CN113969453A - Glass cloth, prepreg and printed circuit board - Google Patents

Glass cloth, prepreg and printed circuit board Download PDF

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Publication number
CN113969453A
CN113969453A CN202110828888.8A CN202110828888A CN113969453A CN 113969453 A CN113969453 A CN 113969453A CN 202110828888 A CN202110828888 A CN 202110828888A CN 113969453 A CN113969453 A CN 113969453A
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glass cloth
glass
mass
content
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远藤正朗
世古宗泉
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Asahi Kasei Corp
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Asahi Kasei Corp
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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D13/00—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
    • D03D13/008—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
    • 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
    • D03D15/50—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 properties of the yarns or threads
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/038—Textiles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Woven Fabrics (AREA)
  • Glass Compositions (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a glass cloth, a prepreg and a printed circuit board. [ problem ] to]The purpose is to provide: low dielectric with suppressed strength reductionGlass cloth, and prepreg and printed wiring board using the low dielectric glass cloth. [ solution ]]A glass cloth comprising glass yarns formed of a plurality of glass filaments as warp yarns and weft yarns, wherein in the following formula (1), the weight loss coefficient obtained as the product of the weight loss ratio derived from the glass component in a heating treatment at 380 ℃ for 2 hours and the average radius of the glass filaments is 0.18 to 0.45, and the Fe content of the glass cloth is Fe2O3More than 0.1 mass% and less than 0.4 mass% in terms of the content. The weight loss coefficient (%) is the weight loss ratio (%) as measured by the average radius (μm) · (1) of the glass filament.

Description

Glass cloth, prepreg and printed circuit board
Technical Field
The invention relates to a glass cloth, a prepreg and a printed circuit board.
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 E glass cloth generally used in the past, for example, low dielectric glass cloth disclosed in patent document 1 is obtained by blending a large amount of B in the glass composition2O3While adjusting SiO2And other components are added 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
However, in order to make the glass cloth have a low dielectric constant, B in the glass yarn is increased2O3When the content is in the range, the modulus of elasticity of the glass yarn is lowered, and the strength of the glass cloth is remarkably lowered by heat treatment such as desizing agent treatment applied in the production process. Therefore, there is a problem that the glass cloth becomes easy to break. When a prepreg is produced using such a glass cloth, the glass cloth is broken when an external load is applied to the glass cloth, such as an operation for controlling the amount of resin deposited, and a problem arises in production.
In this regard, patent document 1 discloses the following method: when spinning glass yarns, by causing B to spin2O3Is less than 20 mass%, and the content of CaO is within a predetermined range, thereby suppressing B2O3And (4) volatilizing. However, let B2O3When the content of (b) is less than 20% by mass, the requirement for lowering the dielectric constant cannot be sufficiently satisfied, and as a result, a glass cloth having a low dielectric constant and suppressed strength reduction cannot be realized. IntoOn the other hand, when the weight loss by the heat treatment is within a specific range, the strength is further reduced.
The present invention has been made in view of the above problems, and an object thereof is to provide: a low dielectric glass cloth with suppressed strength reduction, and a prepreg and a printed circuit board using the 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 above problems can be solved by adjusting the content of Fe in a glass cloth having a predetermined weight loss tendency, and the present invention has been completed.
Namely, the present invention is as follows.
[1]
A glass cloth comprising glass yarns formed of a plurality of glass filaments as warp yarns and weft yarns,
in the following formula (1), the weight loss coefficient obtained as the product of the weight loss ratio derived from the glass component and the average radius of the glass filament in the heating treatment at 380 ℃ for 2 hours is 0.18 to 0.45,
the weight loss coefficient (%) is the average radius (μm) of the glass filament (1)
The Fe content of the glass cloth is Fe2O3More than 0.1 mass% and less than 0.4 mass% in terms of the content.
[2]
The glass cloth according to [1], wherein,
the Fe content of the glass cloth is Fe2O3More than 0.2 mass% and less than 0.4 mass% in terms of the content.
[3]
The glass cloth according to [2], wherein,
the Fe content of the glass cloth is Fe2O3More than 0.3% by mass and less than 0.4% by mass in terms of the content.
[4]
The glass cloth according to any one of [1] to [3],
the glass cloth has an F content of more than 0.005 mass% and less than 0.4 mass%.
[5]
The glass cloth according to [4], wherein,
the glass cloth has an F content of more than 0.005 mass% and less than 0.2 mass%.
[6]
The glass cloth according to [5], wherein,
the glass cloth has an F content of more than 0.005 mass% and less than 0.1 mass%.
[7]
The glass cloth according to any one of [1] to [6],
the above-mentioned glass cloth,
Si content in SiO2Converted into 40-60 mass%,
The content of B is as follows2O3Converted to 15 to 30 mass%.
[8]
The glass cloth according to [7], wherein,
the above-mentioned glass cloth,
Al content is as Al2O310 to 20 mass% in terms of,
The Ca content is 4-12 mass% in terms of CaO,
The Mg content is 1 mass% or less in terms of MgO.
[9]
The glass cloth according to any one of [1] to [8],
the elastic coefficient of the glass cloth is 50-70 GPa.
[10]
The glass cloth according to [9], wherein,
the elastic coefficient of the glass cloth is 50 to 63 GPa.
[11]
The glass cloth according to any one of [1] to [10],
the average diameter of the glass filaments constituting the warp and the weft is 3.5 to 5.4 μm independently of each other.
[12]
The glass cloth according to any one of [1] to [11],
has a dielectric constant of 5.0 or less at a frequency of 1 GHz.
