of the yarn width distribution is 0.0006 to 0.0015,
and/or the glass yarn to be the weft yarn has a yarn width distribution variation coefficient B of 0.013 or more and 0.027 or less,
the yarn width distribution coefficient of variation B is a value obtained by dividing a yarn width distribution CV value, which is obtained by dividing a standard deviation of a yarn width in each 0.5m length (yarn width standard deviation B), by an average value of a standard deviation of the yarn width standard deviation B (yarn width distribution standard deviation), by a diameter of a glass filament constituting a weft yarn.
[4]
The method for producing glass cloth according to any one of [1] to [3], wherein,
the average value of the twist of the weft yarn per 25mm is 0.50 or more and 1.20 or less,
the standard deviation representing the dispersion of twist is 0.10 or more and 0.20 or less.
[5]
The method for producing glass cloth according to any one of [1] to [4], wherein,
the weft is a glass yarn obtained by bundling 80 to 120 glass filaments having an average diameter of more than 4.5 [ mu ] m and 5.5 [ mu ] m or less, and the average yarn width of the glass yarn is 90 to 130 [ mu ] m.
[6]
The method for producing glass cloth according to any one of [1] to [4], wherein,
the weft is a glass yarn formed by binding 180 to 220 glass filaments having an average diameter of more than 4.5 [ mu ] m and 5.5 [ mu ] m, and the average yarn width of the glass yarn is 120 to 175 [ mu ] m.
[7]
The method for producing glass cloth according to any one of [1] to [4], wherein,
the weft is a glass yarn formed by binding 180 to 220 glass filaments having an average diameter of more than 5.5 [ mu ] m and 6.5 [ mu ] m or less, and the average yarn width of the glass yarn is 155 to 195 [ mu ] m.
[8]
The method for producing glass cloth according to any one of [1] to [4], wherein,
the weft is a glass yarn formed by binding 180 to 220 glass filaments having an average diameter of more than 6.5 [ mu ] m and 7.5 [ mu ] m or less, and the average yarn width of the glass yarn is 180 to 220 [ mu ] m.
[9]
The method for producing glass cloth according to any one of [1] to [8], wherein,
the elastic coefficient of the glass yarn is 50 to 70 GPa.
[10]
The method for producing glass cloth according to item [9], wherein,
the elastic coefficient of the glass yarn is 50 to 63 GPa.
[11]
The method for producing glass cloth according to any one of [1] to [10], wherein,
the glass cloth has a dielectric constant of 5.0 or less at a frequency of 1 GHz.
[12]
The method for producing glass cloth according to any one of [1] to [11], wherein,
the glass yarn,
Si content in SiO2Converted into 40 to 60 mass%,
the content of B is as follows2O3Converted to 15 to 30 mass%.
[13]
A glass yarn having a density of 2.2g/cm3Above and below 2.5g/cm3，
A yarn width dispersion coefficient representing the dispersion of the yarn width is 0.003 or more and 0.013 or less, and/or,
the yarn width distribution variation coefficient A representing the distribution dispersion of the yarn width is 0.0002 to 0.0015.
The yarn width dispersion coefficient is a value obtained by dividing the standard deviation of the yarn width (yarn width standard deviation a) by the average diameter of the glass filaments
The yarn width distribution coefficient of variation a is a value obtained by dividing a standard deviation of the yarn width standard deviation B (yarn width distribution standard deviation) by the diameter of the glass filament constituting the weft yarn when the standard deviation of the yarn width per 0.5m length (yarn width standard deviation B) is obtained.
[14]
The glass yarn according to [13], wherein,
the density of the glass yarn is more than 2.2g/cm3And less than 2.5g/cm3，
The yarn width dispersion coefficient is more than 0.003 and less than 0.010,
and/or the coefficient of variation A of the yarn width distribution exceeds 0.0003 and is less than 0.0012.
[15]
The glass yarn according to [13], wherein,
the yarn width dispersion coefficient is 0.005 or more and 0.013 or less,
the coefficient of variation A of the yarn width distribution is 0.0006 to 0.0015,
and/or the glass yarn to be the weft yarn has a yarn width distribution variation coefficient B of 0.013 or more and 0.027 or less, the yarn width distribution variation coefficient B representing the distribution dispersion of the yarn width.
The yarn width distribution coefficient of variation B is a value obtained by dividing a yarn width distribution CV value, which is obtained by dividing a standard deviation of a yarn width in each 0.5m length (yarn width standard deviation B), by an average value of a standard deviation of the yarn width standard deviation B (yarn width distribution standard deviation), by a diameter of a glass filament constituting a weft yarn.
[16]
The glass yarn according to any one of [13] to [15], wherein,
the average value of the twist per 25mm is 0.50 or more and 1.20 or less,
the standard deviation representing the dispersion of twist is 0.10 or more and 0.20 or less.
[17]
The glass yarn according to any one of [13] to [16],
the glass yarn is formed by bundling 80 to 120 glass filaments with an average diameter of more than 4.5 mu m and less than 5.5 mu m, and the average value of the yarn width is more than 90 mu m and less than 130 mu m.
[18]
The glass yarn according to any one of [13] to [16],
the glass yarn is formed by bundling 180 to 220 glass filaments with an average diameter of more than 4.5 mu m and less than 5.5 mu m, and the average value of the yarn width is more than 120 mu m and less than 175 mu m.
[19]
The glass yarn according to any one of [13] to [16],
the glass yarn is formed by bundling 180 to 220 glass filaments with an average diameter of more than 5.5 mu m and less than 6.5 mu m, and the average value of the yarn width is more than 155 mu m and less than 195 mu m.
[20]
The glass yarn according to any one of [13] to [16],
the glass yarn is formed by bundling 180-220 glass filaments with an average diameter of more than 6.5 μm and less than 7.5 μm, and the average value of the yarn width is more than 180 μm and less than 220 μm.
[21]
The glass yarn according to any one of [13] to [20], which has an elastic modulus of 50 to 70 GPa.
[22]
The glass yarn according to any one of [13] to [20], which has an elastic modulus of 50 to 63 GPa.
[23]
The glass yarn according to any one of [13] to [22], which has a dielectric constant of 5.0 or less at a frequency of 1 GHz.
[24]
According to [13]～[23]The glass yarn as claimed in any one of the preceding claims, wherein the Si content is SiO2Conversion40 to 60% by mass,
the content of B is as follows2O3Converted to 15 to 30 mass%.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a method for producing a low dielectric glass cloth having uniform quality, and a glass yarn suitable for producing a low dielectric glass cloth.
Drawings
Fig. 1 is a perspective view showing one embodiment of a weaving step in the manufacturing method of the present embodiment.
Detailed Description
Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof.
[ method for producing glass cloth ]
The method for producing a glass cloth according to the present embodiment is a method for producing a glass cloth in which a glass yarn made of a plurality of glass filaments is woven as a warp and a weft, and the density of the glass yarn to be the weft is 2.2g/cm3Above and below 2.5g/cm3The glass yarn to be the weft yarn has a yarn width variation coefficient representing the yarn width variation of 0.003 to 0.013, and/or the glass yarn to be the weft yarn has a yarn width distribution variation coefficient A representing the yarn width distribution variation of 0.0002 to 0.0015.
