TWI790691B - Glass cloth, prepreg, and printed circuit board - Google Patents
Glass cloth, prepreg, and printed circuit board Download PDFInfo
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- TWI790691B TWI790691B TW110126902A TW110126902A TWI790691B TW I790691 B TWI790691 B TW I790691B TW 110126902 A TW110126902 A TW 110126902A TW 110126902 A TW110126902 A TW 110126902A TW I790691 B TWI790691 B TW I790691B
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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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- 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
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- 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
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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
- 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
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- 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
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- 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
Abstract
本發明之目的在於提供一種強度降低受到抑制之低介電玻璃布、以及使用該低介電玻璃布之預浸體及印刷電路板。 本發明之玻璃布係將包含複數根玻璃絲之玻璃紗作為經紗及緯紗而構成者，且於下述式(1)中，作為380℃、2小時之加熱處理中源自玻璃成分之重量減少比率與上述玻璃絲之平均半徑的積而求出之重量減少係數為0.18以上0.45以下，上述玻璃布之Fe含量以Fe2 O3 換算計超過0.1質量%且未達0.4質量%。 重量減少係數＝上述重量減少比率(%)×上述玻璃絲之平均半徑(μm)・・・(1)An object of the present invention is to provide a low-dielectric glass cloth in which strength reduction is suppressed, and a prepreg and a printed circuit board using the low-dielectric glass cloth. The glass cloth of the present invention is composed of glass yarns including a plurality of glass filaments as warp and weft, and in the following formula (1), as the weight loss ratio derived from the glass component during heat treatment at 380°C for 2 hours The weight reduction coefficient obtained by the product of the average radius of the above-mentioned glass filaments is 0.18 to 0.45, and the Fe content of the above-mentioned glass cloth is more than 0.1% by mass and less than 0.4% by mass in terms of Fe2O3 . Weight reduction factor = the above weight reduction ratio (%) × the average radius of the above glass filament (μm)・・・(1)
Description
本發明係關於一種玻璃布、預浸體、及印刷電路板。 The invention relates to a glass cloth, a prepreg, and a printed circuit board.
隨著近年來資訊通信社會之發達，資料通信及/或信號處理開始大容量且高速地進行，電子機器中使用之印刷電路板之低介電常數化正顯著發展。因此，關於構成印刷電路板之玻璃布，亦提出有許多低介電玻璃布。 With the development of the information and communication society in recent years, data communication and/or signal processing has begun to be performed at a large capacity and at a high speed, and the reduction of the dielectric constant of printed circuit boards used in electronic equipment has been significantly developed. Therefore, many low-dielectric glass cloths have been proposed for glass cloths constituting printed circuit boards.
例如，專利文獻1中揭示之低介電玻璃布相對於自先前通常使用之E玻璃布，於玻璃組成中大量調配B2O3，同時調整SiO2等其他成分之調配量，藉此實現了低介電常數。 For example, in the low-dielectric glass cloth disclosed in Patent Document 1, a large amount of B 2 O 3 is blended in the glass composition, and the blending amount of other components such as SiO 2 is adjusted, thereby achieving Low dielectric constant.
[專利文獻1]日本專利特開平11-292567號公報 [Patent Document 1] Japanese Patent Laid-Open No. 11-292567
然而，若為了將玻璃布低介電常數化而增加玻璃紗中之B2O3含有比 率，則玻璃紗之彈性係數降低，進而，由於製造過程中實施之脫上漿劑處理等熱處理，玻璃布之強度顯著降低。因此，存在玻璃布容易斷裂之問題。於使用此種玻璃布製造預浸體之情形時，於如控制樹脂附著量之操作等對玻璃佈施加外在負載之情況下，玻璃布斷裂，而產生生產上之問題。 However, if the B 2 O 3 content ratio in the glass yarn is increased in order to lower the dielectric constant of the glass cloth, the elastic coefficient of the glass yarn will decrease, and further, due to heat treatment such as the sizing agent removal treatment performed in the manufacturing process, the glass The strength of the cloth is significantly reduced. Therefore, there is a problem that the glass cloth is easily broken. When such a glass cloth is used to manufacture a prepreg, when an external load is applied to the glass cloth, such as an operation to control the amount of resin adhesion, the glass cloth breaks, causing problems in production.
關於該方面，於專利文獻1中，揭示有如下方法，即於玻璃紗之紡絲時，將B2O3之含量設為未達20質量%，且將CaO之含量設為特定範圍，藉此抑制B2O3之揮發。然而，將B2O3之含量設為未達20質量%時，無法充分應對低介電常數化之要求，結果未實現低介電且強度降低受到抑制之玻璃布。進而，已知若因加熱處理造成之重量減少為特定範圍，則強度降低更加嚴重化。 In this regard, Patent Document 1 discloses a method in which the content of B 2 O 3 is less than 20% by mass and the content of CaO is in a specific range during spinning of glass yarn. This suppresses the volatilization of B2O3 . However, when the content of B 2 O 3 is less than 20% by mass, the demand for low dielectric constant cannot be sufficiently met, and as a result, a glass cloth with low dielectric constant and suppressed decrease in strength has not been realized. Furthermore, it is known that if the weight loss due to heat treatment falls within a specific range, the strength decrease will become more serious.
本發明係鑒於上述問題點而完成者，本發明之目的在於提供一種強度降低受到抑制之低介電玻璃布、以及使用該低介電玻璃布之預浸體及印刷電路板。 The present invention was made in view of the above-mentioned problems, and an object of the present invention is to provide a low-dielectric glass cloth in which strength reduction is suppressed, and a prepreg and a printed circuit board using the low-dielectric glass cloth.
本發明人等為了解決上述問題而進行了銳意研究，結果發現藉由於具有特定之重量減少傾向之玻璃布中調整Fe之含量，能夠解決上述問題，從而完成了本發明。 The inventors of the present invention conducted earnest research to solve the above-mentioned problems, and as a result, found that the above-mentioned problems can be solved by adjusting the content of Fe in glass cloth having a specific weight reduction tendency, and completed the present invention.
即，本發明如下所述。 That is, the present invention is as follows.
[1] [1]
一種玻璃布，其係將包含複數根玻璃絲之玻璃紗作為經紗及緯紗而構成者，且於下述式(1)中，作為380℃、2小時之加熱處理中源自玻璃成分之重量減少比率與上述玻璃絲之平均半徑的積而求出之重量減少係數為0.18以上0.45以下，重量減少係數=上述重量減少比率(%)×上述玻璃絲之平均半徑(μm)‧‧‧(1) A glass cloth comprising a glass yarn including a plurality of glass filaments as a warp and a weft, and in the following formula (1), as a weight loss ratio derived from a glass component during heat treatment at 380°C for 2 hours The weight reduction coefficient calculated by the product of the average radius of the above-mentioned glass filaments is 0.18 to 0.45, and the weight reduction coefficient = the above-mentioned weight reduction ratio (%) × the average radius of the above-mentioned glass filaments (μm)‧‧‧(1)
上述玻璃布之Fe含量以Fe2O3換算計超過0.1質量%且未達0.4質量%。 The Fe content of the said glass cloth exceeds 0.1 mass % and is less than 0.4 mass % in conversion of Fe2O3 .
[2] [2]
如[1]中記載之玻璃布，其中上述玻璃布之Fe含量以Fe2O3換算計超過0.2質量%且未達0.4質量%。 The glass cloth described in [1], wherein the Fe content of the glass cloth is more than 0.2% by mass and less than 0.4% by mass in terms of Fe 2 O 3 .
[3] [3]
如[2]中記載之玻璃布，其中上述玻璃布之Fe含量以Fe2O3換算計超過0.3質量%且未達0.4質量%。 The glass cloth described in [2], wherein the Fe content of the glass cloth is more than 0.3% by mass and less than 0.4% by mass in terms of Fe 2 O 3 .
[4] [4]
如[1]至[3]中任一項中記載之玻璃布，其中上述玻璃布之F含量超過0.005質量%且未達0.4質量%。 The glass cloth described in any one of [1] to [3], wherein the F content of the glass cloth is more than 0.005% by mass and less than 0.4% by mass.
[5] [5]
如[4]中記載之玻璃布，其中上述玻璃布之F含量超過0.005質量%且未達0.2質量%。 The glass cloth described in [4], wherein the F content of the glass cloth is more than 0.005% by mass and less than 0.2% by mass.
[6] [6]
如[5]中記載之玻璃布，其中上述玻璃布之F含量超過0.005質量%且 未達0.1質量%。 The glass cloth described in [5], wherein the F content of the glass cloth exceeds 0.005% by mass and Less than 0.1% by mass.
[7] [7]
如[1]至[6]中任一項中記載之玻璃布，其中上述玻璃布之Si含量以SiO2換算計為40~60質量%，B含量以B2O3換算計為15~30質量%。 The glass cloth described in any one of [1] to [6], wherein the glass cloth has a Si content of 40 to 60% by mass in terms of SiO 2 and a B content of 15 to 30 in terms of B 2 O 3 quality%.
[8] [8]
如[7]中記載之玻璃布，其中上述玻璃布之Al含量以Al2O3換算計為10~20質量%，Ca含量以CaO換算計為4~12質量%，Mg含量以MgO換算計為1質量%以下。 The glass cloth described in [7], wherein the above-mentioned glass cloth has an Al content of 10 to 20% by mass in terms of Al 2 O 3 , a Ca content of 4 to 12 mass% in terms of CaO, and a Mg content in terms of MgO 1% by mass or less.
[9] [9]
如[1]至[8]中任一項中記載之玻璃布，其中上述玻璃布之彈性係數為50~70GPa。 The glass cloth described in any one of [1] to [8], wherein the coefficient of elasticity of the glass cloth is 50 to 70 GPa.
[10] [10]
如[9]中記載之玻璃布，其中上述玻璃布之彈性係數為50~63GPa。 Such as the glass cloth described in [9], wherein the elastic coefficient of the glass cloth is 50~63GPa.
[11] [11]
如[1]至[10]中任一項中記載之玻璃布，其中構成上述經紗及上述緯紗之上述玻璃絲之平均直徑各自獨立地為3.5~5.4μm。 The glass cloth according to any one of [1] to [10], wherein the average diameters of the glass filaments constituting the warp and the weft are each independently 3.5 to 5.4 μm.
[12] [12]
如[1]至[11]中任一項中記載之玻璃布，其於1GHz之頻率下具有5.0以下之介電常數。 The glass cloth described in any one of [1] to [11], which has a dielectric constant of 5.0 or less at a frequency of 1 GHz.
[13] [13]
一種預浸體，其具有：如[1]至[12]中任一項中記載之玻璃布；及該玻璃布中含浸之基質樹脂。 A prepreg comprising: the glass cloth described in any one of [1] to [12]; and a matrix resin impregnated in the glass cloth.
[14] [14]
一種印刷電路板，其具備如[1]至[12]中任一項中記載之玻璃布。 A printed circuit board comprising the glass cloth described in any one of [1] to [12].
