JP2018127750A - Glass cloth, prepreg and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: glass cloth low in dielectric constant with which a substrate excellent in dimensional stability can be manufactured (concept of the "substrate" includes prepregs, a printed wiring board or a laminate or the like therefor); and prepregs and a printed wiring board using the glass cloth.SOLUTION: The glass cloth is made by weaving a glass thread, as warp and weft, composed of a plurality of glass filaments. An average filament diameter of the glass filaments constituting the warp and the weft is 3-10 μm, the number of filaments of the warp and the weft is 20-300, the warp and the weft have each independently the placing density of 20-140/inch, the dielectric constant of the glass cloth is 4.4 or lower and the warpage of a printed wiring board constituted of the glass cloth is 10 mm or lower.SELECTED DRAWING: None

Description

  The present invention relates to a glass cloth, a prepreg, and a printed wiring board.

  Currently, along with the high performance and high speed communication of information terminals such as smartphones, the printed wiring boards used are becoming increasingly dense and extremely thin, and are also becoming increasingly low dielectric constant and low dielectric loss tangent. .

  As an insulating material of this printed wiring board, a laminated board obtained by laminating a prepreg obtained by impregnating a glass cloth with a thermosetting resin such as an epoxy resin (hereinafter referred to as “matrix resin”) and curing by heating and pressing. Is widely used. The dielectric constant of the matrix resin used for the high-speed communication substrate is about 3, whereas the dielectric constant of a general E glass cloth is about 6.7. It has become apparent. Note that the signal transmission loss is Edward A. As shown by the Wolff equation: transmission loss ∝√ε × tan δ, it is known that a material having a smaller dielectric constant (ε) and dielectric loss tangent (tan δ) is improved.

  Therefore, low dielectric constant glass cloths such as D glass, NE glass, and L glass having a glass composition different from that of E glass have been proposed (for example, see Patent Documents 1 to 4).

Japanese Patent Laid-Open No. 5-170483 JP2009-263569 JP2009-19150 JP 2009-263824 A

However, in future 5G communication applications and the like, these low dielectric constant glass cloths still have room for improvement from the viewpoint of achieving sufficient transmission speed performance. Here, it is conceivable to further lower the dielectric constant and lower the dielectric loss tangent by setting the amount of SiO ₂ in the glass composition to approximately 100%. However, when the amount of SiO _{2 in} the glass composition is increased to almost 100%, the hole workability with a mechanical drill generally used for a low dielectric constant substrate is significantly deteriorated.

Therefore, there is a method in which a general glass yarn and a glass yarn having a SiO ₂ blending amount of about 100% are mixed. In particular, the mechanical drill workability can be improved by using a glass thread having a SiO ₂ blending amount of almost 100% for the weft which does not adversely affect the mechanical drill workability. In the case of a glass yarn having a SiO ₂ blending amount of almost 100%, the glass spinning temperature is high, and it is difficult to produce a glass yarn having a thin filament diameter with high quality and low cost. Therefore, it is necessary to manufacture a glass cloth having a low dielectric constant by using a glass yarn having a thick filament diameter SiO ₂ content of almost 100% for the weft. However, due to the anisotropy due to the characteristic difference between the warp and weft, and the deterioration of quality such as skew (flection) and fluff due to the large filament diameter, problems arise in the warpage of the substrate and the dimensional stability of the substrate. . If dimensional stability is poor, wiring and processing cannot be performed as designed, and printed wiring boards cannot be mass-produced and manufactured.

  The present invention has been made in view of the above problems, and includes a substrate having a low dielectric constant and excellent dimensional stability (“substrate” includes a prepreg, a printed wiring board, or a laminated board thereof). An object of the present invention is to provide a glass cloth capable of producing a concept), a prepreg using the glass cloth, and a printed wiring board.

  As a result of investigations to solve the above problems, the present inventors have found that a predetermined glass cloth can solve the above problems, and have completed the present invention.