Glass cloth produced using glass yarns of low dielectric constant had a fluctuation in quality as compared with conventional E glass cloth, and it was found that glass cloth having poor quality was rarely obtained. When the glass cloth with poor quality is examined in detail, the glass cloth with poor quality has the following common points: the glass yarn has a non-uniform yarn width portion and a non-uniform yarn width portion, and the glass yarn having a large dispersion of yarn width is used. In the glass cloth composed of the glass yarn having a large dispersion of the yarn width distribution, knitting defects such as a portion where a large number of filament portions constituting the glass yarn are cut to become wool, a portion where weft yarns are loosened, and the like were confirmed.
The reason is not limited, and it is considered that it is difficult to obtain a stable jump-shuttle track when a glass yarn (weft yarn) having a non-uniform yarn width portion and a non-uniform yarn width portion is woven in, and it is difficult to pass straight between warp yarns, and a burr or a knitting defect is likely to occur.
In addition, it is considered that the glass yarn of E glass used so far is heavier than the glass yarn of low dielectric constant, and the influence on the weaving due to the fluctuation of the yarn width is small, but in the glass yarn of low dielectric constant which is lighter, the weft is easily influenced by the shape of the yarn width at the time of weaving, and the generation of the fluff and the knitting defect is easily promoted.
Further, it is considered that low dielectric glass yarns having a small elastic modulus and not withstanding mechanical load are likely to cause filament breakage, and thus generation of fuzz is likely to be promoted. It is considered that these influences are expressed as the quality of the woven glass cloth.
In contrast, in the present embodiment, the density of the glass yarn used is 2.2g/cm3Above and below 2.5g/cm3And the fluctuation range of the yarn width of the weft (the yarn width dispersion coefficient) is 0.003 or more and 0.013 or less, or the distribution range of the yarn width of the weft (the yarn width distribution variation coefficient a) is 0.0002 or more and 0.0015 or less, thereby reducing the influence of the shape of the yarn width at the time of weaving even in the case of using a light glass yarn with low dielectric constant. This can suppress the occurrence of shot and knitting defects, and can obtain glass cloth having uniform quality.
(Density of glass yarn)
The density of the glass yarn of the weft is 2.2g/cm3Above and below 2.5g/cm3Preferably more than 2.2g/cm3And less than 2.5g/cm3More preferably 2.22g/cm3Above and 2.45g/cm3The lower, more preferably 2.25g/cm3Above and 2.4g/cm3The following. If the density of the glass yarn of the weft is less than 2.5g/cm3When weft is woven into the discharged air, the shuttle jump track is easily affected by the shape of the glass yarn, and the weft is easily producedHowever, by setting the yarn width dispersion coefficient and the yarn width distribution variation coefficient a of the weft yarn within the specific ranges of the present invention, the shuttle jump track can be stabilized, and high-quality glass cloth can be stably obtained. The density of the glass yarn of the weft is 2.2g/cm3As described above, when the range of fluctuation of the yarn width of the weft yarn and the range of fluctuation of the yarn width distribution of the weft yarn are within the range of the present invention, the skip track of the weft yarn can be stabilized. The glass density of the warp may be the same as or different from the above range, and the same range is preferable from the viewpoint of making uniform the characteristics such as air permeability, resin impregnation property, resin adhesion property, and electrical characteristics of the glass cloth, and from the viewpoint of obtaining a low dielectric glass cloth. The density of the glass strands may be in the range of 1cm3The density of the bulk glass was determined.
(yarn Width Dispersion coefficient of yarn bundle of weft yarn)
The yarn width dispersion coefficient of the yarn bundle of the weft is 0.003 or more, preferably more than 0.003, more preferably 0.004 or more, further preferably 0.005 or more, further preferably 0.006 or more, and particularly preferably 0.007 or more. The yarn width dispersion coefficient of the yarn bundle of the weft is 0.013 or less, preferably less than 0.010, more preferably 0.009 or less. The yarn width dispersion coefficient is within the above range, so that when the weft yarn is inserted into the air jet loom, the weft yarn can be inserted from the insertion side to the opposite side in a stable shuttle jumping path without requiring excessive air pressure, and therefore, a high-quality glass cloth with less shot and less knitting defects can be stably obtained.
The yarn width dispersion coefficient of a yarn bundle is a value obtained by dividing the standard deviation of measured values of the yarn width of the yarn bundle by the average diameter of the glass filaments constituting the yarn bundle. The yarn width dispersion coefficient of the yarn bundle of the warp may be the same as or different from the above range, and the same range is preferable from the viewpoint of further suppressing the occurrence of the shot and the knitting defect.
The yarn width dispersion coefficient is a value obtained by dividing the standard deviation of the yarn width (yarn width standard deviation a) by the average diameter of the glass filaments
(coefficient of variation of yarn Width distribution of weft yarn A)
The coefficient of variation a in the yarn width distribution of the weft yarn is 0.0002 or more, preferably more than 0.0003, more preferably 0.0004 or more. The coefficient of variation a in the yarn width distribution of the weft yarn is 0.0015 or less, preferably less than 0.0012, and more preferably 0.0010 or less. The coefficient of variation a in yarn width distribution is within the above range, so that shuttle jumping can be easily performed straight and stably without disturbing the shuttle jumping trajectory, and high-quality glass cloth with less fluff and knitting defects can be stably obtained. This is presumably because the weft yarn can receive the compressed air uniformly in the longitudinal direction. Further, since the coefficient of variation a in yarn width distribution is in the above range, the detachment resistance when detaching the yarn bundle from the bobbin falls in a small range, and therefore, a high-quality glass cloth with less fluff and knitting defects can be stably obtained. This is presumably because the yarns on the bobbin on which the yarns are wound can be prevented from overlapping each other excessively. When the yarn bundle is worn at the time of unraveling and 1 or more filaments are separated, the filaments are cut at the portion in the weaving and the subsequent process, and the portion becomes a shot or a knitting defect.
When the shuttle jumping property of the weft yarn is to be stabilized and weaving productivity is to be emphasized, the coefficient of variation a in the yarn width distribution of the weft yarn is 0.0002 or more and 0.0015 or less, preferably 0.0006 or more and 0.0015 or less.
The yarn width distribution coefficient of variation a of the yarn bundle is a value obtained as follows: the yarn width distribution state of the large length range (for example, 50m) is determined by the standard deviation (standard deviation B: standard deviation of standard deviation a) of the measured value of the yarn width in the specific small length range (for example, 0.5m), and divided by the average diameter of the filaments constituting the yarn bundle. The coefficient of variation a in the yarn width distribution of the warp yarn bundle may be the same as or different from the above range, and the same range is preferable from the viewpoint of further suppressing the occurrence of shot and knitting defects.