[13]
A prepreg, having:
[1] the glass cloth according to any one of [1] to [12 ]; and the combination of (a) and (b),
a matrix resin impregnated into the glass cloth.
[14]
A printed wiring board comprising the glass cloth according to any one of [1] to [12 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a low dielectric glass cloth with suppressed strength reduction, and a prepreg and a printed circuit board using the low dielectric glass cloth.
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.
[ glass cloth ]
The glass cloth of the present embodiment is a glass cloth composed of glass yarns formed of a plurality of glass filaments as warp yarns and weft yarns, and in the following formula (1), the weight loss coefficient obtained as the product of the weight loss ratio derived from the glass component and the average radius of the glass filaments in a heating treatment at 380 ℃ for 2 hours is 0.18 to 0.45, and the Fe content of the glass cloth is Fe2O3More than 0.1 mass% and less than 0.4 mass% in terms of the content.
Weight loss coefficient (%) x average radius of glass filament (μm) · (1)
In the glass cloth having a low dielectric constant, strength reduction of the glass yarn progresses in heat treatment in the manufacturing process thereof or heat treatment in a subsequent process. Since the strength is reduced and the elastic modulus of the glass yarn constituting the low dielectric glass cloth is low, the low dielectric glass cloth is more likely to be broken than a case where other glass yarn is used such as E glass. In contrast, in the present embodiment, in the glass cloth having a predetermined weight loss tendency, the content of Fe (iron) in the glass is adjusted, and more preferably, the content of F (fluorine) is adjusted, so that the strength reduction due to the heat treatment is suppressed.
The reason why the strength can be suppressed from decreasing by adjusting the Fe content is not limited, but is considered as follows. In the spinning, even if a portion where the glass component volatilizes under high temperature conditions and the glass yarn is sparse is generated, the molten glass can flow so as to fill the portion, and the portion where the glass yarn is sparse due to the volatilization of the glass component accompanied by weight loss can be eliminated by the flow. On the other hand, even if the glass yarn constituting the glass cloth generates a sparse portion due to volatilization of the glass component, the glass cannot flow so as to fill the portion. In this case, it is considered that the glass cloth of the present embodiment may play a role in Fe bonding of a portion where glass yarn is thinned due to volatilization of the glass component.
The reason why the strength can be further suppressed from decreasing by adjusting the F content is not limited, but is considered as follows. F reduces the viscosity of the molten glass during the glass making process. Therefore, when the content of F is within the predetermined range, when a metal component such as Fe is incorporated into the glass structure, it can be uniformly dispersed without being localized, and a uniform glass can be formed. It is considered that the uniform dispersion of Fe makes it possible to more effectively exhibit the function of Fe binding the above-described portion where glass yarn is thinned due to volatilization of the glass component. Further, it is considered that since Fe and the like are locally present, if hard portions are unevenly present in the glass, breakage easily occurs from the portions as starting points, but it is considered that such local presence is alleviated by adjusting the F content, and the strength reduction can be further suppressed.
With the above configuration, in the present embodiment, the problem of breakage of the low dielectric glass cloth is solved, and a glass cloth having high breakage resistance and a low dielectric constant can be provided. The structure of the present embodiment will be described in more detail below.
(weight loss factor)
The weight loss coefficient (hereinafter, also simply referred to as "weight loss coefficient") obtained as the product of the weight loss ratio derived from the glass component and the average radius of the glass filaments when the glass cloth is subjected to heat treatment at 380 ℃ for 2 hours is 0.18 or more and 0.45 or less, preferably 0.19 or more and 0.42 or less, more preferably 0.20 or more and 0.39 or less, and further preferably 0.20 or more and 0.35 or less.
The "weight loss ratio derived from the glass component" means that the weight loss ratio when heat treatment is performed at 380 ℃ for 2 hours is derived from the loss due to volatilization of the glass component during the heat treatment. As will be described later, the weight loss ratio of the present embodiment is calculated after removing the surface treatment agent such as a silane coupling agent and the organic impurity adhering component physically adsorbed by a good solvent such as alcohols and acetone in advance when the surface treatment agent such as a silane coupling agent adheres to the glass cloth and when a large amount of organic impurities adheres to the glass cloth. Therefore, the weight loss ratio of the glass cloth after the heat treatment after the removal of the adhering component that thermally decomposes at 380 ℃ becomes the reduction ratio derived from the glass component.
In addition, it was confirmed that the weight loss ratio depends on the filament diameter of the glass yarn. The weight loss ratio varies depending on the diameter of the glass filament, and the smaller the filament diameter, the larger the weight loss. On the other hand, the product of the weight loss ratio and the filament radius becomes substantially constant, independent of the filament diameter. Therefore, in the present embodiment, the weight loss coefficient is normalized by the filament diameter.
The weight loss coefficient is 0.18 or more, and thus the strength is likely to be directly reduced. However, by adjusting the Fe content described later and, as a more preferable mode, also adjusting the F content, in the present embodiment, it is possible to suppress the decrease in strength and to obtain a glass cloth having a lower dielectric constant depending on the composition of the glass cloth. In addition, since the weight loss coefficient is 0.45 or less, the strength reduction suppression effect by Fe effectively acts, and a significant strength reduction can be suppressed.