根據本發明，能夠提供一種強度降低受到抑制之低介電玻璃布、以及使用該低介電玻璃布之預浸體及印刷電路板。 According to the present invention, it is possible to provide a low-dielectric glass cloth in which a decrease in strength is suppressed, and a prepreg and a printed wiring board using the same.
以下，詳細地對本發明之實施形態(以下，稱作「本實施形態」)進行說明，但本發明並不限定於此，可於不脫離其主旨之範圍內進行各種變化。 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 changes can be made without departing from the gist.
本實施形態之玻璃布係將包含複數根玻璃絲之玻璃紗作為經紗及緯紗而構成者，且於下述式(1)中，作為380℃、2小時之加熱處理中源自玻璃成分之重量減少比率與玻璃絲之平均半徑的積而求出之重量減少係數為 0.18以上0.45以下，玻璃布之Fe含量以Fe2O3換算計超過0.1質量%且未達0.4質量%。 The glass cloth of this embodiment is composed of glass yarns including a plurality of glass filaments as warp and weft, and in the following formula (1), as the weight loss derived from the glass component during heat treatment at 380°C for 2 hours The weight reduction coefficient obtained by the product of the ratio and the average radius of the glass filament is 0.18 to 0.45, and the Fe content of the glass cloth exceeds 0.1% by mass and is less than 0.4% by mass in terms of Fe 2 O 3 .
重量減少係數=重量減少比率(%)×玻璃絲之平均半徑(μm)‧‧‧(1) Weight reduction factor = weight reduction ratio (%) × average radius of glass filament (μm)‧‧‧(1)
具有低介電常數之玻璃布於其製造過程中之熱處理或者其後續步驟中之熱處理中，玻璃紗之強度降低。由於該強度降低、及構成低介電玻璃布之玻璃紗之彈性係數較低，與E玻璃等使用其他玻璃紗者相比，低介電玻璃布成為容易產生斷裂者。相對於此，於本實施形態中，藉由於具有特定之重量減少傾向之玻璃布中，調整玻璃中之Fe(鐵)之含量、進而較佳為F(氟)之含量，來抑制因熱處理造成之強度降低。 In the heat treatment of the glass cloth having a low dielectric constant during its manufacturing process or the heat treatment in its subsequent step, the strength of the glass yarn decreases. Due to the decrease in strength and the low modulus of elasticity of the glass yarn constituting the low-dielectric glass cloth, the low-dielectric glass cloth is more likely to break than those using other glass yarns such as E glass. On the other hand, in the present embodiment, by adjusting the content of Fe (iron) in the glass, preferably the content of F (fluorine), in the glass cloth having a specific weight reduction tendency, the damage caused by heat treatment is suppressed. The strength is reduced.
作為能夠藉由該Fe含量之調整來抑制強度降低之理由，並無限定，但有如下觀點。於紡絲時，即便於高溫條件下玻璃成分揮發而於玻璃紗產生稀疏部分，熔融狀態之玻璃亦可流動而填埋該部分，由於伴隨重量減少之玻璃成分之揮發而使玻璃紗變得稀疏之部分能夠藉由該流動而消除。另一方面，構成玻璃布之玻璃紗即便由於玻璃成分之揮發而產生稀疏部分，玻璃亦無法流動而填埋該部分。於該狀況下，於本實施形態之玻璃布中，Fe對於由於玻璃成分之揮發而使玻璃紗變得稀疏之部分可能發揮維繫作用。 The reason why the reduction in strength can be suppressed by the adjustment of the Fe content is not limited, but there are the following points of view. During spinning, even if the glass component volatilizes under high temperature conditions to produce a sparse part in the glass yarn, the glass in the molten state can flow and fill this part, and the glass yarn becomes sparse due to the volatilization of the glass component accompanied by weight reduction Parts can be eliminated by this flow. On the other hand, even if the glass yarn constituting the glass cloth has a sparse part due to the volatilization of the glass component, the glass cannot flow and fills the part. In this situation, in the glass cloth of the present embodiment, Fe may play a role of maintaining the part where the glass yarn becomes sparse due to the volatilization of the glass component.
又，作為能夠藉由F含量之調整來進一步抑制強度降低之理由，並無限定，但有如下觀點。F使玻璃製造過程之熔融玻璃之黏性減小。因此，藉由F含量為特定範圍，於Fe等金屬成分被納入玻璃結構時，會均勻地分 散而不會局部化，從而能夠形成均勻之玻璃。認為藉由Fe均勻分散，能夠更有效地表現出上述Fe對於由於玻璃成分之揮發而使玻璃紗變得稀疏之部分的維繫作用。又，認為若由於Fe等局部化而於玻璃中偏集存在較硬之部分，則容易以該部分為起點產生斷裂，但認為藉由調整F含量來緩和此種局部化，能夠進一步抑制強度降低。 In addition, there is no limitation as to the reason why the reduction in strength can be further suppressed by adjusting the F content, but there are the following viewpoints. F reduces the viscosity of molten glass in the glass manufacturing process. Therefore, when the F content is in a specific range, when metal components such as Fe are incorporated into the glass structure, they will be uniformly distributed. Scatter without localization, so that a uniform glass can be formed. It is considered that by uniformly dispersing Fe, it is possible to express more effectively the maintenance effect of Fe on the part where the glass yarn becomes sparse due to the volatilization of the glass components. In addition, it is considered that if a relatively hard part is concentrated in the glass due to localization of Fe, etc., fractures will easily occur starting from this part, but it is considered that by adjusting the F content to alleviate this localization, it is possible to further suppress the decrease in strength. .
藉由具有上述構成，於本實施形態中，能夠解決低介電玻璃布所具有之斷裂之問題，並提供一種具有較高之抗斷裂性及較低之介電常數的玻璃布。以下，更詳細地對本實施形態之構成進行說明。 With the above structure, in this embodiment, the problem of breakage of low-dielectric glass cloth can be solved, and a glass cloth with higher break resistance and lower dielectric constant can be provided. Hereinafter, the configuration of this embodiment will be described in more detail.
作為對玻璃布進行380℃、2小時之加熱處理時源自玻璃成分之重量減少比率與玻璃絲之平均半徑的積而求出之重量減少係數(以下，亦簡稱為「重量減少係數」)為0.18以上0.45以下，較佳為0.19以上0.42以下，更佳為0.20以上0.39以下，進而較佳為0.20以上0.35以下。 The weight reduction coefficient obtained as the product of the weight reduction ratio derived from the glass component and the average radius of the glass filament when the glass cloth is heat-treated at 380°C for 2 hours (hereinafter also referred to as "weight reduction coefficient") is 0.18 More than 0.45, preferably 0.19 to 0.42, more preferably 0.20 to 0.39, still more preferably 0.20 to 0.35.
「源自玻璃成分之重量減少比率」係指進行380℃、2小時之加熱處理時的重量減少比率起因於在加熱處理中由於玻璃成分之揮發等而消失。如下所述，於玻璃布上附著有矽烷偶合劑等表面處理劑之情形時或附著有大量有機系雜質之情形時，本實施形態之重量減少比率係預先用醇類或丙酮等良溶劑去除物理吸附的矽烷偶合劑等表面處理劑或有機系雜質附著成分後算出。因此，去除此種於380℃下加熱分解之附著成分後的玻璃布之加熱處理後之重量減少比率成為源自玻璃成分之減少比率。 The "weight loss ratio derived from the glass component" refers to the weight loss ratio when heat treatment at 380°C for 2 hours is caused by the volatilization of the glass component during the heat treatment. As described below, when a surface treatment agent such as a silane coupling agent is attached to the glass cloth or when a large amount of organic impurities are attached, the weight reduction ratio of this embodiment is based on the removal of the physical substance with a good solvent such as alcohol or acetone in advance. Calculated after adsorbed surface treatment agents such as silane coupling agents or organic impurities. Therefore, the weight reduction ratio after the heat treatment of the glass cloth after removing such an adhering component decomposed by heating at 380° C. becomes a reduction ratio derived from the glass component.
又，確認到該重量減少比率取決於玻璃紗之絲直徑。重量減少比率因玻璃絲直徑而異，絲直徑越小，重量減少量越大。另一方面，重量減少比率與絲半徑之積不受絲直徑之影響，大致為固定值。因此，於本實施形態中，作為重量減少係數，以絲直徑進行標準化。 Also, it was confirmed that the weight reduction rate depends on the diameter of the glass yarn. The weight reduction ratio varies with the diameter of the glass filament, the smaller the filament diameter, the greater the weight reduction. On the other hand, the product of the weight reduction ratio and the wire radius is not affected by the wire diameter, and is approximately a constant value. Therefore, in the present embodiment, the filament diameter is standardized as the weight reduction coefficient.
由於重量減少係數為0.18以上，若保持此狀態則容易引起強度降低。然而，藉由調整下述Fe含量，進而作為較佳樣態亦調整F含量，於本實施形態中，能夠抑制強度降低，又，根據構成玻璃布之組成之關係，亦能夠獲得具有更低介電常數之玻璃布。又，藉由重量減少係數為0.45以下，由Fe帶來之強度降低抑制效果得到有效發揮，能夠抑制顯著之強度降低。 Since the weight reduction coefficient is 0.18 or more, if this state is maintained, the strength will easily decrease. However, by adjusting the Fe content described below, and further adjusting the F content as a preferred mode, in the present embodiment, it is possible to suppress the decrease in strength, and, depending on the relationship between the composition of the glass cloth, it is also possible to obtain a glass cloth with a lower dielectric strength. Electrical constant glass cloth. In addition, when the weight reduction coefficient is 0.45 or less, the effect of suppressing strength reduction due to Fe is effectively exhibited, and significant strength reduction can be suppressed.
重量減少比率之測定方法可按以下順序進行。首先，將玻璃布放入105℃±5℃之乾燥機中乾燥60分鐘，然後，將玻璃布移至乾燥器中，放置冷卻直至室溫為止。放置冷卻後，以0.1mg以下之單位稱量玻璃布之重量(玻璃布重量a)。繼而，將玻璃布於380℃下加熱2小時，然後，將玻璃布移至乾燥器中，放置冷卻直至室溫為止。放置冷卻後，以0.1mg以下之單位稱量玻璃布之重量(加熱處理後之玻璃布重量b)。繼而，求出由於加熱處理而減少之重量，利用下述式(2)算出重量減少比率(%)。 The method for measuring the weight loss ratio can be performed in the following order. First, put the glass cloth in a drier at 105°C±5°C to dry for 60 minutes, then move the glass cloth to the drier, let it cool down until room temperature. After standing to cool, measure the weight of the glass cloth (glass cloth weight a) in units of 0.1 mg or less. Next, the glass cloth was heated at 380° C. for 2 hours, then the glass cloth was moved to a desiccator, and left to cool until room temperature. After standing to cool, measure the weight of the glass cloth in units of 0.1 mg or less (the weight of the glass cloth after heat treatment b). Next, the weight decreased by the heat treatment was obtained, and the weight reduction ratio (%) was calculated by the following formula (2).