The coefficient of variation a of yarn width distribution is a value obtained by dividing the standard deviation of yarn width B (standard deviation of yarn width distribution) by the diameter of the glass filaments constituting the weft yarn when the standard deviation of yarn width per 0.5m length (standard deviation of yarn width B) is obtained
The yarn width dispersion coefficient and the yarn width distribution variation coefficient a of the yarn bundle are preferably within the above ranges.
The yarn width dispersion coefficient, the yarn width distribution variation coefficient a, and the average value of the yarn bundle can be calculated as follows: the yarn width of the glass yarn of 10m or more was measured at equal intervals shorter than 1mm, and calculated from the obtained yarn width data.
The method of measuring the yarn width in this case is not particularly limited, and may be measured, for example, as follows: the yarn width of the glass yarn is obtained by a method of irradiating LED light from the side and obtaining the yarn width of the glass yarn according to the projection width of the part shielded by the glass yarn by the LED light, and the glass yarn is continuously conveyed and continuously measured. The yarn width may be measured while observing the yarn with a microscope.
(coefficient of variation of yarn Width distribution of weft yarn B)
The coefficient of variation B in the yarn width distribution of the glass yarn to be the weft yarn, which represents the dispersion of the distribution of the yarn width, is preferably 0.013 or more, more preferably 0.014 or more, and still more preferably 0.015 or more. The coefficient of variation B in the yarn width distribution is preferably 0.027 or less, more preferably 0.024 or less, and still more preferably 0.021 or less. The yarn width distribution coefficient of variation B is in the above range, and the skip stability of the weft tends to be further improved.
The yarn width distribution coefficient of variation B is a value obtained by dividing a yarn width distribution CV value, which is obtained by dividing a standard deviation of a yarn width in each 0.5m length (yarn width standard deviation B), by an average value of a standard deviation of the yarn width standard deviation B (yarn width distribution standard deviation), by a diameter of a glass filament constituting a weft yarn.
(average value of yarn width)
In the method for producing a glass cloth of the present invention, when a glass cloth having a thickness of 20 μm or more and 38 μm or less is produced, it is preferable that a glass yarn obtained by bundling 80 or more and 120 or less glass filaments having an average diameter of more than 4.5 μm and 5.5 μm or less is used for a weft yarn having an average yarn width of 90 μm or more and 130 μm or less. The average value of the yarn width in this case is more preferably 95 μm or more, still more preferably 100 μm or more, and particularly preferably 102 μm or more. The average value of the yarn width is more preferably 125 μm or less, still more preferably 122 μm or less, and particularly preferably 120 μm or less.
When glass cloth having a thickness of 39 μm or more and 63 μm or less is produced, it is preferable that glass yarns obtained by bundling 180 to 220 glass filaments having an average diameter of more than 4.5 μm and 5.5 μm or less are used for weft yarns, and the average yarn width of the weft yarns is 120 μm or more and 175 μm or less. The average value of the yarn width in this case is more preferably 125 μm or more, and still more preferably 130 μm or more. The average value of the yarn width is more preferably 170 μm or less, still more preferably 165 μm or less, and particularly preferably 150 μm or less.
When glass cloth having a thickness of 64 μm or more and 83 μm or less is produced, it is preferable that a glass yarn obtained by bundling 180 to 220 glass filaments having an average diameter of more than 5.5 μm and 6.5 μm or less is used for a weft yarn, and the average yarn width of the weft yarn is 155 μm or more and 195 μm or less. The average value of the yarn width in this case is more preferably 160 μm or more, and still more preferably 162 μm or more. The average value of the yarn width is more preferably 191 μm or less, still more preferably 183 μm or less, and particularly preferably 170 μm or less.
When glass cloth having a thickness of 84 μm or more and 100 μm or less is produced, it is preferable that a glass yarn obtained by bundling 180 to 220 glass filaments having an average diameter of more than 6.5 μm and 7.5 μm or less is used for a weft yarn, and the average yarn width of the weft yarn is 180 to 220 μm or more. The average value of the yarn width in this case is more preferably 185 μm or more, and still more preferably 190 μm or more. The average value of the yarn width is more preferably 215 μm or less, and still more preferably 210 μm or less.
Since the average value of the yarn width of the weft is equal to or less than the upper limit value, even if the yarn width fluctuates, the influence thereof is small, and the occurrence of shot and knitting defects in the obtained glass cloth tends to be suppressed. Further, since the average value of the yarn width is equal to or greater than the lower limit value, the glass yarn appropriately receives the jet air during beating-up, and therefore, the weft yarn can be skipped at a relatively stable jet pressure, and therefore, the occurrence of shot and knitting defects tends to be suppressed in the obtained glass cloth. The average value of the yarn width of the warp yarn may be the same as or different from the above range, and the same range is preferable from the viewpoint of further suppressing the occurrence of the shot and the knitting defect.
(twist dispersion)
The standard deviation representing the twist dispersion per 25mm of the weft yarn is preferably 0.03 or more, more preferably 0.05 or more, and further preferably 0.10 or more. The standard deviation indicating the twist dispersion per 25mm of the weft yarn is preferably 0.20 or less, more preferably 0.18 or less, further preferably 0.15 or less, and particularly preferably 0.13 or less. When the standard deviation of the twist is within the above range, the influence of the shape of the yarn width at the time of knitting is reduced, and the occurrence of shot and knitting defects in the obtained glass cloth tends to be suppressed. In addition, since the standard deviation of the twist is within the above range, the welding heat resistance tends to be excellent.
The standard deviation representing the twist dispersion per 25mm of the warp yarn is preferably 0.03 or more, more preferably 0.05 or more, and further preferably 0.10 or more. The standard deviation indicating the twist dispersion per 25mm of the warp yarn is preferably 0.20 or less, more preferably 0.18 or less, further preferably 0.15 or less, and particularly preferably 0.13 or less. From the viewpoint of further suppressing the occurrence of shot and knitting defects, the standard deviation of the twist is preferably within the above range. In addition, since the standard deviation of the twist is within the above range, the welding heat resistance tends to be excellent. The standard deviation of the twist of the weft yarn and the twist of the warp yarn may be the same or different.
The reason why the standard deviation representing the dispersion of twist per 25mm of the weft yarn and/or the warp yarn is within the above range and thus the welding heat resistance is excellent is not particularly limited, but is considered as follows. The standard deviation indicating the twist dispersion is 0.10 or more, so that the adjacent yarns can be prevented from excessively adhering to each other, and the adjacent yarns form an appropriate gap with each other, and therefore, the impregnation property of the resin into the glass cloth is good, and the adhesiveness between the glass yarn and the resin tends to be improved. Therefore, it is considered that the welding heat resistance is further improved. Further, the standard deviation indicating the twist dispersion is 0.20 or less, and the glass cloth and the substrate in which the glass cloth is impregnated with the resin obtained thereby tend to have a more uniform distribution of glass yarns and to suppress a portion having a locally weak productivity. Therefore, it is considered that the welding heat resistance is further improved.