That is, the present invention is as follows.
[1]
A glass cloth formed by weaving glass yarns composed of a plurality of glass filaments as warps and wefts,
The average filament diameters of the glass filaments constituting the warp and the weft are each independently 3 to 10 μm,
The number of filaments of the warp and the weft are each independently 20 to 300,
The driving density of the warp and the weft is 20 to 140 pieces / inch independently of each other,
The dielectric constant of the glass cloth is 4.4 or less,
The warp of the printed wiring board composed of the glass cloth is 10 mm or less,
Glass cloth.
[2]
One of the warp and the weft is a glass yarn containing a glass filament whose SiO ₂ composition is 98 to 100% by mass,
The other of the warp and the weft is a glass yarn including a glass filament having a SiO ₂ composition amount of 45 to 60% by mass and a B ₂ O ₃ composition amount of 15 to 30% by mass,
The dielectric constant of the glass cloth is more than 3.8 and less than 4.4.
The glass cloth according to [1].
[3]
The average filament diameter of the glass filament whose SiO ₂ composition is 98 to 100% by mass is 6 to 9 μm.
The glass cloth according to [1] or [2].
[4]
The thickness is 30 to 90 μm.
The glass cloth according to any one of [1] to [3].
[5]
The tensile elastic modulus of the glass yarn composed of the glass filament with the SiO ₂ composition amount of 98 to 100% by mass is 70 GPa or more,
The SiO ₂ composition amount is 45 to 60 wt%, relative to the tensile modulus of the glass fiber in which the B ₂ O ₃ composition amount is made of the glass filaments is 15 to 30 wt%, the SiO ₂ composition weight 98 to The ratio of the tensile elastic modulus of the glass yarn comprising the glass filament that is 100% by mass is 1.3 or less,
The glass cloth according to any one of [1] to [4].
[6]
One of the warp and the weft is a glass yarn containing a glass filament whose SiO ₂ composition is 98 to 99.95% by mass,
The glass cloth according to any one of [1] to [5].
[7]
The other of the warp and the weft is a glass yarn containing a glass filament whose SiO ₂ composition is 50 to 60% by mass and whose B ₂ O ₃ composition is 20 to 30% by mass,
The glass cloth according to any one of [1] to [6].
[8]
The ignition loss value of the glass cloth is 0.2% by mass or more and 1.0% by mass or less.
The glass cloth according to any one of [1] to [7].
[9]
The skew of the weft and the warp of the glass cloth is 0 to 20 mm per meter when one glass yarn is vertical.
The glass cloth according to any one of [1] to [8].
[10]
The surface of the glass yarn was treated with a silane coupling agent,
The glass cloth according to any one of [1] to [9].
[11]
The glass cloth according to any one of [1] to [10];
A matrix resin impregnated in the glass cloth,
Prepreg.
[12]
[11] having the prepreg according to
Printed wiring board.

  ADVANTAGE OF THE INVENTION According to this invention, the dielectric constant and the glass cloth which can produce the board | substrate excellent in dimensional stability, the prepreg using this glass cloth, and a printed wiring board can be provided.

  Hereinafter, the embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications are possible without departing from the scope of the present invention. It is.

〔Glass cloth〕
The glass cloth of the present embodiment is a glass cloth formed by weaving glass yarns composed of a plurality of glass filaments as warp yarns and weft yarns, and the average filament diameters of the glass filaments constituting the warp yarns and the weft yarns are respectively Independently, the number of filaments of the warp and the weft is independently 20 to 300, and the driving density of the warp and the weft is independently 20 to 140. The dielectric constant of the glass cloth is 4.4 or less, and the warp of the printed wiring board composed of the glass cloth is 10 mm or less.

Among them, one of the warp and the weft is a glass yarn containing a glass filament having a SiO ₂ composition amount of 98 to 100 mass%, and the other of the warp and the weft is a SiO ₂ composition amount of 45 to 60 mass. The glass cloth includes a glass filament having a B ₂ O ₃ composition of 15 to 30% by mass, and the glass cloth has a dielectric constant of more than 3.8 and not more than 4.4. preferable.

When the SiO ₂ composition amount is set to 98 to 100% by mass, the dielectric constant decreases, but the drillability of the substrate tends to deteriorate. A typical glass has a Vickers hardness of about 640 kgf / mm ² , but a glass having a SiO ₂ composition of almost 100% has a Vickers hardness of about 820 kgf / mm ² , and the tip of the drill tip is significantly worn during drilling. There is a case.

Further, when the SiO ₂ composition amount is set to 98 to 100% by mass, the bending resistance of the glass filament is significantly lowered, and the glass filament may be broken or broken. Broken or broken glass filaments contribute to the fluff of glass cloth. Such fuzz, warping of the glass cloth, woven, because that may occur in the spreading step, SiO ₂ composition weight with glass filaments is 98 to 100 wt%, to produce a small glass cloth fluff Is not easy. In particular, in the case of warp yarns, in the warping and weaving processes, the glass yarn is in contact with many members such as a roll, so that fuzz is more likely to occur. In addition, in prepreg applications, glass filaments having such low bending resistance may cause fuzz during processing and tend to be less practical. The fluffing increases the probability that the fluffing part collides with the conductive layer when producing a laminated plate, and causes a defective projection and an interlayer insulation failure. Therefore, it is assumed that the glass cloth using the glass filament with the SiO ₂ composition amount of 98 to 100% by mass has a problem from the viewpoint of practicality.