重量減少比率(%)=(a-b)/a×100‧‧‧(2) Weight reduction ratio (%)=(a-b)/a×100‧‧‧(2)
以上述方式獲得之重量減少比率較佳為0.04~0.5%，更佳為0.05~ 0.3%，進而較佳為0.06~0.25%。由於重量減少比率為0.04%以上，若保持此狀態則容易引起強度降低。然而，藉由調整下述Fe含量，進而作為較佳樣態亦調整F含量，於本實施形態中，能夠抑制強度降低，又，根據構成玻璃布之組成之關係，亦能夠獲得具有更低介電常數之玻璃布。又，藉由重量減少比率為0.5%以下，由Fe帶來之強度降低抑制效果得到有效發揮，能夠抑制顯著之強度降低。 The weight reduction ratio obtained in the above manner is preferably 0.04~0.5%, more preferably 0.05~ 0.3%, more preferably 0.06~0.25%. Since the weight loss ratio is 0.04% or more, if it remains in this state, it will easily cause a decrease in strength. However, by adjusting the Fe content described below, and further adjusting the F content as a preferred mode, in the present embodiment, it is possible to suppress the decrease in strength, and, depending on the relationship between the composition of the glass cloth, it is also possible to obtain a glass cloth with a lower dielectric strength. Electrical constant glass cloth. In addition, when the weight reduction rate is 0.5% or less, the effect of suppressing strength reduction due to Fe is effectively exhibited, and a remarkable strength reduction can be suppressed.
繼而，依據JIS R3420測定構成玻璃布之玻璃紗之玻璃絲之平均直徑，求出作為該絲直徑之一半量之平均絲半徑。於本實施形態中，簡稱為玻璃絲時，係指玻璃單絲。又，用於計算重量減少係數的玻璃絲之平均半徑係加熱處理前之平均半徑。以此方式求出之玻璃絲之平均半徑較佳為1.25~4.5μm，更佳為1.5~3.75μm，進而較佳為1.75~2.7μm。 Next, the average diameter of the glass filaments constituting the glass yarn of the glass cloth was measured in accordance with JIS R3420, and the average filament radius which was a half of the filament diameter was obtained. In the present embodiment, when simply referred to as glass filaments, it refers to glass monofilaments. In addition, the average radius of glass filaments used for calculating the weight reduction factor is the average radius before heat treatment. The average radius of the glass filaments obtained in this way is preferably 1.25 to 4.5 μm, more preferably 1.5 to 3.75 μm, and still more preferably 1.75 to 2.7 μm.
再者，能夠對上述重量減少比率之測定方法中使用之玻璃布進行適當預處理。例如，自脫糊處理(熱清洗(heat cleaning))後之中間捲拉出之玻璃布中，玻璃絲上未附著附著物，因此，能夠直接用於上述重量減少比率之測定方法。 In addition, the glass cloth used for the measuring method of the said weight loss ratio can be pretreated suitably. For example, in the glass cloth pulled out from the intermediate roll after the depaste treatment (heat cleaning), there is no adhering material on the glass filament, so it can be directly used in the measurement method of the above-mentioned weight loss ratio.
另一方面，將玻璃布上塗佈有矽烷偶合劑等表面處理劑之玻璃布作為對象來求出重量減少比率時，可預先用醇類、丙酮等良溶劑洗淨去除物理吸附之矽烷偶合劑等表面處理劑後，藉由上述方法求出重量減少係數。 On the other hand, when the glass cloth coated with a surface treatment agent such as a silane coupling agent is used as the object to obtain the weight loss ratio, it can be washed with a good solvent such as alcohol or acetone in advance to remove the physically adsorbed silane coupling agent. After waiting for the surface treatment agent, the weight reduction coefficient was obtained by the above-mentioned method.
再者，「物理吸附之矽烷偶合劑」係指附著在玻璃絲上之矽烷偶合 劑，並非藉由化學鍵與玻璃絲鍵結之矽烷偶合劑。相對於此，將藉由化學鍵與玻璃絲鍵結之矽烷偶合劑稱為「化學吸附之矽烷偶合劑」。 Furthermore, "physisorbed silane coupling agent" refers to the silane coupling agent attached to the glass filament. It is not a silane coupling agent bonded to glass filaments by chemical bonds. On the other hand, a silane coupling agent bonded to glass filaments by a chemical bond is called a "chemisorbed silane coupling agent".
又，於玻璃布中包含有機系雜質(玻璃紗製造過程中塗佈之澱粉系上漿劑、前期之上漿劑於熱清洗步驟中之燃燒殘留物等)之情形時，亦可同樣地預先藉由醇類、丙酮等之洗淨去除操作去除玻璃布上附著之有機系雜質後，藉由上述方法求出重量減少係數。 In addition, when the glass cloth contains organic impurities (starch-based sizing agent applied during the glass yarn manufacturing process, combustion residue of the previous sizing agent in the thermal cleaning step, etc.), it can also be pre-treated in the same way. After removing the organic impurities adhering to the glass cloth by cleaning and removing with alcohols, acetone, etc., the weight reduction factor was obtained by the above method.
上述洗淨係去除物理吸附之矽烷偶合劑或有機系雜質，並非去除化學吸附之矽烷偶合劑。然而，即便於380℃下加熱2小時，化學吸附之矽烷偶合劑亦不會分解，或者即便一部分分解亦不會超出誤差範圍，因此，於本實施形態之重量減少比率之測定中，無需藉由預處理去除化學吸附之矽烷偶合劑。 The above cleaning is to remove physically adsorbed silane coupling agents or organic impurities, not chemically adsorbed silane coupling agents. However, even if it is heated at 380°C for 2 hours, the chemically adsorbed silane coupling agent will not decompose, or even partially decompose, it will not exceed the error range. Pretreatment to remove chemisorbed silane coupling agents.
再者，基於簡化是否進行預處理之判斷之觀點而言，亦可一律使用預先利用醇類、丙酮等良溶劑洗淨之玻璃布來進行重量減少比率之測定。藉此，無論是自脫糊處理(熱清洗)後之中間捲拉出之玻璃布，抑或是附著有物理吸附之矽烷偶合劑或有機系雜質之玻璃布，均能夠以相同狀態進行重量減少比率之測定。 Furthermore, from the standpoint of simplifying the judgment of whether to perform pretreatment, it is also possible to uniformly use glass cloth washed in advance with good solvents such as alcohols and acetone to measure the weight loss ratio. In this way, whether it is the glass cloth pulled out from the middle roll after the depaste treatment (heat cleaning), or the glass cloth with the physically adsorbed silane coupling agent or organic impurities attached, the weight reduction rate can be achieved in the same state The determination.
又，作為其他方法，亦可於求出上述重量減少係數時，對加熱前後之表面處理劑量或有機系雜質進行定量，自所獲得之重量減少中減去起因於表面處理劑之重量減少量，藉此求出源自玻璃成分之重量減少係數。作 為求出起因於表面處理劑之重量減少量之方法，亦可使用日本專利6472082號公報等中記載之矽烷偶合劑之定量方法等公知方法。 In addition, as another method, when obtaining the above-mentioned weight loss coefficient, the amount of surface treatment or organic impurities before and after heating can be quantified, and the weight loss caused by the surface treatment agent can be subtracted from the obtained weight loss. From this, the weight reduction coefficient derived from the glass component was obtained. do For the method of determining the amount of weight loss caused by the surface treatment agent, known methods such as the quantitative method of the silane coupling agent described in Japanese Patent No. 6472082 and the like can also be used.
重量減少係數可藉由玻璃布之組成中之例如相對容易揮發之成分、例如B含量等之增減來進行調整，根據相同之觀點，亦可藉由其他成分之增減來進行調整。 The weight reduction coefficient can be adjusted by the increase or decrease of relatively volatile components in the composition of the glass cloth, such as B content, etc. From the same point of view, it can also be adjusted by the increase or decrease of other components.
又，重量減少係數亦可藉由玻璃布中之玻璃之空間填充率之調整(織密度或厚度)、利用開纖加工等進行之構成玻璃紗束之單絲之解離情況之調整、使用之玻璃紗之單絲徑之調整等來進行調整，亦可藉由玻璃表面暴露於高溫氣體氛圍之機會之增減來進行調整。 In addition, the weight reduction factor can also be adjusted by adjusting the space filling rate of the glass in the glass cloth (weaving density or thickness), adjusting the dissociation of the monofilaments constituting the glass yarn bundle by fiber opening processing, etc., and the glass used. Adjustment can be made by adjusting the single-filament diameter of the yarn, etc., or by increasing or decreasing the chance of the glass surface being exposed to a high-temperature gas atmosphere.
即，重量減少係數並非僅由玻璃布之組成決定者。 That is, the weight reduction coefficient is not determined only by the composition of the glass cloth.
以下，對本實施形態之玻璃布之組成進行說明。再者，玻璃布之組成與構成玻璃布之玻璃紗之組成同義。於本實施形態之玻璃布之組成中，Fe含量以Fe2O3換算計超過0.1質量%且未達0.4質量%，較佳為超過0.2質量%且未達0.4質量%，更佳為超過0.3質量%且未達0.4質量%，最佳範圍係超過0.3質量%且為0.38質量%以下。藉由Fe含量超過0.1質量%，能夠抑制玻璃布之因熱處理造成之強度降低。又，藉由Fe含量未達0.4質量%，能夠抑制由於Fe含量過多反而使熱處理前之玻璃布本身之強度降低的情況。Fe含量可根據用於玻璃絲製作之原料使用量或者於玻璃絲製作中精製去除或追加來進行調整。 Hereinafter, the composition of the glass cloth of this embodiment is demonstrated. In addition, the composition of glass cloth is synonymous with the composition of the glass yarn which comprises glass cloth. In the composition of the glass cloth of this embodiment, the Fe content is more than 0.1% by mass and less than 0.4% by mass in terms of Fe2O3 , preferably more than 0.2% by mass and less than 0.4% by mass, more preferably more than 0.3% by mass. % by mass and less than 0.4% by mass, the optimum range is more than 0.3% by mass and 0.38% by mass or less. When the Fe content exceeds 0.1% by mass, it is possible to suppress a reduction in the strength of the glass cloth due to heat treatment. Moreover, since Fe content is less than 0.4 mass %, it can suppress that the intensity|strength of the glass cloth itself before heat processing falls by Fe content too much. The content of Fe can be adjusted according to the amount of raw materials used in the production of glass wool or by refining removal or addition in the production of glass wool.