(average value of twist)
The average value of the twist per 25mm of the weft yarn is preferably 0.50 or more and 1.20 or less, more preferably 0.60 or more and 1.10 or less, further preferably 0.65 or more and 1.05 or less. When the average twist value is within the above range, the influence of the shape of the yarn width at the time of knitting is reduced, and the occurrence of shot and knitting defects in the obtained glass cloth tends to be suppressed.
The average value of the twist per 25mm of the warp yarn is preferably 0.50 or more and 1.20 or less, more preferably 0.60 or more and 1.10 or less, further preferably 0.65 or more and 1.05 or less. From the viewpoint of further suppressing the occurrence of shot and knitting defects, the average value of the twist is preferably within the above range. The average twist of the weft and warp yarns may be the same or different.
(constitution of glass yarn)
Next, the structure of the glass yarn will be described. The glass yarn is obtained by bundling a plurality of glass filaments and twisting them as necessary. At this time, the glass yarn is divided into multifilaments and the glass filament is divided into monofilaments.
The average diameter of the glass filaments constituting the warp and the weft is preferably 2.5 to 9 μm, more preferably 3.0 to 7.5 μm, and further preferably 3.5 to 5.4 μm. The glass filaments have an average diameter of 9 μm or less, and thus the workability is further improved, and a printed wiring board that is thin and can be mounted at high density can be realized. Further, the average diameter is 3.5 μm or more, and the glass cloth tends to be less likely to be broken.
Examples of the element constituting the glass yarn include Si, B, Al, Ca, Mg, P, Na, K, Ti, Zn, Fe, F and the like.
Si content of the glass yarn is SiO2The content is preferably 40 to 60% by mass, more preferably 45 to 55% by mass, still more preferably 47 to 53% by mass, and yet more preferably 48 to 52% by mass in terms of mass. Si is a component forming the skeleton structure of the glass yarn, and the Si content is 40 mass% or more, so that the strength of the glass yarn is further improved, and breakage of the glass cloth tends to be further suppressed in the subsequent steps such as the production step of the glass cloth and the production of a prepreg using the glass cloth. In addition, the Si content is 40 mass% or more, and the dielectric constant of the glass cloth tends to be further lowered. On the other hand, when the Si content is 60 mass% or less, the viscosity at the time of melting is further reduced in the process of producing the glass filaments, and glass fibers having a more homogeneous glass composition tend to be obtained. Therefore, a portion of the obtained glass filament which is easily devitrified and a portion from which bubbles are not easily removed are not easily formed, and therefore, a portion having a weak strength is not easily formed in part of the glass filament, and as a result, the glass cloth made of the glass yarn obtained by using the glass filament is not easily broken. The Si content can be adjusted according to the amount of raw materials used in the production of the glass filaments.
The B content of the glass yarn is defined as B2O3The content is preferably 15 to 30% by mass, more preferably 17 to 28% by mass, further preferably 20 to 27% by mass, further preferably 21 to 25% by mass, and further more preferably 21.5 to 24% by mass in terms of mass. The content of B is 15 mass% or more, and the dielectric constant tends to be further lowered. In addition, the content of B is 30 mass% or less, and therefore, moisture absorption resistance is improved, and insulation reliability tends to be further improved. The content of B can be adjusted according to the amount of raw materials used in the production of the glass filaments. When there is a possibility of variation in the production of the glass filaments, the amount of the glass filaments to be fed can be adjusted by estimating the variation in the production in advance.
The Al content of the glass yarn is calculated as Al2O3The content is preferably 11 to 18% by mass, more preferably 11 to 16% by mass, and further preferably 12 to 16% by mass in terms of mass. The Al content is in the above range, and the electric characteristics and strength are further improvedThe tendency of (c). The Al content can be adjusted according to the amount of raw materials used in the production of the glass filaments.
The Ca content of the glass yarn is preferably 5 to 10 mass%, preferably 5 to 9 mass%, more preferably 5 to 8.5 mass% in terms of CaO. When the Ca content is 4 mass% or more, the viscosity at the time of melting is further reduced in the process of producing the glass filaments, and glass fibers having a more homogeneous glass composition tend to be obtained. Further, the content of Ca is 10 mass% or less, and the dielectric constant tends to be further improved. The Ca content can be adjusted according to the amount of raw materials used for producing the glass filaments.
The contents can be measured by ICP emission spectrometry. Specifically, the Si content and the B content were obtained as follows: and melting the weighed glass cloth sample by using sodium carbonate, dissolving by using dilute nitric acid, fixing the volume, and measuring the obtained sample by using an ICP emission spectrometry to obtain the glass cloth sample. In addition, the Fe content is obtained as follows: and dissolving the weighed glass cloth sample by an alkali dissolution method, fixing the volume, and measuring the obtained sample by an ICP emission spectrum analysis method to obtain the glass cloth. Further, the Al content, Ca content and Mg content were obtained as follows: and (3) heating and decomposing the weighed glass cloth sample by sulfuric acid, nitric acid and hydrogen fluoride, dissolving the glass cloth sample by using dilute nitric acid, fixing the volume, and measuring the obtained sample by an ICP emission spectrum analysis method to obtain the glass cloth sample. As an ICP emission spectrometer, PS3520VDD II manufactured by Hitachi High-Tech Science Corporation was used.
The elastic modulus of the glass yarn is preferably 50 to 70GPa, more preferably 50 to 63GPa, and still more preferably 53 to 63 GPa. The elastic modulus is 50GPa or more, so that the rigidity of the glass yarn is improved, and the generation of burrs in the manufacturing process is not easy. Further, the glass yarn has a modulus of elasticity of 70GPa or less, so that the glass yarn has improved brittleness resistance and is not easy to generate fuzz particles in the manufacturing process. Further, the glass yarn has a modulus of elasticity within the above range, and therefore has appropriate flexibility, and when a mechanical load is applied, breakage of the filament or the like is less likely to occur, and the occurrence of shot or knitting defects is less likely to occur.
The dielectric constant of the obtained glass cloth is preferably 5.0 or less, more preferably 4.8 or less, further preferably 4.6 or less, and particularly preferably 4.0 or less at a frequency of 1 GHz. The dielectric constant can be measured, for example, by a cavity resonance method. In the present embodiment, the term "dielectric constant" refers to a dielectric constant at a frequency of 1GHz, unless otherwise specified. The glass cloth preferably has a dielectric constant of 5.0 or less at a frequency of 1GHz, because the glass cloth can satisfy the requirement of reducing the dielectric constant.
The method for producing the glass cloth of the present embodiment is not particularly limited as long as the weft is used, and a method including the following steps: a yarn width adjustment step of adjusting the yarn width so that the yarn width dispersion coefficient of the weft yarn is 0.003 to 0.013 inclusive and/or the yarn width distribution variation coefficient is 0.0002 to 0.0015 inclusive; a weaving step of weaving glass yarn to obtain glass cloth; and a fiber opening step of opening the glass yarn of the glass cloth. Further, the method may further include, as necessary, the steps of: a desizing step of removing the sizing agent attached to the glass yarn of the glass cloth; a surface treatment step using a silane coupling agent. Hereinafter, each step of the present embodiment will be described in more detail.