The method of measuring the weight loss ratio can be performed according to the following procedure. First, the glass cloth was put into a drier at 105 ℃. + -. 5 ℃ and dried for 60 minutes, and then, the glass cloth was transferred to a drier and naturally cooled to room temperature. After natural cooling, the weight of the glass cloth was measured in units of 0.1mg or less (glass cloth weight a). Subsequently, the glass cloth was heated at 380 ℃ for 2 hours, and then, the glass cloth was transferred to a dryer and naturally cooled to room temperature. After natural cooling, the weight of the glass cloth was measured in units of 0.1mg or less (weight b of the glass cloth after heat treatment). Then, the weight loss due to the heat treatment was determined, and the weight loss ratio (%) was calculated from the following formula (2).
Weight loss ratio (%) - (a-b)/a × 100 · (2)
The weight loss ratio obtained as described above is preferably 0.04 to 0.5%, more preferably 0.05 to 0.3%, and still more preferably 0.06 to 0.25%. The weight loss ratio is 0.04% or more, and thus the strength is likely to be directly reduced. However, by adjusting the Fe content described later and, as a more preferable mode, also adjusting the F content, in the present embodiment, it is possible to suppress the decrease in strength and to obtain a glass cloth having a lower dielectric constant depending on the composition of the glass cloth. In addition, the weight loss ratio is 0.5% or less, so that the strength reduction-suppressing effect by Fe effectively acts, and a significant strength reduction can be suppressed.
Next, the average diameter of the glass filaments of the glass yarn constituting the glass cloth was measured in accordance with JIS R3420, and the average filament radius was determined as a half of the filament diameter. In the present embodiment, the glass filaments are simply referred to as glass filaments. The average radius of the glass filaments used for calculating the weight loss coefficient was the average radius before the heat treatment. The average radius of the glass filaments thus obtained is preferably 1.25 to 4.5. mu.m, more preferably 1.5 to 3.75. mu.m, and still more preferably 1.75 to 2.7. mu.m.
The glass cloth used in the above-described method for measuring the weight loss ratio may be appropriately subjected to pretreatment. For example, since the adhered matter does not adhere to the glass filaments in the glass cloth taken out from the intermediate roll after the desizing treatment (hot washing), it can be used as it is in the above-described method for measuring the weight loss ratio.
On the other hand, when the weight loss ratio is determined for a glass cloth obtained by coating a surface treatment agent such as a silane coupling agent on a glass cloth, the weight loss coefficient can be determined by the above method after the surface treatment agent such as a silane coupling agent physically adsorbed is washed and removed with a good solvent such as alcohols and acetone in advance.
The "physically adsorbed silane coupling agent" refers to a silane coupling agent attached to the glass filaments, and does not refer to a silane coupling agent bonded to the glass filaments by chemical bonding. In contrast, a silane coupling agent that is chemically bonded to a glass filament is referred to as a "chemisorbed silane coupling agent".
In addition, when the glass cloth contains organic impurities (e.g., a starch-based sizing agent applied in the process of producing glass yarns, combustion residues in the heat washing step of the sizing agent in the previous stage), the weight loss coefficient can be determined by the above-described method after removing the organic impurities adhering to the glass cloth in advance by washing and removing operations with alcohols, acetone, and the like.
The cleaning is performed to remove the physisorbed silane coupling agent and organic impurities, but not to remove the chemisorbed silane coupling agent. However, even if the heating is performed at 380 ℃ for 2 hours, the chemisorbed silane coupling agent is not decomposed, or it is assumed that a part of the decomposition does not exceed the error range, and therefore, in the measurement of the weight loss ratio in the present embodiment, it is not necessary to remove the chemisorbed silane coupling agent in the pretreatment.
In order to simplify the judgment of whether or not to perform pretreatment, glass cloth previously washed with a good solvent such as alcohol or acetone may be uniformly used for the measurement of the weight loss ratio. Thus, the weight loss ratio can be measured in the same state regardless of the glass cloth taken out from the intermediate roll after the desizing treatment (thermal washing) or the glass cloth to which the physically adsorbed silane coupling agent or organic impurities are attached.
As another method, when the weight loss coefficient is determined, the amount of the surface treatment agent and the organic impurities before and after heating are quantified, and the weight loss amount derived from the surface treatment agent is subtracted from the obtained weight loss, whereby the weight loss coefficient derived from the glass component can be determined. As a method for determining the weight loss amount derived from the surface treatment agent, a known method such as a method for quantifying the silane coupling agent described in japanese patent No. 6472082, etc. can be used.
The weight loss coefficient can be adjusted by increasing or decreasing, for example, a relatively volatile component, for example, the B content, in the composition of the glass cloth, and from the same viewpoint, it can be adjusted by increasing or decreasing other components.
In addition, the weight loss coefficient may be adjusted as follows: the adjustment is performed by increasing or decreasing the chance of the glass surface being exposed to a high-temperature atmosphere by adjusting the space filling rate (weaving density, thickness) of glass in the glass cloth, adjusting the state of unraveling of monofilaments constituting the glass yarn bundle by a fiber opening process or the like, adjusting the monofilament diameter of the glass yarn used, and the like.
That is, the weight loss coefficient is determined not only by the composition of the glass cloth.
(composition)
The composition of the glass cloth of the present embodiment is explained below. The composition of the glass cloth is the same as the composition of the glass yarn constituting the glass cloth. In the composition of the glass cloth of the present embodiment, the content of Fe is Fe2O3In terms of the content, the content is more than 0.1% by mass and less than 0.4% by mass, preferably more than 0.2% by mass and less than 0.4% by mass, more preferably more than 0.3% by mass and less than 0.4% by mass, and the most preferred range is more than 0.3% by mass and 0.38% by mass or less. The Fe content exceeds 0.1 mass%, so that the strength reduction due to the heat treatment of the glass cloth can be suppressed. In addition, the content of Fe is less than 0.4 mass%, so that it is possible to suppress the strength of the glass cloth itself before heat treatment from being lowered inversely due to an excessive content of Fe. The Fe content can be adjusted depending on the amount of raw materials used for producing the glass filaments, purification removal in producing the glass filaments, or addition.