再者，因Fe含量過多造成之強度降低並無特別限制，但有如下觀點。可認為玻璃紗基本上由非晶質之部分構成，但Fe存在之部分係結晶性相對較高之部分。認為根據結晶性較高之部分之存在方式，局部強度較弱之部分會變得明顯，但於本實施形態中，藉由將Fe含量調整為一定量以下，能夠抑制玻璃布之強度降低。 In addition, there is no particular limitation on the decrease in strength due to excessive Fe content, but there are the following points of view. It can be considered that the glass yarn is basically composed of amorphous parts, but the part where Fe exists is a part with relatively high crystallinity. It is considered that depending on the presence of the highly crystalline portion, the locally weak portion becomes conspicuous, but in this embodiment, by adjusting the Fe content to a certain amount or less, it is possible to suppress the decrease in the strength of the glass cloth.
又，本實施形態之玻璃布之組成中之F含量較佳為超過0.005質量%且未達0.4質量%，更佳為超過0.005質量%且未達0.2質量%，進而較佳為超過0.005質量%且未達0.1質量%。藉由F含量超過0.005質量%，存在玻璃布之因熱處理造成之強度降低進而受到抑制之傾向。又，藉由F含量未達0.4質量%，能夠抑制由於F含量過多反而使熱處理前之玻璃布本身之強度降低之情況。F含量能夠根據用於玻璃絲製作之原料使用量來進行調整。 In addition, the F content in the composition of the glass cloth of this 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 more preferably more than 0.005 mass % And it is less than 0.1% by mass. When the F content exceeds 0.005% by mass, there is a tendency for the strength of the glass cloth to be reduced by heat treatment to be suppressed. Moreover, since F content is less than 0.4 mass %, it can suppress that the intensity|strength of the glass cloth itself before heat processing falls by the fact that F content is too much. The F content can be adjusted according to the amount of raw materials used for glass fiber production.
再者，因F含量過多造成之強度降低並無特別限制，但有如下觀點。認為F含量越多，則玻璃組成之分相性越強，反而難以使玻璃成分均勻。 Furthermore, there is no particular limitation on the reduction in strength due to an excessive F content, but the following viewpoints are considered. It is considered that the greater the F content, the stronger the phase separation of the glass composition, and it is conversely difficult to make the glass composition uniform.
於本實施形態之較佳態樣中，藉由將Fe含量及F含量均設為上述特定範圍，存在因熱處理造成之強度降低之抑制效果進一步提昇之傾向。 In a preferred aspect of this embodiment, there exists a tendency for the suppression effect of the intensity|strength reduction by heat processing to improve further by making Fe content and F content into the said specific range.
玻璃布之Si含量以SiO2換算計，較佳為40~60質量%，更佳為45~55質量%，進而較佳為47~53質量%，進而更佳為48~52質量%。Si係形 成玻璃紗之骨架結構之成分，藉由Si含量為40質量%以上，除了抑制因熱處理造成之強度降低以外，熱處理前之玻璃紗本身之強度進一步提昇，於玻璃布之製造步驟及使用玻璃布之預浸體之製造等後續步驟中，存在玻璃布之斷裂進而受到抑制之傾向。又，藉由Si含量為40質量%以上，存在玻璃布之介電常數進一步降低之傾向。另一方面，藉由Si含量為60質量%以下，於玻璃絲之製造過程中，熔融時之黏度進一步降低，存在獲得更均質之玻璃組成之玻璃纖維之傾向。因此，由於於所獲得之玻璃絲產生局部容易失透之部位或局部氣泡不易逸出之部位困難，故不易於玻璃絲產生局部強度較弱之部位，結果包含使用該玻璃絲所得之玻璃紗之玻璃布成為不易斷裂者。Si含量能夠根據用於玻璃絲製作之原料使用量來進行調整。 The Si content of the glass cloth is, in terms of SiO 2 , preferably 40-60 mass%, more preferably 45-55 mass%, further preferably 47-53 mass%, further preferably 48-52 mass%. Si is a component that forms the skeleton structure of the glass yarn. With a Si content of 40% by mass or more, in addition to suppressing the reduction in strength caused by heat treatment, the strength of the glass yarn itself before heat treatment is further improved. It is used in the manufacturing steps and use of glass cloth. In subsequent steps such as production of a glass cloth prepreg, there is a tendency for the glass cloth to be broken and suppressed. Moreover, there exists a tendency for the dielectric constant of glass cloth to fall further because Si content is 40 mass % or more. On the other hand, when the Si content is 60% by mass or less, the viscosity at the time of melting is further lowered in the production process of glass filaments, and there is a tendency to obtain glass fibers with a more homogeneous glass composition. Therefore, since it is difficult to generate a local portion easily devitrified or a portion where local air bubbles are not easy to escape in the obtained glass filament, it is not easy to generate a locally weaker portion of the glass filament. As a result, the glass cloth comprising the glass yarn obtained by using the glass filament becomes Those who are not easy to break. The Si content can be adjusted according to the amount of raw materials used for glass fiber production.
玻璃布之B含量以B2O3換算計，較佳為15~30質量%，更佳為17~28質量%，進而較佳為20~27質量%，進而更佳為21~25質量%，進而更佳為21.5~24質量%。藉由B含量為15質量%以上，存在介電常數進一步降低之傾向。藉由B含量為30質量%以下，玻璃布之強度較強，耐吸濕性亦優異，故而較佳。又，藉由B含量為30質量%以下，可將由脫上漿劑處理等加熱處理引起之玻璃成分之揮發量抑制地較小，因此，能夠抑制強度降低，而且耐吸濕性之降低亦得到抑制，存在絕緣可靠性進一步提昇之傾向。B含量能夠根據用於玻璃絲製作之原料使用量來進行調整。再者，於在玻璃絲製作中可能發生變動之情形時，可預先預料該情況而調整饋入量。 The B content of the glass cloth is calculated as B2O3 , preferably 15-30% by mass, more preferably 17-28% by mass , more preferably 20-27% by mass, even more preferably 21-25% by mass , and more preferably 21.5 to 24% by mass. When the B content is 15 mass % or more, there exists a tendency for a dielectric constant to fall further. When the B content is 30% by mass or less, the strength of the glass cloth is strong and the moisture absorption resistance is also excellent, so it is preferable. In addition, when the B content is 30% by mass or less, the volatilization of glass components caused by heat treatment such as sizing agent removal treatment can be suppressed to a small extent, so that the reduction in strength can be suppressed, and the reduction in moisture absorption resistance can also be suppressed. , there is a tendency to further improve insulation reliability. The content of B can be adjusted according to the amount of raw materials used for glass fiber production. Furthermore, when there may be fluctuations in the production of glass strands, the feeding amount can be adjusted in anticipation of the situation.
又，玻璃布除了上述組成以外，亦可具有其他組成。作為其他組 成，並無特別限定，例如可例舉Al、Ca、Mg、P、Na、K、Ti、Zn等。 Moreover, glass cloth may have other compositions other than the said composition. as other group It does not specifically limit, For example, Al, Ca, Mg, P, Na, K, Ti, Zn etc. are mentioned.
玻璃布之Al含量以Al2O3換算計，較佳為10~20質量%，更佳為11~18質量%，進而較佳為12~17質量%。藉由Al含量為上述範圍內，存在電氣特性、強度進一步提昇之傾向。Al含量能夠根據用於玻璃絲製作之原料使用量來進行調整。 The Al content of the glass cloth is, in terms of Al 2 O 3 , preferably 10 to 20% by mass, more preferably 11 to 18% by mass, further preferably 12 to 17% by mass. When the Al content is within the above range, electrical characteristics and strength tend to be further improved. The Al content can be adjusted according to the amount of raw materials used for glass fiber production.
玻璃布之Ca含量以CaO換算計，較佳為4.0~12質量%，較佳為5.7~10質量%，更佳為6.0~9.0質量%。藉由Ca含量為4.0質量%以上，於玻璃絲之製造過程中，熔融時之黏度進一步降低，存在獲得更均質之玻璃組成之玻璃纖維之傾向。又，藉由Ca含量為10質量%以下，存在介電常數進一步提昇之傾向。Ca含量能夠根據用於玻璃絲製作之原料使用量來進行調整。 The Ca content of the glass cloth is, in terms of CaO, preferably 4.0 to 12% by mass, more preferably 5.7 to 10% by mass, more preferably 6.0 to 9.0% by mass. When the Ca content is 4.0% by mass or more, the viscosity at the time of melting is further lowered in the production process of glass filaments, and there is a tendency to obtain glass fibers with a more homogeneous glass composition. In addition, when the Ca content is 10% by 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 glass fiber production.
玻璃布之Mg含量以MgO換算計，較佳為1.0質量%以下，更佳為0.7質量%以下，進而較佳為0.01質量%以上0.7質量%以下，進而更佳為0.05質量%以上0.6質量%以下，進而更佳為0.05質量%以上0.45質量%以下。藉由Mg含量為5質量%以下，於玻璃布製造時之開纖步驟或表面處理步驟等中，於玻璃布在濕潤狀態下通過擠壓輥或夾輥等時，存在不易產生斷裂之傾向。又，玻璃絲製造時之相分離受到抑制，所獲得之玻璃絲之耐吸濕性進一步提昇。藉此，所獲得之印刷電路板不易受到高濕度環境之使用環境之影響，能夠降低介電常數之環境依賴性。Mg含量能夠根據用於玻璃絲製作之原料使用量來進行調整。 The Mg content of the glass cloth is, in terms of MgO, preferably at most 1.0% by mass, more preferably at most 0.7% by mass, more preferably at least 0.01% by mass and at most 0.7% by mass, still more preferably at least 0.05% by mass and 0.6% by mass or less, and more preferably not less than 0.05% by mass and not more than 0.45% by mass. When the Mg content is 5% by mass or less, breakage tends to be less likely to occur when the glass cloth passes through squeeze rolls or nip rolls in a wet state during the fiber opening step or surface treatment step during glass cloth production. In addition, phase separation during the production of glass filaments is suppressed, and the moisture absorption resistance of the obtained glass filaments is further improved. Thereby, the obtained printed circuit board is not easily affected by the 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 for glass fiber production.
Ca含量相對於Mg含量之比較佳為5.0~50，更佳為10~45，進而較佳為15~40，進而更佳為20~35，進而更佳為20~30。藉由Ca含量相對於Mg含量之比處於上述範圍內，可獲得更均質故而強度較強、耐吸濕性亦優異之玻璃纖維，有不易產生斷裂且介電常數之環境依賴性降低之傾向。 The ratio of the Ca content to the Mg content is preferably 5.0-50, more preferably 10-45, still more preferably 15-40, still more preferably 20-35, still more preferably 20-30. When the ratio of the Ca content to the Mg content is within the above range, glass fibers that are more homogeneous, stronger in strength, and excellent in moisture absorption resistance are obtained, tend to be less prone to breakage, and have a lower environmental dependence of the dielectric constant.