[ yarn width adjustment Process ]
The yarn width adjusting process comprises the following steps: and adjusting the yarn width distribution coefficient of the weft yarn to be 0.003 to 0.013 and/or the yarn width distribution variation coefficient A to be 0.0002 to 0.0015. More specifically, in the yarn width adjustment step, the yarn width dispersion coefficient and/or the yarn width distribution variation coefficient a of the weft yarn is measured so that the yarn width dispersion coefficient is 0.003 or more and 0.013 or less and/or the yarn width distribution variation coefficient a is in the range of 0.0002 or more and 0.0015 or less, and if the yarn is used in the next weaving step, the yarn is discarded or untwisted so that the yarn width dispersion coefficient is 0.003 or more and 0.013 or less and/or the yarn width distribution variation coefficient a is in the range of 0.0002 or more and 0.0015 or less. Alternatively, it is also considered to perform feedback on the glass yarn production process and adjust the yarn production conditions. The yarn width of the glass yarn is affected by the dispersion of the twist degree between the high twist density portion and the low twist density portion, and the dispersion of the yarn width of the glass filament. Therefore, the coefficient of variation of the glass yarn to be subjected to the weaving step can be adjusted by untwisting or untwisting. Further, when the yarn width dispersion coefficient and/or the yarn width distribution variation coefficient a of the weft yarn are measured and as a result, the quality of the glass yarn exceeds the range of the variation coefficient that can be adjusted by twisting, the glass yarn itself may be replaced as a part of the adjustment of the variation coefficient.
[ weaving procedure ]
The weaving step is a step of weaving glass yarn to obtain glass cloth. The weaving method is not particularly limited as long as the warp and weft are woven so as to have a predetermined weaving structure. The woven structure of the glass cloth is not particularly limited, and examples thereof include: plain weave, square plain weave, satin weave, twill weave and the like. Among them, a plain weave structure is more preferable.
Fig. 1 is a perspective view showing one embodiment of a weaving step in the manufacturing method of the present embodiment. Fig. 1 is a diagram showing one mode of a weaving process by an air jet weaving machine method, in which a warp yarn 1 pulled in parallel is split in the upper and lower directions, and a weft yarn 4 is sent out and passed through a jet flow of a nozzle 3 by a yarn fed from a weft storage device 2 at the split, thereby performing weaving. In this weaving process, it is difficult to directly feed a light weft yarn having a large dispersion coefficient of yarn width and/or variation coefficient a of yarn width distribution, and the obtained glass cloth may have a shot or a knitting defect. In contrast, in the present embodiment, by using the weft yarn having the yarn width dispersion coefficient of 0.003 to 0.013 and/or the yarn width distribution variation coefficient a of 0.0002 to 0.0015 through the yarn width adjusting step and the like, the occurrence of the shot and the knitting defect is suppressed when the weft yarn is woven. This improves the in-plane uniformity and the batch-to-batch uniformity of the quality of the glass cloth. The weaving method is not limited to the air jet loom method, and may be a water jet loom method or a shuttle (shed) method.
The pick density of the warp and weft constituting the glass cloth is preferably 30 to 120, more preferably 40 to 110, and further preferably 50 to 100. The picking density of the warp yarns can be controlled by adjusting the interval of the warp yarns drawn in parallel, and the picking density of the weft yarns can be controlled according to the number of times of jetting of the weft yarns from the nozzles per unit time and the flow rate of the warp yarns.
The thickness of the glass cloth finally obtained through the opening step or the like is preferably 8 to 100 μm, more preferably 9 to 90 μm, and still more preferably 9.5 to 80 μm. The thickness of the glass cloth is in the above range, and thus a thin glass cloth having high strength tends to be obtained.
The weight (weight per unit area) of the glass cloth is preferably 8 to 250g/m2More preferably 8 to 130g/m2More preferably 8 to 100g/m2Particularly preferably 8 to 90g/m2。
[ opening procedure ]
The opening step is a step of opening glass yarns of the glass cloth. The method of opening the fiber is not particularly limited, and examples thereof include: a method of splitting with a water jet (high-pressure water splitting), an oscillation washer, ultrasonic water, a cloth calender, or the like.
[ desizing Process ]
The desizing step is a step of removing the sizing agent attached to the glass yarn of the glass cloth. The desizing method is not particularly limited, and examples thereof include a method of removing a sizing agent by heating.
[ surface treatment procedure ]
The surface treatment step is a step of performing surface treatment with a silane coupling agent. Further, as the surface treatment method, the following methods can be mentioned: a surface treatment agent containing a silane coupling agent is brought into contact with the glass cloth and dried, and the like. The contact of the surface treatment agent with the glass cloth may include: a method of immersing a glass cloth in a surface treatment agent; a method of applying the surface treatment agent to the glass cloth by a roll coater, die coater, gravure coater, or the like. The method of drying the surface treatment agent is not particularly limited, and examples thereof include hot air drying and drying by electromagnetic waves.
(surface treatment)
The glass cloth may be surface-treated by a surface treatment agent. The surface treatment agent is not particularly limited, and examples thereof include a silane coupling agent, and water, an organic solvent, an acid, a dye, a pigment, a surfactant, and the like may be used in combination as necessary.
The silane coupling agent is not particularly limited, and examples thereof include compounds represented by formula (1).
X(R)3-nSiYn···(1)
(in the formula (1), X is an organic functional group with at least 1 or more of amino and unsaturated double bond groups, Y is an alkoxy group independently, n is an integer of more than 1 and less than 3, R is a group selected from the group consisting of methyl, ethyl and phenyl independently.)
X is preferably an organic functional group having at least 3 or more of an amino group and an unsaturated double bond group, and more preferably an organic functional group having at least 4 or more of an amino group and an unsaturated double bond group.
The alkoxy group may be in any form, and is preferably an alkoxy group having 5 or less carbon atoms from the viewpoint of stable treatment of the glass cloth.
Specific examples of the silane coupling agent include known simple substances such as N- β - (N-vinylbenzylaminoethyl) - γ -aminopropyltrimethoxysilane and a hydrochloride thereof, N- β - (N-vinylbenzylaminoethyl) - γ -aminopropylmethyldimethoxysilane and a hydrochloride thereof, N- β - (N-bis (vinylbenzyl) aminoethyl) - γ -aminopropyltrimethoxysilane and a hydrochloride thereof, N- β - (N-bis (vinylbenzyl) aminoethyl) -N- γ - (N-vinylbenzyl) - γ -aminopropyltrimethoxysilane and a hydrochloride thereof, N- β - (N-benzylaminoethyl) - γ -aminopropyltrimethoxysilane and a hydrochloride thereof, N- β - (N-benzylaminoethyl) - γ -aminopropyltriethoxysilane and a hydrochloride thereof, γ - (2-aminoethyl) aminopropyltrimethoxysilane, γ - (2-aminoethyl) aminopropyltriethoxysilane, aminopropyltrimethoxysilane, vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, and the like, and mixtures thereof.