The strength reduction caused by an excessive Fe content is not particularly limited, and can be considered as follows. The glass yarn is basically composed of an amorphous portion, but a portion where Fe is present is considered to be a portion having high crystallinity. It is considered that the portion having a weak strength is locally conspicuous depending on the existence mode of the portion having a high crystallinity, but in the present embodiment, the decrease in strength of the glass cloth can be suppressed by adjusting the Fe content to a constant amount or less.
The content of F in the composition of the glass cloth of the present embodiment is preferably more than 0.005 mass% and less than 0.4 mass%, more preferably more than 0.005 mass% and less than 0.2 mass%, and still more preferably more than 0.005 mass% and less than 0.1 mass%. The content of F exceeds 0.005 mass%, and the strength reduction due to the heat treatment of the glass cloth tends to be further suppressed. In addition, the F content is less than 0.4 mass%, so that the strength of the glass cloth itself before heat treatment can be suppressed from being lowered inversely due to an excessive F content. The content of F can be adjusted according to the amount of raw materials used in the production of the glass filaments.
The strength reduction due to the excessive F content is not particularly limited, and is considered as follows. It is considered that the larger the F content is, the stronger the phase separation property of the glass composition becomes, and it becomes difficult to make the glass component uniform.
In a preferred embodiment of the present embodiment, both the Fe content and the F content are in the above-described predetermined ranges, and the effect of suppressing the strength reduction by the heat treatment tends to be further improved.
The Si content of the glass cloth 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 still more preferably 48 to 52% by mass in terms of mass. Si is a component forming the skeleton structure of the glass yarn, and when the Si content is 40 mass% or more, the strength of the glass yarn itself before heat treatment is further improved in addition to the suppression of the strength reduction by heat treatment, and breakage of the glass cloth tends to be further suppressed in the subsequent steps such as the production process of the glass cloth and the production of a prepreg using the glass cloth. When the Si content is 40 mass% or more, the dielectric constant of the glass cloth tends to be further reduced. 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, the glass filaments obtained become difficult to produceSince the glass filaments are not likely to locally form a portion having a weak strength, the glass cloth made of glass yarns obtained using the glass filaments is not likely to be broken. The Si content can be adjusted according to the amount of raw materials used in the production of the glass filaments.
The content of B in the glass cloth is 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. When the B content is 15 mass% or more, the dielectric constant tends to be further lowered. The content of B is preferably 30 mass% or less, because the strength of the glass cloth is high and the moisture absorption resistance is excellent. Further, since the content of B is 30 mass% or less, volatilization of the glass component due to heat treatment such as a sizing agent removal treatment is suppressed to be small, and thus, a decrease in strength is suppressed, and a decrease in moisture absorption resistance is also suppressed, 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 may be estimated in advance and adjusted.
In addition, the glass cloth may have other compositions than those described above. The other composition is not particularly limited, and examples thereof include Al, Ca, Mg, P, Na, K, Ti, Zn, and the like.
The Al content of the glass cloth is Al2O3The content is preferably 10 to 20% by mass, more preferably 11 to 18% by mass, and further preferably 12 to 17% by mass in terms of mass. When the Al content is within the above range, the electrical characteristics and strength tend to be further improved. 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 cloth is preferably 4.0 to 12 mass%, preferably 5.7 to 10 mass%, and more preferably 6.0 to 9.0 mass% in terms of CaO. When the Ca content is 4.0 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. When the Ca content is 10 mass% or less, 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 Mg content of the glass cloth is preferably 1.0 mass% or less, more preferably 0.7 mass% or less, further preferably 0.01 mass% or more and 0.7 mass% or less, further preferably 0.05 mass% or more and 0.6 mass% or less, further more preferably 0.05 mass% or more and 0.45 mass% or less in terms of MgO. When the Mg content is 1.0 mass% or less, the glass cloth tends to be less likely to be broken when passing through a squeeze roll, a rolling roll or the like in a wet state in a fiber opening step, a surface treatment step or the like in the production of the glass cloth. In addition, phase separation during the production of the glass filaments is suppressed, and the moisture absorption resistance of the resulting glass filaments is further improved. Thus, the printed wiring board obtained is less susceptible to the use environment of a high humidity environment, and the environmental dependence of the dielectric constant can be reduced. The Mg content can be adjusted according to the amount of raw materials used in the production of the glass filaments.
The ratio of the Ca content to the Mg content is preferably 5.0 to 50, more preferably 10 to 45, still more preferably 15 to 40, still more preferably 20 to 35, and still more preferably 20 to 30. When the ratio of the Ca content to the Mg content is within the above range, the glass fiber is more homogeneous, and therefore, a glass fiber having high strength and excellent moisture absorption resistance can be obtained, and the glass fiber is less likely to be broken, and the environmental dependence of the dielectric constant tends to be reduced.
The contents can be measured by ICP emission spectrometry. Specifically, the Si content and the B content can be obtained as follows: after the weighed glass cloth sample is decomposed by sodium hydroxide under pressure, the glass cloth sample is dissolved by dilute nitric acid and filtered. Then, the insoluble matter was melted in sodium carbonate, combined with the filtrate to a constant volume, and the resulting sample was measured by ICP emission spectrometry, whereby it was obtained.