再者，上述各含量可藉由ICP(inductively coupled plasma，感應耦合電漿)發射光譜分析法進行測定。具體而言，關於Si含量及B含量，可將稱取之玻璃布樣品利用氫氧化鈉加壓分解後，利用稀硝酸溶解後進行過濾，繼而，將不溶解成分利用碳酸鈉熔解後，合併濾液並定容，藉由ICP發射光譜分析法對所獲得之樣品進行測定而獲得。 Furthermore, the above contents can be measured by ICP (inductively coupled plasma, inductively coupled plasma) emission spectrometry. Specifically, regarding the Si content and B content, the weighed glass cloth sample can be decomposed under pressure with sodium hydroxide, dissolved in dilute nitric acid, and then filtered, and then the insoluble components are dissolved in sodium carbonate, and the filtrates are combined And constant volume, obtained by measuring the obtained sample by ICP emission spectrometry.
關於Fe含量、Al含量、Ca含量、Ma含量，可將稱取之玻璃布樣品利用過氯酸、硝酸、鹽酸及氟化氫加熱分解後，利用稀王水加熱溶解後進行過濾分離，將濾液定容，繼而，將不溶解成分利用硫酸、硝酸、鹽酸及氟化氫加熱分解後定溶，藉由ICP發射光譜分析法對所獲得之樣品進行測定而獲得。再者，作為ICP發射光譜分析裝置，可使用Hitachi High-Tech Science公司製造之PS3520VDD II。 Regarding the Fe content, Al content, Ca content, and Ma content, the weighed glass cloth sample can be heated and decomposed with perchloric acid, nitric acid, hydrochloric acid, and hydrogen fluoride, then heated and dissolved with dilute aqua regia, then filtered and separated, and the filtrate constant volume , and then, the insoluble components are heated and decomposed by sulfuric acid, nitric acid, hydrochloric acid and hydrogen fluoride, and then dissolved, and the obtained samples are measured by ICP emission spectrometry. In addition, as an ICP emission spectrometer, PS3520VDD II manufactured by Hitachi High-Tech Science Co., Ltd. can be used.
又，關於F含量，可將稱取之玻璃布樣品於管狀電爐中進行燃燒後，將產生之氣體吸收至吸收液中。針對該溶液，用離子層析儀測定氟化物離子(F-)，而求出試樣中之含量。再者，燃燒裝置可使用Mitsubishi Chemical Analytech製造之自動試樣燃燒裝置(AQF-2100S)，測定裝置可使用Thermo Fisher Scientific製造之離子層析儀ICS-1500。 Also, regarding the F content, the weighed glass cloth sample can be burned in a tubular electric furnace, and the gas generated can be absorbed into the absorbing liquid. Fluoride ions (F - ) were measured for this solution with an ion chromatograph to obtain the content in the sample. Furthermore, an automatic sample combustion device (AQF-2100S) manufactured by Mitsubishi Chemical Analytech can be used for the combustion device, and an ion chromatograph ICS-1500 manufactured by Thermo Fisher Scientific can be used for the measurement device.
玻璃布之彈性係數較佳為50~70GPa，更佳為50~63GPa，進而較佳為53~63GPa。玻璃布之彈性係數越低，則越容易產生斷裂。因此，藉由彈性係數為50GPa以上，於開纖步驟或表面處理步驟等玻璃布之製造步驟中，於玻璃布在濕潤狀態下通過擠壓輥或夾輥等時，存在不易產生斷裂之傾向。又，於預浸體之製造等後續步驟中，於因控制樹脂向玻璃布中之含浸量之目的而使玻璃布通過狹縫時，亦存在不易產生斷裂之傾向。藉由玻璃佈線之彈性模數為70GPa以下，玻璃布之質地變得柔軟，於玻璃布通過擠壓輥或夾輥等較窄之間隔時，存在不易產生斷裂之傾向。又，藉由玻璃布之彈性係數為70GPa以下，存在介電常數進一步相對降低之傾向。彈性係數可藉由實施例中記載之方法進行測定。又，彈性係數可利用玻璃紗之組成來進行調整。 The elastic coefficient of the glass cloth is preferably 50-70 GPa, more preferably 50-63 GPa, and still more preferably 53-63 GPa. The lower the modulus of elasticity of the glass cloth, the easier it is to break. Therefore, when the elastic modulus is 50 GPa or more, in the glass cloth manufacturing steps such as the fiber opening step and the surface treatment step, when the glass cloth passes through squeeze rolls or nip rolls in a wet state, it tends to be less likely to break. In addition, in subsequent steps such as the manufacture of the prepreg, when the glass cloth is passed through the slit for the purpose of controlling the amount of impregnation of the resin into the glass cloth, there is a tendency that breakage does not easily occur. When the modulus of elasticity of the glass wiring is 70 GPa or less, the texture of the glass cloth becomes soft, and when the glass cloth passes through a narrow space such as squeeze rollers or nip rollers, it tends to be less likely to break. In addition, since the elastic coefficient of the glass cloth is 70 GPa or less, the dielectric constant tends to relatively decrease further. The modulus of elasticity can be measured by the method described in the examples. Also, the modulus of elasticity can be adjusted by using the composition of the glass yarn.
本實施形態之玻璃布之介電常數於1GHz之頻率下，較佳為5.0以下，更佳為4.7以下，進而較佳為4.5以下，尤佳為4.0以下。再者，於本實施形態中，於言及介電常數時，只要未特別事先指明，則係指1GHz之頻率下之介電常數。 The dielectric constant of the glass cloth of this embodiment is preferably 5.0 or less, more preferably 4.7 or less, further preferably 4.5 or less, and most preferably 4.0 or less at a frequency of 1 GHz. In addition, in this embodiment, when referring to a dielectric constant, unless otherwise specified, it refers to the dielectric constant at a frequency of 1 GHz.
玻璃紗係將複數根玻璃絲收束並視需要撚絞所得者，玻璃布係將上述玻璃紗作為經紗及緯紗而織造所得者。將玻璃紗分類為複絲，將玻璃絲 分類為單絲。 Glass yarn is obtained by bundling a plurality of glass filaments and optionally twisting them, and glass cloth is obtained by weaving the above-mentioned glass yarns as warp and weft. Classify glass yarn as multifilament, glass yarn Classified as monofilament.
構成經紗及緯紗之玻璃絲之平均直徑各自獨立地較佳為2.5~9μm，更佳為3.0~7.5μm，進而較佳為3.5~5.4μm。藉由玻璃絲之平均直徑為上述範圍內，於利用機械鑽孔器或二氧化碳氣體雷射、UV-YAG(Ultraviolet-Yttrium Aluminum Garnet，紫外線-釔鋁石榴石)雷射對所獲得之基板進行加工時，存在加工性進一步提昇之傾向。因此，能夠實現薄且高密度封裝之印刷電路板。尤其是，若平均直徑成為5.4μm以下，則由於每單位體積之表面積增加，而容易產生因熱處理造成之強度降低，因此，本實施形態之強度降低之抑制效果變得更加重要。又，藉由平均直徑為2.5μm以上，表面積變小，玻璃成分之揮發受到抑制，除此以外，於開纖步驟或表面處理步驟等玻璃布之製造步驟中，於玻璃布在濕潤狀態下通過擠壓輥或夾輥等時，存在不易產生斷裂之傾向。又，於預浸體之製造等後續步驟中，於因控制樹脂向玻璃布中之含浸量之目的而使玻璃布通過狹縫時，亦存在不易產生斷裂之傾向。 The average diameter of the glass filaments constituting the warp and the weft is independently preferably 2.5 to 9 μm, more preferably 3.0 to 7.5 μm, and still more preferably 3.5 to 5.4 μm. When the average diameter of the glass filament is within the above range, when the obtained substrate is processed by a mechanical drill or a carbon dioxide gas laser or UV-YAG (Ultraviolet-Yttrium Aluminum Garnet, ultraviolet-Yttrium Aluminum Garnet) laser , there is a tendency to further improve the processability. Therefore, a thin and high-density packaged printed circuit board can be realized. In particular, when the average diameter is 5.4 μm or less, since the surface area per unit volume increases, strength reduction due to heat treatment tends to occur. Therefore, the effect of suppressing strength reduction in this embodiment becomes more important. In addition, since the average diameter is 2.5 μm or more, the surface area becomes smaller, and the volatilization of glass components is suppressed. In addition, in the glass cloth manufacturing steps such as the fiber opening step and the surface treatment step, the glass cloth is passed in a wet state. When pressing rolls or nip rolls, etc., there is a tendency to be less prone to breakage. In addition, in subsequent steps such as the manufacture of the prepreg, when the glass cloth is passed through the slit for the purpose of controlling the amount of impregnation of the resin into the glass cloth, there is a tendency that breakage does not easily occur.
構成玻璃布之經紗及緯紗之織入密度較佳為30~130根/25mm，更佳為40~120根/25mm，進而較佳為50~110根/25mm。 The weaving density of warp yarns and weft yarns constituting the glass cloth is preferably 30-130 yarns/25mm, more preferably 40-120 yarns/25mm, and further preferably 50-110 yarns/25mm.
玻璃布之厚度較佳為8~100μm，更佳為10~50μm，進而較佳為12~35μm，最佳為12μm~30μm。藉由玻璃布之厚度為上述範圍內，存在獲得薄且強度相對較高之玻璃布之傾向。尤其是，藉由厚度為8μm以上，佔據玻璃布之表面附近之玻璃絲之比率減少，因此，存在玻璃成分之 揮發量降低之傾向。又，藉由厚度為100μm以下，佔據玻璃布之表面附近之玻璃絲之比率增加，因此，容易產生因玻璃成分之揮發量之增大造成的強度降低，本發明之強度降低之抑制效果變得更加重要。再者，重量減少係數取決於構成玻璃布之絲之直徑，因此，難以取決於厚度。該傾向至少於上述厚度範圍內得以保持。 The thickness of the glass cloth is preferably 8-100 μm, more preferably 10-50 μm, further preferably 12-35 μm, most preferably 12-30 μm. When the thickness of the glass cloth is within the above range, there is a tendency to obtain a thin glass cloth with relatively high strength. In particular, when the thickness is 8 μm or more, the ratio of the glass filaments occupying the vicinity of the surface of the glass cloth decreases, and therefore, there is a gap in the glass composition. Tendency to decrease volatility. In addition, when the thickness is 100 μm or less, the ratio of the glass filaments occupying the vicinity of the surface of the glass cloth increases, and therefore, the reduction in strength due to the increase in the volatilization amount of the glass component tends to occur, and the suppression effect of the strength reduction of the present invention becomes even stronger. important. Furthermore, the weight reduction factor depends on the diameter of the filaments constituting the glass cloth, and thus is difficult to depend on the thickness. This tendency is maintained at least within the above thickness range.
玻璃布之布重量(單位面積重量)較佳為8~250g/m2，更佳為8~100g/m2，進而較佳為8~50g/m2，尤佳為8~35g/m2。 The cloth weight (weight per unit area) of the glass cloth is preferably 8~250g/m 2 , more preferably 8~100g/m 2 , further preferably 8~50g/m 2 , especially preferably 8~35g/m 2 .