The molecular weight of the silane coupling agent is preferably 100 to 600, more preferably 150 to 500, and further preferably 200 to 450. Among them, 2 or more silane coupling agents having different molecular weights are preferably used. When the surface of the glass yarn is treated by using 2 or more silane coupling agents having different molecular weights, the density of the surface treatment agent in the surface of the glass cloth tends to be high, and the reactivity with the matrix resin tends to be further improved.
[ methods for producing other glass cloths ]
In the present embodiment, as another embodiment, the following manufacturing method can be used: the method for manufacturing glass cloth is characterized in that glass yarns formed by a plurality of glass filaments are used as warp yarns and weft yarns and are woven into the glass cloth, the average value of the twist of the weft yarns in each 25mm is more than 0.50 and less than 1.20, the standard deviation of the twist is more than 0.03 and less than 0.18, and the density of the glass yarns used as the weft yarns is 2.2g/cm3Above and below 2.5g/cm3。
[ glass yarn ]
The glass yarn of the present embodiment is a glass yarn used in the above-described method for producing a glass cloth, and particularly a glass yarn used as a weft. The structure of the glass yarn is the same as described above.
The glass cloth of the present embodiment is obtained by the method for producing glass cloth described above, and has at least the glass yarn as a weft.
[ prepreg ]
The prepreg of the present embodiment has: the glass cloth obtained as described above; and a matrix resin composition impregnated in the glass cloth. The prepreg having the glass cloth has less variation in quality, and the yield of the final product is increased. Further, since the dielectric characteristics are excellent and the moisture absorption resistance is excellent, the following effects are exhibited: a printed wiring board which has little influence of the use environment, particularly little variation in dielectric constant in a high humidity environment can be provided.
The prepreg of the present embodiment can be manufactured by a conventional method. For example, it can be produced as follows: the glass cloth of the present embodiment is impregnated with a varnish obtained by diluting a matrix resin such as an epoxy resin with an organic solvent, and then the organic solvent is volatilized in a drying oven to cure the thermosetting resin to a B-stage state (semi-cured state).
Examples of the matrix resin composition include thermosetting resins such as bismaleimide resin, cyanate resin, unsaturated polyester resin, polyimide resin, BT resin, and functionalized polyphenylene ether resin; thermoplastic resins such as polyphenylene ether resins, polyether imide resins, Liquid Crystal Polymers (LCP) of wholly aromatic polyesters, polybutadiene, and fluorine resins; and mixed resins thereof, and the like. From the viewpoint of improving dielectric characteristics, heat resistance, solvent resistance, and press moldability, a resin obtained by modifying a thermoplastic resin with a thermosetting resin may be used as the matrix resin composition.
In addition, the matrix resin composition may contain inorganic fillers such as silica and aluminum hydroxide; flame retardants such as bromine, phosphorus, and metal hydroxides; other silane coupling agents; a heat stabilizer; an antistatic agent; an ultraviolet absorber; a pigment; a colorant; lubricants, and the like.
[ printed circuit board ]
The printed wiring board of the present embodiment includes the prepreg. The printed wiring board provided with the prepreg of the present embodiment has less variation in quality, and the yield of the final product is high. Further, since the dielectric characteristics are excellent and the moisture absorption resistance is excellent, the following effects are exhibited: the influence of the use environment, particularly the fluctuation of the dielectric constant under a high humidity environment is small.
Examples
The present invention will be described more specifically below with reference to examples and comparative examples. The present invention is not limited to the following examples.
[ physical Properties of glass cloth ]
The physical properties of the glass cloth, specifically, the thickness of the glass cloth, the diameters of the filaments constituting the warp and weft, the number of filaments, and the picking density (weaving density) of the warp and weft were measured in accordance with JIS R3420.
[ elastic modulus ]
The elastic modulus was measured by a pulse echo superposition method.
[ composition of glass yarn ]
The composition of the constituent glass strands was determined by ICP emission spectroscopy. Specifically, the Si content and the B content were obtained as follows: and melting the weighed glass cloth sample by using sodium carbonate, dissolving by using dilute nitric acid, fixing the volume, and measuring the obtained sample by using an ICP emission spectrometry to obtain the glass cloth sample. In addition, the Fe content is obtained as follows: and dissolving the weighed glass cloth sample by an alkali dissolution method, fixing the volume, and measuring the obtained sample by an ICP emission spectrum analysis method to obtain the glass cloth. Further, the Al content, Ca content and Mg content were obtained as follows: and (3) heating and decomposing the weighed glass cloth sample by sulfuric acid, nitric acid and hydrogen fluoride, dissolving the glass cloth sample by using dilute nitric acid, fixing the volume, and measuring the obtained sample by an ICP emission spectrum analysis method to obtain the glass cloth sample. As an ICP emission spectrometry device, PS3520VDD II manufactured by Hitachi High-Tech Science Corporation was used.
[ measurement of yarn Width Standard deviation A and mean value of yarn Width ]
The yarn width of 50m of the glass yarn was measured by a transmission type dimension measuring instrument (HIGHACCURACY CMOS MICROMETER LS-9006MR/Keyence Corporation) of an LED projection system while the glass yarn was conveyed at a speed of 1 m/min, and the standard deviation of the yarn width of the glass yarn (yarn width standard deviation A) and the average value of the yarn width were calculated from the obtained yarn width data.
The tension acting on the glass yarn during conveyance of the glass yarn was measured by a tensiometer (Conrolin instruments ETPB-100-C0585, SCHMIDT Co.) and expressed as:
examples 1 to 18, comparative example 1 and reference examples 1 to 3 were 0.12 to 0.18N
Examples 19 to 29, comparative examples 2 and 3 were 0.10 to 0.17N
Examples 30 to 40, comparative examples 4 and 5 were 0.08 to 0.16N
Examples 41 to 48 and comparative examples 6 and 7 were 0.07 to 0.14N.
[ measurement of yarn Width Standard deviation B and yarn Width distribution Standard deviation of yarn Width ]
The yarn width data of 50m glass yarn obtained as described above was divided into 100 pieces in the longitudinal direction, and 100 pieces of yarn width data per 0.5m length of glass yarn were obtained. Based on the yarn width data per 0.5m of the glass yarn, the standard deviation (yarn width standard deviation B) was calculated. Then, in order to confirm the dispersion of the yarn width standard deviation B, the standard deviation was calculated based on the obtained 100 yarn width standard deviations B, and the yarn width distribution standard deviation was obtained.
[ dispersion of twist ]
The twist of 50cm of the glass yarn was measured with a twist checker (Teknos Co., Ltd.) and converted into a twist per 25 mm. The value of the standard deviation calculated from 30 pieces of the obtained twist data (10 points measured on the outer layer side, 10 points measured in the middle, and 10 points measured on the inner layer side of the bobbin) was taken as the twist dispersion.