The Fe content, Al content, Ca content, and Ma content can be obtained as follows: heating and decomposing weighed glass cloth samples by using perchloric acid, nitric acid, hydrochloric acid and hydrogen fluoride, heating and dissolving by using dilute aqua regia, and filtering. And (5) performing volume fixing on the filtrate. Then, the insoluble component was decomposed by heating in sulfuric acid, nitric acid, hydrochloric acid and hydrogen fluoride and fixed in solution, and the obtained sample was measured by ICP emission spectrometry, whereby it was obtained. As an ICP emission spectrometer, PS3520VDD II manufactured by Hitachi High-Tech Science Corporation was used.
The F content can be determined as follows: after burning the weighed glass cloth sample in a tubular electric furnace, the generated gas is absorbed in the absorption liquid. With respect to the solution, fluorine ion (F) was measured by ion chromatography-) The content in the sample can be determined. The combustion apparatus may be an automatic sample combustion apparatus (AQF-2100S) manufactured by Mitsubishi Chemical analytical Co., Ltd., and the measurement apparatus may be an ion chromatograph ICS-1500 manufactured by Thermo Fisher Scientific.
The elastic modulus of the glass cloth is preferably 50 to 70GPa, more preferably 50 to 63GPa, and still more preferably 53 to 63 GPa. The lower the elastic coefficient of the glass cloth, the more likely the glass cloth is to be broken. Therefore, when the elastic modulus is 50GPa or more, the glass cloth tends to be less likely to be broken when the glass cloth passes through a squeeze roll, a rolling roll or the like in a wet state in a glass cloth manufacturing process such as a fiber opening process or a surface treatment process. In addition, in the subsequent steps such as the production of a prepreg, when the glass cloth is passed through the slit for the purpose of controlling the amount of penetration of the resin into the glass cloth, the glass cloth tends to be less likely to be broken. When the elastic coefficient of the glass cloth yarn is 70GPa or less, the texture of the glass cloth is soft, and when the glass cloth passes through a narrow interval such as a squeeze roll or a roll, the glass cloth tends to be less likely to be broken. Further, when the elastic coefficient of the glass cloth is 70GPa or less, the dielectric constant tends to be relatively further lowered. The modulus of elasticity can be measured by the method described in examples. In addition, the elastic modulus can be adjusted according to the composition of the glass yarn.
The glass cloth of the present embodiment has a dielectric constant of preferably 5.0 or less, more preferably 4.7 or less, further preferably 4.5 or less, and particularly preferably 4.0 or less at a frequency of 1 GHz. In the present embodiment, the term "dielectric constant" refers to a dielectric constant at a frequency of 1GHz, unless otherwise specified.
(constitution)
The glass yarn is obtained by binding and twisting a plurality of glass filaments as needed, and the glass cloth is obtained by weaving the glass yarn as warp and weft. Glass yarns are classified as multifilaments and glass filaments as monofilaments, respectively.
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. When the average diameter of the glass filaments is within the above range, the processability tends to be further improved when the obtained substrate is processed by a mechanical drill, a carbon dioxide gas laser, or a UV-YAG laser. Therefore, a printed circuit board that is thin and high-density mounted can be realized. In particular, when the average diameter is 5.4 μm or less, the surface area per unit volume increases, and the strength reduction by the heat treatment is likely to occur, and therefore, the effect of suppressing the strength reduction of the present embodiment becomes more important. Further, the average diameter of 2.5 μm or more reduces the surface area and suppresses volatilization of the glass component, and in the production process of the glass cloth such as the fiber opening process and the surface treatment process, the glass cloth tends to be less likely to be broken when passing through a squeeze roll, a nip roll or the like in a wet state. In addition, in the subsequent steps such as the production of a prepreg, when the glass cloth is passed through the slit for the purpose of controlling the amount of penetration of the resin into the glass cloth, the glass cloth tends to be less likely to be broken.
The picking density of the warp and weft constituting the glass cloth is preferably 30 to 130 pieces/25 mm, more preferably 40 to 120 pieces/25 mm, and further preferably 50 to 110 pieces/25 mm.
The thickness of the glass cloth is preferably 8 to 100 μm, more preferably 10 to 50 μm, further preferably 12 to 35 μm, and most preferably 12 to 30 μm. When the thickness of the glass cloth is within the above range, a thin glass cloth having high strength tends to be obtained. In particular, when the thickness is 8 μm or more, the ratio of the glass filaments in the vicinity of the surface of the glass cloth is reduced, and therefore, the amount of volatilization of the glass component tends to be reduced. Further, since the ratio of the glass filaments in the vicinity of the surface of the glass cloth is increased by the thickness of 100 μm or less, the strength reduction due to the increase in the amount of volatilization of the glass component is likely to occur, and the effect of suppressing the strength reduction of the present invention becomes more important. The weight loss coefficient depends on the diameter of the filaments constituting the glass cloth, and thus, it is difficult to depend on the thickness. This tendency can be maintained at least in the above thickness range.
The weight (weight per unit area) of the glass cloth is preferably 8 to 250g/m2More preferably 8 to 100g/m2More preferably 8 to 50g/m2Particularly preferably 8 to 35g/m2。
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, the plain weave structure is more preferable.
(surface treatment)
The glass cloth may be surface-treated with 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 can be used in combination as needed.