玻璃布之編織結構並無特別限定，例如可例舉平紋織物、方平織物、緞紋織物、斜紋織物等編織結構。其中，更佳為平紋織物結構。 The weaving structure of the glass cloth is not particularly limited, and for example, weaving structures such as plain weave, basket weave, satin weave, and twill weave may be mentioned. Among them, the plain weave structure is more preferable.
玻璃布亦可為利用表面處理劑進行過表面處理者。作為表面處理劑，並無特別限制，例如可例舉矽烷偶合劑，亦可視需要一起使用水、有機溶劑、酸、染料、顏料、界面活性劑等。 The glass cloth may also be surface-treated with a surface treatment agent. The surface treatment agent is not particularly limited, and for example, a silane coupling agent may be used, and water, an organic solvent, an acid, a dye, a pigment, a surfactant, or the like may be used together if necessary.
矽烷偶合劑並無特別限制，例如可例舉式(1)所表示之化合物。 The silane coupling agent is not particularly limited, for example, a compound represented by formula (1) may be mentioned.
X(R)3-nSiYn‧‧‧(1) X(R) 3-n SiY n ‧‧‧(1)
(式(1)中，X係具有胺基及不飽和雙鍵基中之至少1個以上之有機官能基，Y各自獨立地為烷氧基，n係1以上3以下之整數，R各自獨立地為選自由甲基、乙基及苯基所組成之群中之基)。 (In formula (1), X is an organic functional group having at least one of an amino group and an unsaturated double bond group, Y is each independently an alkoxy group, n is an integer ranging from 1 to 3, and R is independently is a group selected from the group consisting of methyl, ethyl and phenyl).
X較佳為具有胺基及不飽和雙鍵基中之至少3個以上之有機官能基，X更佳為具有胺基及不飽和雙鍵基中之至少4個以上之有機官能基。 X is preferably an organic functional group having at least 3 or more of an amine group and an unsaturated double bond group, and X is more preferably an organic functional group having at least 4 or more of an amine group and an unsaturated double bond group.
作為上述烷氧基，可使用任一形態，但就向玻璃布之穩定處理化之觀點而言，較佳為碳數5以下之烷氧基。 As the above-mentioned alkoxy group, any form can be used, but an alkoxy group having 5 or less carbon atoms is preferable from the viewpoint of stabilization treatment to glass cloth.
作為矽烷偶合劑，具體而言，可例舉N-β-(N-乙烯基苄基胺基乙基)-γ-胺基丙基三甲氧基矽烷及其鹽酸鹽、N-β-(N-乙烯基苄基胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷及其鹽酸鹽、N-β-(N-二(乙烯基苄基)胺基乙基)-γ-胺基丙基三甲氧基矽烷及其鹽酸鹽、N-β-(N-二(乙烯基苄基)胺基乙基)-N-γ-(N-乙烯基苄基)-γ-胺基丙基三甲氧基矽烷及其鹽酸鹽、N-β-(N-苄基胺基乙基)-γ-胺基丙基三甲氧基矽烷及其鹽酸鹽、N-β-(N-苄基胺基乙基)-γ-胺基丙基三乙氧基矽烷及其鹽酸鹽、γ-(2-胺基乙基)胺基丙基三甲氧基矽烷、γ-(2-胺基乙基)胺基丙基三乙氧基矽烷、胺基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、甲基丙烯醯氧基丙基三甲基矽烷、丙烯醯氧基丙基三甲氧基矽烷等公知之單體、或該等之混合物。 As the silane coupling agent, specifically, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane and its hydrochloride, N-β-( N-vinylbenzylaminoethyl)-γ-aminopropylmethyldimethoxysilane and its hydrochloride, N-β-(N-di(vinylbenzyl)aminoethyl) -γ-Aminopropyltrimethoxysilane and its hydrochloride, N-β-(N-di(vinylbenzyl)aminoethyl)-N-γ-(N-vinylbenzyl)- γ-aminopropyltrimethoxysilane and its hydrochloride, N-β-(N-benzylaminoethyl)-γ-aminopropyltrimethoxysilane and its hydrochloride, N-β -(N-Benzylaminoethyl)-γ-aminopropyltriethoxysilane and its hydrochloride, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ- (2-Aminoethyl)aminopropyltriethoxysilane, Aminopropyltrimethoxysilane, Vinyltrimethoxysilane, Methacryloxypropyltrimethylsilane, Acryloxy Known monomers such as propylpropyltrimethoxysilane, or a mixture thereof.
表面處理劑之分子量較佳為100~600，更佳為150~500，進而較佳為200~450。其中，較佳為使用分子量不同之2種以上之表面處理劑。藉由使用分子量不同之2種以上之表面處理劑對玻璃紗之表面進行處理，玻璃布之表面中之表面處理劑密度變高，存在與基質樹脂之反應性進而提昇之傾向。 The molecular weight of the surface treatment agent is preferably 100-600, more preferably 150-500, further preferably 200-450. Among them, it is preferable to use two or more surface treatment agents having different molecular weights. By treating the surface of the glass yarn with two or more surface treatment agents having different molecular weights, the density of the surface treatment agent on the surface of the glass cloth increases, and the reactivity with the matrix resin tends to increase.
本實施形態之玻璃布之製造方法並無特別限定，例如可例舉如下方法，該方法具有對玻璃紗進行織造而獲得玻璃布之織造步驟、及對玻璃布之玻璃紗進行開纖之開纖步驟。又，亦可視需要具有將附著於玻璃布之玻璃紗之上漿劑去除之脫糊步驟、利用表面處理劑等進行之表面處理步驟。 The manufacturing method of the glass cloth of this embodiment is not particularly limited, for example, a method including a weaving step of weaving glass yarns to obtain glass cloth, and fiber opening of glass yarns of the glass cloth step. In addition, a depaste process for removing the sizing agent attached to the glass yarn attached to the glass cloth, a surface treatment process with a surface treatment agent, etc. may be provided as needed.
織造方法只要為以成為特定之編織結構之方式編織緯紗及經紗者即可，並無特別限制。又，作為開纖方法，並無特別限制，例如可例舉利用噴水(高壓水開纖)、振盪洗滌機(vibro washer)、超音波水、軋壓機等進行開纖加工之方法。進而，作為脫糊方法，並無特別限制，例如可例舉將上漿劑加熱去除之方法。又，作為表面處理方法，可例舉使表面處理劑與玻璃布接觸並進行乾燥等之方法。再者，表面處理劑與玻璃布之接觸可例舉使玻璃布浸漬於表面處理劑中之方法或使用輥式塗佈機、模嘴塗佈機、或凹版塗佈機等於玻璃布塗佈表面處理劑之方法等。作為表面處理劑之乾燥方法，並無特別限制，例如可例舉使用熱風乾燥或電磁波之乾燥方法。 The weaving method is not particularly limited as long as the weft and warp are woven so as to form a specific weaving structure. Also, the fiber opening method is not particularly limited, and examples thereof include methods of fiber opening using water jets (high-pressure water fiber opening), vibro washers, ultrasonic water, and calenders. Furthermore, it does not specifically limit as a depaste method, For example, the method of heating and removing a sizing agent is mentioned. Moreover, as a surface treatment method, the method of bringing a surface treatment agent into contact with glass cloth and drying it is mentioned. Furthermore, the contact between the surface treatment agent and the glass cloth can be, for example, the method of immersing the glass cloth in the surface treatment agent or using a roll coater, a die coater, or a gravure coater to coat the surface of the glass cloth. The method of treating agent, etc. The drying method of the surface treatment agent is not particularly limited, and for example, a drying method using hot air or electromagnetic waves may be mentioned.
本實施形態之預浸體具有上述玻璃布、及該玻璃布中含浸之基質樹脂組合物。具有上述玻璃布之預浸體不易引起強度降低，成為最終製品之良率較高者。又，由於介電特性優異、耐吸濕性優異，故亦可發揮如下效果，即，能夠提供使用環境之影響、尤其高濕度環境下之介電常數之變動較小之印刷電路板。 The prepreg of this embodiment has the said glass cloth, and the matrix resin composition impregnated in this glass cloth. The prepreg having the above-mentioned glass cloth is less prone to decrease in strength and has a higher yield rate of the final product. In addition, since it has excellent dielectric properties and excellent moisture absorption resistance, it is also possible to provide a printed circuit board that is less affected by the use environment, especially in a high-humidity environment, with less variation in dielectric constant.
本實施形態之預浸體可按照慣例進行製造。例如，可藉由如下方法進行製造，即，於本實施形態之玻璃布中含浸將如環氧樹脂之基質樹脂利用有機溶劑進行稀釋所得之清漆後，於乾燥爐內使有機溶劑揮發，使熱固性樹脂硬化至B階段狀態(半硬化狀態)。 The prepreg of this embodiment can be manufactured conventionally. For example, it can be produced by impregnating the glass cloth of this embodiment with a varnish obtained by diluting a matrix resin such as an epoxy resin with an organic solvent, and then volatilizing the organic solvent in a drying oven to make the thermosetting The resin hardens to a B-stage state (semi-cured state).
作為基質樹脂組合物，除了上述環氧樹脂以外，亦可例舉：雙馬來醯亞胺樹脂、氰酸酯樹脂、不飽和聚酯樹脂、聚醯亞胺樹脂、BT(polybismaleimide triazine，順丁烯二醯亞胺三嗪)樹脂、官能基化聚苯醚樹脂等熱固性樹脂；聚苯醚樹脂、聚醚醯亞胺樹脂、全芳香族聚酯之液晶聚合物(LCP)、聚丁二烯、氟樹脂等熱塑性樹脂；及其等之混合樹脂等。就提昇介電特性、耐熱性、耐溶劑性、及加壓成形性之觀點而言，作為基質樹脂組合物，亦可使用將熱塑性樹脂利用熱固性樹脂改性所得之樹脂。 As the matrix resin composition, in addition to the above-mentioned epoxy resin, also can exemplify: bismaleimide resin, cyanate resin, unsaturated polyester resin, polyimide resin, BT (polybismaleimide triazine, cis-butyl Thermosetting resins such as alkene imide triazine) resin, functionalized polyphenylene ether resin; polyphenylene ether resin, polyetherimide resin, liquid crystal polymer (LCP) of wholly aromatic polyester, polybutadiene , fluororesin and other thermoplastic resins; and their mixed resins, etc. From the viewpoint of improving dielectric properties, heat resistance, solvent resistance, and press-formability, resins obtained by modifying thermoplastic resins with thermosetting resins can also be used as the matrix resin composition.
又，基質樹脂組合物亦可於樹脂中包含：二氧化矽及氫氧化鋁等無機填充劑；溴系、磷系、金屬氫氧化物等阻燃劑；其他矽烷偶合劑；熱穩定劑；抗靜電劑；紫外線吸收劑；顏料；著色劑；潤滑劑等。 Moreover, the matrix resin composition may also include in the resin: inorganic fillers such as silicon dioxide and aluminum hydroxide; flame retardants such as bromine, phosphorus, and metal hydroxides; other silane coupling agents; heat stabilizers; Antistatic agents; UV absorbers; pigments; colorants; lubricants, etc.