[ evaluation 1: quality of wool and knitting defects
From the glass cloth rolls obtained in examples and comparative examples, 1000m of glass cloth was wound, and the presence or absence of shot and knitting defects was confirmed, and the quality was evaluated according to the following evaluation criteria.
5: less than 3 hairiness or knitting defects were observed.
4: 3-5 hairiness or knitting defects were observed.
3: 6-15 hairiness or knitting defects were observed.
2: 15-30 hairiness or knitting defects were observed.
1: more than 30 hairiness or knitting defects were observed.
[ evaluation 2: texture property ]
In the weaving process by the air jet loom of the examples and comparative examples, the number of times of weaving stop was counted in the process of weaving 2100 glass cloth, and the weaving property was evaluated according to the following evaluation criteria.
5: stop 0 times.
4: stopping for 1-2 times.
3: stopping for 3-4 times.
2: stopping for 5-7 times.
1: stopping for more than 8 times.
[ evaluation 3: heat resistance ]
After impregnating the glass cloths obtained in examples and comparative examples with a polyphenylene ether resin varnish, excess varnish was scraped off through a predetermined slit, and the resultant was dried in a drying oven at 105 ℃ for a predetermined time to remove toluene, thereby obtaining a prepreg.
The obtained prepregs were stacked in 8 sheets, and copper foils (FV-WS foils, manufactured by Kogawa electric Co., Ltd.) having a thickness of 12 μm and a surface roughness Rz2.0 μm were further stacked on both sides of the prepregs. Then, the mixture was heated from room temperature at a heating rate of 3 ℃ per minute while keeping the pressure at 5kg/cm2Vacuum pressurizing under the condition of (1), heating at a temperature rising speed of 3 ℃/min and under a pressure of 40kg/cm after reaching 130 DEG C2Under the condition of vacuum pressurization, the temperature is kept at 200 ℃ and the pressure is kept at 40kg/cm without changing the temperature after the temperature reaches 200 DEG C2And vacuum pressing was performed for 60 minutes to produce a copper-clad laminate.
Only one side of the copper foil was removed by etching, and a heat resistance test was performed. The heat resistance test was performed as follows: the test piece was cut into a 50mm square, and then dried in an oven at 105 ℃ for 2 hours, followed by carrying out an autoclave test under 2 atmospheres for 4 hours. Thereafter, the test was repeated 30 times by immersing the substrate in a solder bath at 260 ℃ or 288 ℃ for 20 seconds to perform a heat resistance test. The interval between the impregnations was set to 20 seconds.
In the heat resistance test, evaluation was performed based on the following observation by visual observation.
5: a laminated sheet in which any of swelling, peeling and whitening was not observed at 288 ℃
3: a laminated sheet in which neither swelling, peeling, nor whitening was observed under a condition of 260 ℃
(any one of swelling, peeling and whitening was observed at 288 ℃ C.)
1: a laminated sheet in which any one of swelling, peeling and whitening occurs at 260 DEG C
Examples 1 to 18, comparative example 1 and reference examples 1 to 3
Glass yarns (average diameter of glass filaments: 5.0 μm, number of filaments: 100) having the compositions shown in Table 1 were woven by an air jet loom to obtain glass cloth having a picking density of 65 pieces/25 mm for warp yarns, 67 pieces/25 mm for weft yarns and a thickness of 30 μm. Next, desizing treatment was performed by heating, a fiber opening step was performed by high-pressure water jetting, and then surface treatment was performed with a silane coupling agent to produce a glass cloth. In addition, glass cloth was produced by using glass of E glass as reference examples 1 to 3 in the same manner.
[ examples 19 to 29, comparative examples 2 and 3]
Glass yarns (average diameter of glass filaments: 5.0 μm, number of filaments: 200) having the compositions shown in Table 2 were woven to obtain glass cloths having picking densities of warp and weft of 52.5 pieces/25 mm and a thickness of 45 μm, respectively.
[ examples 30 to 40, comparative examples 4 and 5]
Glass yarns (average diameter of glass filaments: 6.0 μm, number of filaments: 200) having the compositions shown in Table 2 were woven to obtain glass cloths having a picking density of 59/25 mm for the warp yarns, a picking density of 61/25 mm for the weft yarns and a thickness of 70 μm.
[ examples 41 to 48, comparative examples 6 and 7 ]
Glass yarns (average diameter of glass filaments: 7.0 μm, number of filaments: 200) having the compositions shown in Table 2 were woven to obtain glass cloths having a picking density of 60/25 mm for the warp yarns, 57/25 mm for the weft yarns and a thickness of 88 μm.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
Industrial applicability
The present invention has industrial applicability as a method for producing a glass cloth used for a prepreg or the like.
Claims (24)
1. A method for manufacturing glass cloth, which is formed by weaving glass yarns formed by a plurality of glass filaments as warp yarns and weft yarns,
the density of the glass yarn to be the weft yarn was 2.2g/cm3Above and below 2.5g/cm3，
A yarn width dispersion coefficient of the glass yarn to be the weft yarn, which represents a dispersion of the yarn width, is 0.003 to 0.013, and/or,
the glass yarn to be the weft yarn has a yarn width distribution variation coefficient A of 0.0002 to 0.0015,
a yarn width dispersion coefficient which is a value obtained by dividing a standard deviation A of a yarn width, which is a standard deviation of a yarn width, by an average diameter of the glass filaments
The yarn width distribution coefficient of variation a is a value obtained by dividing a standard deviation of the yarn width standard deviation B, i.e., a yarn width distribution standard deviation, by the diameter of the glass filaments constituting the weft yarn, when the yarn width standard deviation B, i.e., a standard deviation of the yarn width per 0.5m of length, is obtained.
2. The method for producing glass cloth according to claim 1,
the density of the glass yarn exceeds 2.2g/cm3And less than 2.5g/cm3，
The yarn width dispersion coefficient exceeds 0.003 and is less than 0.010,
and/or the coefficient of variation a of the yarn width distribution exceeds 0.0003 and is lower than 0.0012.
3. The method for producing glass cloth according to claim 1,
the yarn width dispersion coefficient is 0.005 or more and 0.013 or less,
the coefficient of variation A of the yarn width distribution is 0.0006 to 0.0015,
and/or the glass yarn to be the weft yarn has a yarn width distribution variation coefficient B of 0.013 or more and 0.027 or less,
the yarn width distribution coefficient of variation B is a value obtained by dividing a yarn width distribution CV value, which is an average value of a yarn width distribution standard deviation, which is a standard deviation of the yarn width standard deviation B, by the yarn width standard deviation B, when the yarn width standard deviation B, which is a standard deviation of the yarn width per 0.5m of length, is obtained.
4. The method for producing glass cloth according to any one of claims 1 to 3,
the average value of the twist of the weft yarn per 25mm is 0.50 or more and 1.20 or less,
the standard deviation representing the dispersion of twist is 0.10 or more and 0.20 or less.