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: n-beta- (N-vinylbenzylaminoethyl) -gamma-aminopropyltrimethoxysilane and the hydrochloride thereof, N-beta- (N-vinylbenzylaminoethyl) -gamma-aminopropylmethyldimethoxysilane and the hydrochloride thereof, N-beta- (N-bis (vinylbenzyl) aminoethyl) -gamma-aminopropyltrimethoxysilane and the hydrochloride thereof, N-beta- (N-benzylaminoethyl) -gamma-aminopropyltrimethoxysilane and the hydrochloride thereof, and, N-beta- (N-benzylaminoethyl) -gamma-aminopropyltriethoxysilane and its hydrochloride, gamma- (2-aminoethyl) aminopropyltrimethoxysilane, gamma- (2-aminoethyl) aminopropyltriethoxysilane, aminopropyltrimethoxysilane, vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane and the like, or a mixture thereof.
The molecular weight of the surface treatment agent is preferably 100 to 600, more preferably 150 to 500, and further preferably 200 to 450. Among them, 2 or more surface treatment agents having different molecular weights are preferably used. When the surface of the glass yarn is treated by using 2 or more surface-treating agents having different molecular weights, the density of the surface-treating agent in the surface of the glass cloth tends to be high, and the reactivity with the matrix resin tends to be further improved.
[ method for producing glass cloth ]
The method for producing the glass cloth of the present embodiment is not particularly limited, and examples thereof include a method including the steps of: 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 from the glass yarn adhered to the glass cloth, and a surface treatment step using a surface treatment agent.
The weaving method is not particularly limited as long as the weft yarns and the warp yarns are woven so as to have a predetermined weaving structure. 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. Further, the desizing method is not particularly limited, and examples thereof include: a method for removing sizing agent by heating. Further, examples of the surface treatment method include: a method of bringing the surface treatment agent into contact with a glass cloth and drying it. The contact of the surface treatment agent with the glass cloth may be performed by the following method: 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, a die coater, a 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 using electromagnetic waves.
[ prepreg ]
The prepreg of the present embodiment has: the above glass cloth; and a matrix resin composition impregnated in the glass cloth. The prepreg having the glass cloth is less likely to cause a decrease in strength, 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: a printed wiring board which has little influence on 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 circuit board of the present embodiment includes the glass cloth. The printed wiring board of the present embodiment is less likely to cause a decrease in strength, and the yield of the final product is high. Further, since the dielectric characteristics are excellent and the moisture absorption resistance is excellent, the effect of reducing the influence of the use environment, particularly the effect of reducing the variation in dielectric constant in a high humidity environment can be exhibited.
The various measurement values are measured by the measurement methods described in the examples described below, unless otherwise specified.
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.
[ weight loss coefficient ]
The weight loss coefficient was measured according to the following procedure.
First, the glass cloth taken out of the middle roll was put into a drier at 105 ℃. + -. 5 ℃ for drying for 60 minutes, and then, the glass cloth was transferred to a drier and naturally cooled to room temperature. After natural cooling, the weight of the glass cloth (weight a of the glass cloth) was measured in units of 0.1mg or less. Subsequently, the glass cloth was heated at 380 ℃ for 2 hours, and then, the glass cloth was transferred to a dryer and naturally cooled to room temperature. After natural cooling, the weight of the glass cloth was measured in units of 0.1mg or less (weight b of the glass cloth after heat treatment). Then, the weight loss due to the heat treatment was determined, and the weight loss ratio (%) was calculated from the following formula (2).
Weight loss ratio (%) - (a-b)/a × 100 · (2)
Next, the diameter of the monofilament was measured according to method B of JIS R3420, and its value of 1/2 was used as the radius of the monofilament. In the B method of JIS R3420, when the diameters of 25 filament sections are measured at random, the diameters of all the filaments constituting the glass yarn (multifilament) are measured and the average value thereof is determined as the filament diameter.
The weight loss coefficient was calculated from the weight loss ratio (%) and the average radius (μm) of the glass filaments according to the following formula (1).
Weight loss coefficient (%) x average radius of glass filament (μm) · (1)
[ elastic modulus ]
The elastic modulus is as follows: for the modulus of elasticity of the glass yarn, a glass block was used for the test piece and measured by a pulse echo superposition method.
[ dielectric constant of glass yarn ]
The glass yarn was melted to prepare a block-shaped glass test piece having a length of about 50mm and a width of about 1.5 mm. Measured with a cavity resonator. The test piece was dried in an oven at 105. + -. 2 ℃ for 2 hours, allowed to stand in a thermostatic chamber at 23. + -. 2 ℃ and a relative humidity of 50. + -. 5% for 96 hours, and then the dielectric constant at 10GHz was measured.
The measurement was carried out using a network analyzer (N5230A, manufactured by Agilent technologies) and a Cavity resonator (Cavity resonator CP series) manufactured by Kanton electronic applications, Inc. under an environment of 23. + -. 2 ℃ and a relative humidity of 50. + -. 5%.
[ composition of glass cloth ]
The composition of the glass cloth was determined by ICP emission spectroscopy. Specifically, the Si content and the B content were obtained as follows: after the weighed glass cloth sample is decomposed by sodium hydroxide under pressure, the glass cloth sample is dissolved by dilute nitric acid and filtered. The insoluble component was melted with sodium carbonate, combined with the filtrate to a constant volume, and the resulting sample was measured by ICP emission spectrometry.