本實施形態之印刷電路板具備上述玻璃布。本實施形態之印刷電路板不易引起強度降低，成為最終製品之良率較高者。又，由於介電特性優異、耐吸濕性優異，故亦可發揮使用環境之影響、尤其高濕度環境下之介電常數之變動較小之效果。 The printed wiring board of this embodiment is equipped with the said glass cloth. The printed circuit board of this embodiment is less prone to decrease in strength and has a higher yield rate of the final product. In addition, due to its excellent dielectric properties and excellent moisture absorption resistance, it can also exhibit the effect of small changes in the dielectric constant under the influence of the use environment, especially in a high-humidity environment.
再者，關於上述各種測定值，只要未特別事先指明，則根據下述實施例中記載之測定方法進行測定。 In addition, about the above-mentioned various measured values, unless otherwise specified, it measured according to the measuring method described in the following Example.
以下，使用實施例及比較例更具體地對本發明進行說明。本發明並不受以下之實施例之任何限定。 Hereinafter, the present invention will be described more specifically using examples and comparative examples. The present invention is not limited by the following examples.
玻璃布之物性、具體而言玻璃布之厚度、構成經紗及緯紗之長絲之徑、長絲數、經紗及緯紗之織入密度(織密度)係依據JIS R3420進行測定。 The physical properties of the glass cloth, specifically the thickness of the glass cloth, the diameter of the filaments constituting the warp and weft, the number of filaments, and the weaving density (weaving density) of the warp and weft were measured in accordance with JIS R3420.
重量減少係數係按照以下之順序進行測定。 The weight reduction coefficient was measured in the following procedure.
首先，將自中間捲拉出之玻璃布放入105℃±5℃之乾燥機中乾燥60分鐘，然後，將玻璃布移至乾燥器中，放置冷卻直至室溫為止。放置冷卻後，以0.1mg以下之單位稱量玻璃布之重量(玻璃布之重量a)。繼而，將玻璃布於380℃下加熱2小時，然後，將玻璃布移至乾燥器中，放置冷卻直至室溫為止。放置冷卻後，以0.1mg以下之單位稱量玻璃布之重量(加熱處理後之玻璃布重量b)。然後，求出由於加熱處理而減少之重量，根據下述式(2)算出重量減少比率(%)。 First, put the glass cloth pulled out from the middle roll into a drier at 105°C±5°C for 60 minutes to dry, then move the glass cloth to the drier, let it cool down until room temperature. After standing to cool, measure the weight of the glass cloth (weight of glass cloth a) in units of 0.1 mg or less. Next, the glass cloth was heated at 380° C. for 2 hours, then the glass cloth was moved to a desiccator, and left to cool until room temperature. After standing to cool, measure the weight of the glass cloth in units of 0.1 mg or less (the weight of the glass cloth after heat treatment b). Then, the weight decreased by the heat treatment was obtained, and the weight loss ratio (%) was calculated from the following formula (2).
重量減少比率(%)=(a-b)/a×100‧‧‧(2) Weight reduction ratio (%)=(a-b)/a×100‧‧‧(2)
繼而，依據JIS R3420之B法測定單絲之直徑，將其1/2之值作為單絲之半徑。再者，雖JIS R3420之B法中隨機測定25個長絲截面之直徑，但此處係測定構成玻璃紗(複絲)之全部單絲之直徑，求出作為其平均值之絲直徑。 Then, the diameter of the monofilament was measured according to B method of JIS R3420, and the value of 1/2 thereof was regarded as the radius of the monofilament. In the B method of JIS R3420, the diameters of 25 cross-sections of filaments are randomly measured, but here, the diameters of all the monofilaments constituting the glass yarn (multifilament) are measured, and the average value of the filament diameter is obtained.
使用重量減少比率(%)及玻璃絲之平均半徑(μm)，利用下述式(1)算出重量減少係數。 Using the weight reduction ratio (%) and the average radius (μm) of the glass filaments, the weight reduction coefficient was calculated by the following formula (1).
重量減少係數=重量減少比率(%)×玻璃絲之平均半徑(μm)‧‧‧(1) Weight reduction factor = weight reduction ratio (%) × average radius of glass filament (μm)‧‧‧(1)
關於彈性係數，玻璃紗之彈性係數係將玻璃塊用作試驗片並藉由脈衝回波重疊法進行測定。 Regarding the modulus of elasticity, the modulus of elasticity of the glass yarn was measured by the pulse-echo superposition method using a glass block as a test piece.
將玻璃紗熔融，製作長度約50mm、寬度約1.5mm之塊狀玻璃試驗片，利用空腔共振器進行測定。將該試驗片放入105℃±2℃之烘箱中乾燥2小時後，於23±2℃、相對濕度50±5%之恆溫室中靜置96小時後，測定10GHz之介電常數。 Melt the glass yarn to make a block glass test piece with a length of about 50 mm and a width of about 1.5 mm, and measure it with a cavity resonator. Put the test piece in an oven at 105°C±2°C to dry for 2 hours, then place it in a constant temperature room at 23°C±2°C and a relative humidity of 50±5% for 96 hours, then measure the dielectric constant at 10GHz.
再者，測定裝置係使用網路分析儀(N5230A，AgilentTechnologies公司製造)、及關東電子應用開發公司製造之空腔共振器(Cavity Resornator CP系列)，於23±2℃、相對濕度50±5%之環境下進行測定。 Furthermore, the measurement device uses a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resornator CP series) manufactured by Kanto Electronics Application Development Co., Ltd., at 23±2°C and relative humidity of 50±5%. environment for measurement.
玻璃布之組成係藉由ICP(inductively coupled plasma，感應耦合電漿)發射光譜分析法進行測定。具體而言，關於Si含量及B含量，可將稱取之玻璃布樣品利用氫氧化鈉加壓分解後，利用稀硝酸溶解後進行過濾，將不溶解成分利用碳酸鈉熔解後，合併濾液並定容，藉由ICP發射光譜分析法對所獲得之樣品進行測定而獲得。 The composition of the glass cloth is determined by ICP (inductively coupled plasma, inductively coupled plasma) emission spectrometry. Specifically, regarding the Si content and B content, the weighed glass cloth sample can be decomposed by sodium hydroxide under pressure, dissolved in dilute nitric acid and then filtered, and the insoluble components can be dissolved by sodium carbonate, and the filtrates can be combined and determined. The content was obtained by measuring the obtained samples by ICP emission spectrometry.
又，Fe含量、Al含量、Ca含量、Ma含量係將稱取之玻璃布樣品利用過氯酸、硝酸、鹽酸及氟化氫加熱分解後，利用稀王水加熱溶解後進行過濾分離，將濾液定容，將不溶解成分利用硫酸、硝酸、鹽酸及氟化氫加熱分解後定溶，藉由ICP發射光譜分析法對所獲得之樣品進行測定而獲得。再者，作為ICP發射光譜分析裝置，使用Hitachi High-Tech Science公司製造之PS3520VDD II。 In addition, the Fe content, Al content, Ca content, and Ma content are obtained by heating and decomposing the weighed glass cloth sample with perchloric acid, nitric acid, hydrochloric acid, and hydrogen fluoride, then heating and dissolving with dilute aqua regia, and then filtering and separating the filtrate to volume. , the insoluble components are heated and decomposed by sulfuric acid, nitric acid, hydrochloric acid and hydrogen fluoride, and then dissolved, and the obtained samples are measured by ICP emission spectrometry. In addition, as an ICP emission spectrometer, PS3520VDD II manufactured by Hitachi High-Tech Science was used.
進而，F含量係將稱取之玻璃布樣品於管狀電爐中進行燃燒後，將產生之氣體吸收至吸收液中，針對該溶液，用離子層析儀測定氟化物離子(F-)，而求出試樣中之含量。再者，燃燒裝置係使用Mitsubishi Chemical Analytech製造之自動試樣燃燒裝置(AQF-2100S)，測定裝置係使用Thermo Fisher Scientific製造之離子層析儀ICS-1500。 Furthermore, the F content is obtained by burning the weighed glass cloth sample in a tubular electric furnace, absorbing the generated gas into the absorption solution, and measuring the fluoride ion (F - ) with an ion chromatography on the solution. The content in the sample. In addition, the combustion apparatus used the automatic sample combustion apparatus (AQF-2100S) manufactured by Mitsubishi Chemical Analytech, and the measurement apparatus used the ion chromatograph ICS-1500 manufactured by Thermo Fisher Scientific.
使用實施例及比較例中獲得之玻璃布，於以下之條件下進行預浸體之製作，評價強度是否充分。一面將玻璃布連續地拉出並搬送，一面將玻 璃布浸漬於清漆，並使其通過狹縫以調整清漆之塗佈量。繼而，通過120℃之乾燥爐使其乾燥，從而獲得預浸體。又，清漆係使用包含甲基丙烯酸化聚苯醚65質量份、異氰尿酸三烯丙酯35質量份、氫化苯乙烯系熱塑性彈性體10質量份、溴系阻燃劑25質量份、球形二氧化矽65質量份、有機過氧化物1質量份、甲苯210質量份者。 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. While pulling out and conveying the glass cloth continuously, the glass cloth is The glass cloth is dipped in the varnish and passed through the slit to adjust the coating amount of the varnish. Then, it dried in the drying oven of 120 degreeC, and obtained the prepreg. In addition, the varnish system uses 65 parts by mass of methacrylated polyphenylene ether, 35 parts by mass of triallyl isocyanurate, 10 parts by mass of hydrogenated styrene-based thermoplastic elastomer, 25 parts by mass of brominated flame retardant, spherical bismuth 65 parts by mass of silicon oxide, 1 part by mass of organic peroxide, and 210 parts by mass of toluene.
針對各實施例及比較例中獲得之玻璃布，分別對2000m之製品捲各10根，藉由上述方法實施預浸體之製作。基於該製作結果，按照以下之評價基準進行強度降低之確認。 About the glass cloth obtained in each Example and the comparative example, 2000 m of product rolls were each 10, and the preparation of the prepreg was implemented by the method mentioned above. Based on the production results, the strength reduction was confirmed according to the following evaluation criteria.
◎：玻璃布不斷裂，能夠使用10根玻璃布之捲進行預浸體之製作之情形。判斷為生產性、操作性優異之玻璃布。 ◎: The glass cloth is not broken, and the roll of 10 glass cloths can be used for the production of the prepreg. Glass cloth judged to be excellent in productivity and operability.
O：於預浸體之製作過程中，1根玻璃布之捲中產生斷裂，但剩餘之9根捲能夠於不斷裂之情況下進行預浸體之製作之情形。判斷為具有實用強度之玻璃布。 O: In the prepreg manufacturing process, one glass cloth roll was broken, but the remaining 9 rolls could be used for prepreg production without breaking. Glass cloth judged to have practical strength.