5. The method for producing glass cloth according to any one of claims 1 to 4,
the weft yarn is a glass yarn formed by bundling 80 to 120 glass filaments with an average diameter of more than 4.5 [ mu ] m and less than 5.5 [ mu ] m, and the average value of the yarn width of the glass yarn is more than 90 [ mu ] m and less than 130 [ mu ] m.
6. The method for producing glass cloth according to any one of claims 1 to 4,
the weft yarn is a glass yarn formed by binding 180 to 220 glass filaments having an average diameter of more than 4.5 [ mu ] m and 5.5 [ mu ] m, and the average yarn width of the glass yarn is 120 to 175 [ mu ] m.
7. The method for producing glass cloth according to any one of claims 1 to 4,
the weft yarn is a glass yarn formed by binding 180 to 220 glass filaments having an average diameter of more than 5.5 [ mu ] m and 6.5 [ mu ] m, and the average yarn width of the glass yarn is 155 to 195 [ mu ] m.
8. The method for producing glass cloth according to any one of claims 1 to 4,
the weft yarn is a glass yarn formed by binding 180-220 glass filaments with an average diameter of more than 6.5 [ mu ] m and less than 7.5 [ mu ] m, and the average yarn width of the glass yarn is more than 180 [ mu ] m and less than 220 [ mu ] m.
9. The method for producing glass cloth according to any one of claims 1 to 8,
the elastic coefficient of the glass yarn is 50-70 GPa.
10. The method for manufacturing glass cloth according to claim 9,
the elastic coefficient of the glass yarn is 50-63 GPa.
11. The method for producing glass cloth according to any one of claims 1 to 10,
the glass cloth has a dielectric constant of 5.0 or less at a frequency of 1 GHz.
12. The method for producing glass cloth according to any one of claims 1 to 11,
the glass yarn is made of,
Si content in SiO2Converted into 40 to 60 mass%,
the content of B is as follows2O3Converted to 15 to 30 mass%.
13. A glass yarn having a density of 2.2g/cm3Above and below 2.5g/cm3，
A yarn width dispersion coefficient representing the dispersion of the yarn width is 0.003 or more and 0.013 or less, and/or,
the coefficient of variation A of the yarn width distribution representing the distribution dispersion of the yarn width is 0.0002 to 0.0015,
the yarn width dispersion coefficient is a value obtained by dividing the standard deviation of the yarn width, i.e., the standard deviation a of the yarn width by the average diameter of the glass filaments
The yarn width distribution coefficient of variation a is a value obtained by dividing a standard deviation of the yarn width standard deviation B, i.e., a yarn width distribution standard deviation, by the diameter of the glass filaments constituting the weft yarn, when the yarn width standard deviation B, i.e., a standard deviation of the yarn width per 0.5m of length, is obtained.
14. The glass yarn of claim 13,
the density of the glass yarn exceeds 2.2g/cm3And less than 2.5g/cm3，
The yarn width dispersion coefficient exceeds 0.003 and is less than 0.010,
and/or the coefficient of variation a of the yarn width distribution exceeds 0.0003 and is lower than 0.0012.
15. The glass yarn of claim 13,
the yarn width dispersion coefficient is 0.005 or more and 0.013 or less,
the coefficient of variation A of the yarn width distribution is 0.0006 to 0.0015,
and/or the glass yarn to be the weft yarn has a yarn width distribution variation coefficient B of 0.013 or more and 0.027 or less,
the yarn width distribution coefficient of variation B is a value obtained by dividing a yarn width distribution CV value, which is an average value of a yarn width distribution standard deviation, which is a standard deviation of the yarn width standard deviation B, by the yarn width standard deviation B, when the yarn width standard deviation B, which is a standard deviation of the yarn width per 0.5m of length, is obtained.
16. The glass yarn as claimed in any one of claims 13 to 15,
the average value of the twist per 25mm is 0.50 or more and 1.20 or less,
the standard deviation representing the dispersion of twist is 0.10 or more and 0.20 or less.
17. The glass yarn as claimed in any one of claims 13 to 16,
the glass yarn is formed by bundling 80 to 120 glass filaments with an average diameter of more than 4.5 mu m and less than 5.5 mu m, and the average value of the yarn width is more than 90 mu m and less than 130 mu m.
18. The glass yarn as claimed in any one of claims 13 to 16,
the glass yarn is formed by bundling 180 to 220 glass filaments with an average diameter of more than 4.5 mu m and less than 5.5 mu m, and the average value of the yarn width is more than 120 mu m and less than 175 mu m.
19. The glass yarn as claimed in any one of claims 13 to 16,
the glass yarn is formed by bundling 180 to 220 glass filaments with an average diameter of more than 5.5 mu m and less than 6.5 mu m, and the average value of the yarn width is more than 155 mu m and less than 195 mu m.
20. The glass yarn as claimed in any one of claims 13 to 16,
the glass yarn is formed by bundling 180-220 glass filaments with an average diameter of more than 6.5 μm and less than 7.5 μm, and the average value of the yarn width is more than 180 μm and less than 220 μm.
21. The glass yarn as claimed in any one of claims 13 to 20, having an elastic modulus of 50 to 70 GPa.
22. The glass yarn as claimed in any one of claims 13 to 20, having an elastic modulus of 50 to 63 GPa.
23. The glass yarn as claimed in any one of claims 13 to 22, having a dielectric constant of 5.0 or less at a frequency of 1 GHz.
24. Glass yarn according to any one of claims 13 to 23, having a Si content in SiO2Converted into 40 to 60 mass%,
the content of B is as follows2O3Converted to 15 to 30 mass%.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| JP2018-241658 | 2018-12-25 | ||
| JP2018241658 | 2018-12-25 | ||
| JP2019-206481 | 2019-11-14 | ||
| JP2019206481A JP2020105683A (en) | 2018-12-25 | 2019-11-14 | Glass cloth manufacturing method and glass yarn |
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| CN111379063A true CN111379063A (en) | 2020-07-07 |
| CN111379063B CN111379063B (en) | 2021-06-25 |
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| JP (1) | JP2024119957A (en) |
| CN (1) | CN111379063B (en) |
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| CN112030313A (en) * | 2020-08-24 | 2020-12-04 | 江苏华跃玻璃制品有限公司 | Production process of high-light glass fiber mesh cloth |
| CN113969453A (en) * | 2020-07-22 | 2022-01-25 | 旭化成株式会社 | Glass cloth, prepreg and printed circuit board |
| CN115404584A (en) * | 2021-05-27 | 2022-11-29 | 旭化成株式会社 | Glass yarn, method for producing glass cloth, and glass cloth |
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| CN112030313A (en) * | 2020-08-24 | 2020-12-04 | 江苏华跃玻璃制品有限公司 | Production process of high-light glass fiber mesh cloth |
| CN115404584A (en) * | 2021-05-27 | 2022-11-29 | 旭化成株式会社 | Glass yarn, method for producing glass cloth, and glass cloth |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111379063B (en) | 2021-06-25 |
| JP2024119957A (en) | 2024-09-03 |
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