In addition, the Fe content, Al content, Ca content, Ma content were obtained as follows: heating and decomposing weighed glass cloth samples by using perchloric acid, nitric acid, hydrochloric acid and hydrogen fluoride, heating and dissolving by using dilute aqua regia, and filtering. The filtrate was brought to constant volume. The insoluble component was decomposed by heating with sulfuric acid, nitric acid, hydrochloric acid and hydrogen fluoride to a constant volume, and the obtained sample was measured by ICP emission spectrometry. As an ICP emission spectrometer, PS3520VDD II manufactured by Hitachi High-Tech Science Corporation was used.
Further, the F content was determined as follows: after burning the weighed glass cloth sample in a tubular electric furnace, the generated gas is absorbed in the absorption liquid. With respect to the solution, fluorine ion (F) was measured by ion chromatography-) The content in the sample was determined. The combustion apparatus used was an automatic sample combustion apparatus (AQF-2100S) manufactured by Mitsubishi Chemical analytical Co., Ltd, and the measurement apparatus used was an ion chromatograph ICS-1500 manufactured by Thermo Fisher Scientific.
[ strength reduction confirmation test ]
Using the glass cloths obtained in examples and comparative examples, prepregs were produced under the following conditions, and whether the strength was sufficient was evaluated. The glass cloth was immersed in the varnish while being continuously taken out and conveyed, and the amount of the varnish applied was adjusted by passing through a slit. Subsequently, the resultant was dried in a drying oven at 120 ℃ to obtain a prepreg. The varnish used was a varnish containing 65 parts by mass of methacrylated polyphenylene ether, 35 parts by mass of triallyl isocyanurate, 10 parts by mass of a hydrogenated styrene-based thermoplastic elastomer, 25 parts by mass of a bromine-based flame retardant, 65 parts by mass of spherical silica, 1 part by mass of an organic peroxide, and 210 parts by mass of toluene.
With respect to the glass cloths obtained in the examples and comparative examples, prepregs were produced by the above-described method for 10 product rolls of 2000m each. Based on the production results, the strength reduction was confirmed by the following evaluation criteria.
Very good: the glass cloth was not broken, and a prepreg was produced using a roll of 10 glass cloths. The glass cloth was judged to be excellent in productivity and workability.
Good: in the process of producing the prepreg, although a breakage occurred in the roll of 1 glass cloth, the remaining 9 rolls were not broken, and the prepreg could be produced. The glass cloth was judged to have practical strength.
And (delta): in the prepreg manufacturing process, the rolls of 2 to 3 glass cloths are broken, but the remaining rolls are not broken, and the prepreg can be manufactured. It was judged that a glass cloth having improved strength was required.
X: in the process of producing the prepreg, breakage may occur in a roll of 4 or more glass cloths.
[ dielectric constant and dielectric loss tangent of laminated sheet ]
The prepregs obtained in the strength reduction confirmation test were stacked in a predetermined number so that the thickness of the laminate sheet became about 1mm, and further, copper foils (GTS-MP foils having a thickness of 18 μm, manufactured by guchuan electrical industries, inc.) were stacked on both sides of the stacked prepregs, and vacuum pressing was performed, thereby obtaining a copper-clad laminate sheet. Next, the copper foil is removed from the copper-clad laminate by etching, thereby obtaining a laminate.
A test piece having a length of about 50mm and a width of about 1.5mm was cut out from the resulting laminated sheet so that the warp of the glass cloth became a long side, and the test piece was used for an electrical characteristic test. The obtained test piece was put in an oven at 105 ℃. + -. 2 ℃ and dried for 2 hours, and then the dielectric constant and the dielectric loss tangent were measured at 10GHz under the standard conditions and high humidity conditions shown below.
Standard conditions: the high humidity conditions were determined after standing in a thermostatic chamber at 23. + -. 2 ℃ and a relative humidity of 50. + -. 5% for 96 hours: standing in a thermostatic chamber with 40 + -2 deg.C and relative humidity of 85 + -5% for 96 hr, and determining
The measurement was carried out at a temperature of 23. + -. 2 ℃ and a relative humidity of 50. + -. 5% using a network analyzer (N5230A, manufactured by Agilent technologies) and a Cavity resonator (Cavity resonator CP series) manufactured by Kanton electronic applications and developers. For each measurement, 5 times of repetition was carried out using 5 cut test pieces, and the average value was defined as the value of dielectric constant and dielectric loss tangent.
[ example 1]
A glass cloth having a picking density of 94 pieces/25 mm and a thickness of 14 μm in each of the warp and weft was obtained by weaving a low dielectric glass yarn (dielectric constant 4.8) composed of 50 filaments having an average filament diameter of 4.0 μm and a filament number of 50 with an air jet loom. Subsequently, the glass cloth was heated to perform a desizing treatment, thereby obtaining a glass cloth intermediate roll having a width of 1280mm and a length of 2000 m.
Using the obtained glass cloth middle roll, while continuously taking out and conveying the glass cloth from the glass cloth middle roll, the glass cloth is immersed in a treatment liquid containing a silane coupling agent, the coating amount of the silane coupling agent is adjusted by an extrusion liquid, and then the glass cloth is dried temporarily. Then, the glass cloth was unwound by high-pressure water jet, dried, and wound into a roll shape to obtain a product roll of glass cloth. The coating and fiber opening treatment of the silane coupling agent was continuously performed on 10 rolls. The composition of the obtained glass cloth is shown in table 1.
[ examples 2 to 11]
A roll of glass cloth was obtained in the same manner as in example 1 except that the composition of the glass yarn was different. The composition of the obtained glass cloth is shown in table 1.
[ example 12]
A roll of glass cloth was obtained in the same manner as in example 2, except that the low dielectric glass yarn was used in the same manner as in example 2, and the strength of the high-pressure water jet in the splitting treatment was reduced to reduce the degree of splitting.