△：於預浸體之製作過程中，2~3根玻璃布之捲中產生斷裂，但剩餘之捲能夠於不斷裂之情況下進行預浸體之製作之情形。判斷為需要改善強度之玻璃布。 △: During the production process of the prepreg, 2~3 rolls of glass cloth were broken, but the remaining rolls could be used to produce the prepreg without breaking. It is judged that the glass cloth whose strength needs to be improved.
×：於預浸體之製作過程中，4根以上之玻璃布之捲中產生斷裂之情形。 ×: During the production process of the prepreg, breakage occurred in the roll of 4 or more glass cloths.
將強度降低確認試驗中獲得之預浸體以積層板之厚度成為約1mm之方式重疊特定片數，進而於該重疊之預浸體之兩面，重疊以銅箔(古川電 氣工業股份有限公司製造，厚度18μm，GTS-MP箔)，於該狀態下，進行真空加壓，藉此獲得銅箔積層板。然後，自上述銅箔積層板，藉由蝕刻將銅箔去除，藉此獲得積層板。 The prepregs obtained in the strength reduction confirmation test were stacked by a specific number of sheets so that the thickness of the laminated board became about 1 mm, and copper foil (Furukawa Electric Co., Ltd.) was stacked on both sides of the stacked prepreg Gas Industry Co., Ltd., thickness 18 μm, GTS-MP foil), vacuum pressurization was performed in this state, thereby obtaining a copper foil laminated board. Then, from the above-mentioned copper foil laminated board, the copper foil was removed by etching to obtain a laminated board.
自所獲得之積層板，以玻璃布之經紗成為長邊之方式，切出長度約50mm、寬度約1.5mm之試驗片，作為電氣特性試驗用之試驗片。將所獲得之試驗片放入105℃±2℃之烘箱中乾燥2小時後，於以下所示之標準條件及高濕度條件下測定10GHz之介電常數及介電損耗因數。 From the obtained laminate, a test piece with a length of about 50 mm and a width of about 1.5 mm was cut out so that the warp of the glass cloth became the long side, and was used as a test piece for the electrical characteristic test. The obtained test piece was dried in an oven at 105°C±2°C for 2 hours, and the dielectric constant and dielectric loss factor were measured at 10GHz under the standard conditions and high humidity conditions shown below.
標準條件：於23±2℃、相對濕度50±5%之恆溫室中靜置96小時後進行測定 Standard conditions: measured after standing in a constant temperature room at 23±2°C and relative humidity of 50±5% for 96 hours
高濕度條件：於40±2℃、相對濕度85±5%之恆溫室中靜置96小時後進行測定 High-humidity conditions: measured after standing in a constant temperature room at 40±2°C and relative humidity of 85±5% for 96 hours
再者，測定裝置係使用網路分析儀(N5230A，AgilentTechnologies公司製造)、及關東電子應用開發公司製造之空腔共振器(Cavity Resornator CP系列)，測定本身係於23±2℃、相對濕度50±5%之環境下進行。使用切出之5個試驗片將各測定重複進行5次，並將其平均值作為介電常數、介電正切之值。 Furthermore, the measurement device uses a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resornator CP series) manufactured by Kanto Electronics Application Development Company. ±5% environment. Each measurement was repeated 5 times using the 5 cut-out test pieces, and the average value was used as the value of a dielectric constant and a dielectric tangent.
利用噴氣織機，織造長絲平均直徑4.0μm、包含50根長絲之低介電玻璃紗(介電常數4.8)，獲得經紗及緯紗之織入密度分別為94根/25mm、厚度為14μm之玻璃布。繼而，藉由加熱進行脫糊處理，獲得寬度1280 mm、長度2000m之玻璃布中間捲。 Using an air-jet loom, weave a low-dielectric glass yarn (dielectric constant 4.8) with an average filament diameter of 4.0 μm and 50 filaments, and obtain a glass with a weaving density of 94 yarns/25mm in warp and weft yarns and a thickness of 14 μm. cloth. Then, depaste treatment is carried out by heating to obtain a width of 1280 mm, length 2000m glass cloth middle roll.
使用所獲得之玻璃布中間捲，一面自玻璃布中間捲將玻璃布連續地拉出並搬送，一面將玻璃布浸漬於包含矽烷偶合劑之處理液，並利用擠液調整矽烷偶合劑之塗佈量後，暫時進行乾燥。繼而，利用高壓水噴霧實施開纖，進行乾燥，卷取為捲狀，而獲得玻璃布之製品捲。再者，連續地進行上述矽烷偶合劑之塗佈、及開纖處理係10捲。所獲得之玻璃布之組成係如表1。 Using the intermediate roll of glass cloth obtained, the glass cloth is continuously pulled out from the intermediate roll of glass cloth and transported, while the glass cloth is immersed in the treatment liquid containing the silane coupling agent, and the coating of the silane coupling agent is adjusted by squeezing the liquid After measuring, dry it temporarily. Then, fiber opening was carried out by spraying with high-pressure water, drying was carried out, and the glass cloth was wound into a roll to obtain a product roll of glass cloth. In addition, the coating of the above-mentioned silane coupling agent and the fiber opening treatment were performed continuously for 10 rolls. The composition of the obtained glass cloth is shown in Table 1.
除了玻璃紗之組成不同以外，以與實施例1相同之方式獲得玻璃布之捲。所獲得之玻璃布之組成係如表1及2。 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 Tables 1 and 2.
使用與實施例2相同之低介電玻璃紗，且藉由減弱開纖處理中之高壓水噴霧之強度來降低開纖之程度，除此以外，以與實施例2相同之方式獲得玻璃布之捲。 Use the same low-dielectric glass yarn as in Example 2, and reduce the degree of fiber opening by weakening the intensity of the high-pressure water spray in the fiber opening treatment. In addition, obtain the glass cloth in the same manner as in Example 2. roll.
使用與實施例2相同之低介電玻璃紗，且藉由提高開纖處理中之高壓水噴霧之強度來提高開纖之程度，除此以外，以與實施例2相同之方式獲得玻璃布之捲。 Use the same low-dielectric glass yarn as in Example 2, and improve the degree of fiber opening by increasing the intensity of the high-pressure water spray in the fiber opening treatment. In addition, obtain the glass cloth in the same manner as in Example 2. roll.
織造長絲平均直徑5.0μm、包含100根長絲之低介電玻璃紗(介電常數4.8)，將經紗及緯紗之織入密度分別設為69根/25mm而製作玻璃布，除此以外，以與實施例1相同之方式獲得玻璃布之捲。所獲得之玻璃布之厚度為30μm，組成係如表2。 Weaving low-dielectric glass yarn (dielectric constant 4.8) with an average filament diameter of 5.0 μm and containing 100 filaments, and setting the weaving density of warp and weft yarns to 69 yarns/25mm respectively to make glass cloth. In addition, A roll of glass cloth was obtained in the same manner as in Example 1. The obtained glass cloth has a thickness of 30 μm and its composition is shown in Table 2.
將經紗及緯紗之織入密度分別設為55根/25mm，除此以外，以與實施例14相同之方式獲得玻璃布之捲。所獲得之玻璃布之厚度為30μm，組成係如表2。 A roll of glass cloth was obtained in the same manner as in Example 14 except that the weaving density of the warp and the weft was 55 yarns/25 mm, respectively. The obtained glass cloth has a thickness of 30 μm and its composition is shown in Table 2.
織造長絲平均直徑7.0μm、包含200根長絲之低介電玻璃紗(介電常數4.8)，將經紗及緯紗之織入密度分別設為60根/25mm、57根/25mm而製作玻璃布，除此以外，以與實施例1相同之方式獲得玻璃布之捲。所獲得之玻璃布之厚度為92μm，組成係如表2。 Weaving low-dielectric glass yarns (dielectric constant 4.8) with an average filament diameter of 7.0 μm and 200 filaments, and setting the weaving density of warp yarns and weft yarns to 60 yarns/25mm and 57 yarns/25mm respectively to make glass cloth , except that, in the same manner as in Example 1, a roll of glass cloth was obtained. The obtained glass cloth has a thickness of 92 μm and its composition is shown in Table 2.
除了玻璃紗之組成不同以外，以與實施例1相同之方式獲得玻璃布之捲。所獲得之玻璃布之組成係如表2。 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 2.
除了使用E玻璃組成之玻璃紗以外，以與實施例1相同之方式獲得玻 璃布之捲。 Obtain glass yarn in the same manner as in Example 1, except that glass yarn composed of E glass is used. Roll of Glass Cloth.
實施例1~4、7、12、14~16之玻璃布係10捲均能夠於玻璃布不斷裂之情況下穩定地進行製造。又，實施例5、6、8~11、13之玻璃布係僅 1捲產生玻璃布之斷裂但剩餘之9捲能夠穩定地進行製造。又，參考例1之玻璃布係雖未產生斷裂但電氣特性較差者。 Ten rolls of the glass cloth series of Examples 1 to 4, 7, 12, and 14 to 16 can all be manufactured stably without breaking the glass cloth. Also, the glass cloths of Examples 5, 6, 8-11, and 13 are only One roll produced breakage of the glass cloth but the remaining 9 rolls could be manufactured stably. In addition, although the glass cloth of Reference Example 1 did not break, it had poor electrical characteristics.
另一方面，比較例1、3、5之玻璃布於2捲至3捲產生斷裂。不足以穩定地供給使用低介電玻璃之印刷電路板，需要改善。進而，比較例2、4、6之玻璃布自塗敷開始連續地於4捲產生斷裂，因此，不得不中止塗敷試驗。 On the other hand, the glass cloths of Comparative Examples 1, 3, and 5 were broken in 2 to 3 rolls. It is not enough to stably supply printed circuit boards using low-dielectric glass and needs to be improved. Furthermore, since the glass cloths of Comparative Examples 2, 4, and 6 were continuously broken in 4 rolls from the start of coating, the coating test had to be stopped.
進而，如實施例11所示，可知於Mg含量較多之情形時，於製成積層板時，高濕度條件下之介電正切之增加較大。 Furthermore, as shown in Example 11, it can be seen that when the Mg content is large, the increase in the dielectric tangent under high humidity conditions is large when the laminate is made.
本發明作為用於預浸體等之低介電玻璃布，具有產業上之可利用性。 The present invention has industrial applicability as a low-dielectric glass cloth used for prepregs and the like.
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| CN113337934B (en) * | 2017-02-10 | 2022-12-02 | 旭化成株式会社 | Glass cloth, prepreg, and printed wiring board |
| CN111379063B (en) * | 2018-12-25 | 2021-06-25 | 旭化成株式会社 | Method for producing glass cloth and glass yarn |
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| TW492949B (en) * | 1998-04-14 | 2002-07-01 | Nitto Boseki Co Ltd | Glass fiber having low dielectric constant and woven fabric of glass fiber made therefrom |
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