[ example 13 ]
A roll of glass cloth was obtained in the same manner as in example 2, except that the low dielectric glass yarn was used in the same manner as in example 2, and the strength of the high-pressure water jet in the splitting treatment was increased to increase the degree of splitting.
[ example 14 ]
A roll of glass cloth was obtained in the same manner as in example 1 except that a low dielectric glass yarn (dielectric constant 4.8) having an average filament diameter of 5.0 μm and a filament number of 100 was woven so that the picking densities of the warp and weft were 69 yarns/25 mm, respectively, to produce a glass cloth. The thickness of the obtained glass cloth was 30 μm, and the composition thereof is shown in Table 1.
[ example 15 ]
Rolls of glass cloth were obtained in the same manner as in example 14, except that the picking densities of the warp and weft were 55 tapes/25 mm, respectively. The thickness of the obtained glass cloth was 30 μm, and the composition thereof is shown in Table 1.
[ example 16 ]
Rolls of glass cloth were obtained in the same manner as in example 1 except that low dielectric glass yarns (dielectric constant 4.8) each having an average filament diameter of 7.0 μm and a filament number of 200 were woven so that the picking densities of the warp and weft were 60/25 mm and 57/25 mm, respectively, to produce glass cloth. The thickness of the obtained glass cloth was 92 μm, and the composition thereof is shown in Table 1.
[ comparative examples 1 to 6]
A roll of glass cloth was obtained in the same manner as in example 1 except that the composition of the glass yarn was different. The composition of the obtained glass cloth is shown in table 1.
[ reference example 1]
A roll of glass cloth was obtained in the same manner as in example 1, except that glass yarn (dielectric constant 6.8) composed of E glass was used.
[ Table 1]
Figure BDA0003174758140000211
[ Table 2]
Figure BDA0003174758140000221
The glass cloth of examples 1 to 4, 7, 12, and 14 to 16 was not broken in 10 rolls, and was stably produced. In addition, in the glass cloths of examples 5, 6, 8 to 11, and 13, only 1 roll of the glass cloth was broken, but the remaining 9 rolls were stably manufactured. In addition, the glass cloth of reference example 1 had poor electrical characteristics, although no breakage occurred.
On the other hand, in the glass cloths of comparative examples 1, 3 and 5, breakage occurred in 2 to 3 rolls. It is not sufficient to stably supply a printed wiring board using a low dielectric glass, and improvement is required. Further, in the glass cloths of comparative examples 2, 4, and 6, breakage occurred in 4 rolls continuously from the start of coating, and therefore, the coating test had to be stopped.
Further, as shown in example 11, it is understood that when the Mg content is large, the dielectric loss tangent under high humidity conditions increases greatly when a laminated sheet is produced.
Industrial applicability
The present invention has industrial applicability as a low dielectric glass cloth used for a prepreg or the like.

Claims (14)

1. A glass cloth comprising glass yarns formed of a plurality of glass filaments as warp yarns and weft yarns,
in the following formula (1), the weight loss coefficient obtained as the product of the weight loss ratio derived from the glass component and the average radius of the glass filament in the heating treatment at 380 ℃ for 2 hours is 0.18 to 0.45,
weight loss coefficient (%) as the average radius (μm) of the glass filament (1)
The Fe content of the glass cloth is Fe2O3More than 0.1 mass% and less than 0.4 mass% in terms of the content.
2. Glass cloth according to claim 1,
the Fe content of the glass cloth is Fe2O3More than 0.2 mass% and less than 0.4 mass% in terms of the content.
3. Glass cloth according to claim 2,
the Fe content of the glass cloth is Fe2O3More than 0.3% by mass and less than 0.4% by mass in terms of the content.
4. Glass cloth according to any one of claims 1 to 3,
the glass cloth has an F content of more than 0.005 mass% and less than 0.4 mass%.
5. Glass cloth according to claim 4,
the glass cloth has an F content of more than 0.005 mass% and less than 0.2 mass%.
6. Glass cloth according to claim 5,
the glass cloth has an F content of more than 0.005 mass% and less than 0.1 mass%.
7. Glass cloth according to any one of claims 1 to 6,
the glass cloth is,
Si content in SiO2Converted into 40-60 mass%,
The content of B is as follows2O3Converted to 15 to 30 mass%.
8. Glass cloth according to claim 7,
the glass cloth is,
Al content is as Al2O310 to 20 mass% in terms of,
The Ca content is 4-12 mass% in terms of CaO,
The Mg content is 1 mass% or less in terms of MgO.
9. Glass cloth according to any one of claims 1 to 8,
the elastic coefficient of the glass cloth is 50-70 GPa.
10. Glass cloth according to claim 9,
the elastic coefficient of the glass cloth is 50-63 GPa.
11. Glass cloth according to any one of claims 1 to 10,
the average diameter of the glass filaments constituting the warp and the weft is 3.5 to 5.4 μm independently of each other.
12. Glass cloth according to any one of claims 1 to 11,
has a dielectric constant of 5.0 or less at a frequency of 1 GHz.
13. A prepreg, having:
a glass cloth according to any one of claims 1 to 12; and the combination of (a) and (b),
a matrix resin impregnated into the glass cloth.
14. A printed wiring board comprising the glass cloth according to any one of claims 1 to 12.
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CN115458212A (en) * 2022-09-15 2022-12-09 深圳市米韵科技有限公司 Insulating and voltage-resistant material for cable and preparation method thereof

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