  However, according to the glass cloth of the present embodiment, the warpage of the printed wiring board composed of the glass cloth is 10 mm or less, so that the dielectric constant is lower than before and the dimensional stability is excellent. It is possible to provide a glass cloth capable of producing a substrate. In addition, the substrate using the glass cloth of the present embodiment has achieved further lower dielectric constant and lower dielectric loss tangent, and can achieve each performance required with higher speed communication. .

  That is, as a result of intensive studies, the inventors have determined that the glass cloth of the present embodiment, that is, a glass cloth that satisfies the condition that the magnitude of warpage observed when a substrate is created under a predetermined condition is not more than a certain value. It has been found that when selected and used, it is possible to realize a substrate in which the dimensional change rate in the warp direction / weft direction is suppressed. The details of the mechanism by which the glass cloth that satisfies the certain conditions realizes a substrate with a reduced dimensional change rate are not detailed, but when creating the substrate, a threading process, an impregnation process, a pressing process, a cooling / curing process, etc. While various external forces applied to the glass cloth in the glass cloth are considered to be a cause of expanding the physical performance difference between the warp direction and the weft direction of the glass cloth, in the glass cloth with a small amount of warpage appearing in the film thickness direction under certain conditions, the glass cloth Differences in physical performance within the cloth tend to cancel each other. As a result, expansion of the difference in physical performance between the warp direction and the weft direction is also suppressed, and the dimensional change rate when the substrate state is not suppressed. It is guessed.

[Glass filament composition]
In the present embodiment, the composition of the glass yarn constituting the warp and the weft is not particularly limited, but one of the warp and the weft is a glass filament (hereinafter, referred to as SiO ₂ composition amount of 98 to 100% by mass). The glass yarn including “glass filament A”), and the other of the warp and the weft has a SiO ₂ composition of 45 to 60% by mass and a B ₂ O ₃ composition of 15 to 30% by mass. A glass yarn including a glass filament (hereinafter also referred to as “glass filament B”) is preferable. In this embodiment, one of the warp and the weft is a glass yarn made of glass filament A, and the other of the warp and the weft is a glass yarn made of glass filament B, one of the warp and weft is glass. An embodiment in which the other side of the warp and weft is a glass yarn made of glass filament A or a glass yarn made of glass filament B, and both the warp and weft are glass. The aspect which is a glass thread | yarn which consists of the filament A and the glass filament B is also contained.

[Glass filament A]
SiO ₂ composition of the glass filaments A is 98 to 100 wt%, preferably from 98 to 99.95 mass%, more preferably 98-99 wt%. When the SiO ₂ composition amount is 98% by mass or more, the dielectric constant and the dielectric loss tangent tend to be further reduced. In addition, when the SiO ₂ composition amount is 98% by mass or more, mixing of air during glass melt spinning is suppressed, and the generation of hollow fibers can be suppressed. By reducing the hollow fiber, the insulation reliability of the substrate tends to be further improved. Further, when the SiO ₂ composition amount is 99.95% by mass or less, the bending resistance and brittleness of the glass yarn tend to be further improved. As a result, the drillability of the substrate is further improved, and glass yarn breakage is less likely to occur at the time of fiber opening and water washing after the processing of the glass cloth, and the fluff amount of the glass cloth tends to decrease. . By using such a glass cloth, the dielectric constant is further lowered, and the insulation reliability derived from the hollow fiber reduction, the insulation reliability improved from the drilling workability of the substrate, and the fuzz reduction are reduced. The derived insulation reliability can be improved (prevention of plating soaking, protrusion failure, interlayer insulation failure, etc.). The SiO ₂ composition amount can be adjusted according to the amount of raw material used for glass filament preparation.

Further, the glass filament A may have other composition besides SiO ₂ . Other compositions are not particularly limited, and examples include Al ₂ O ₃ , CaO, MgO, B ₂ O ₃ , TiO ₂ , Na ₂ O, K ₂ O, Sr ₂ O ₃ , Fe ₂ O _{3 and the} like. It is done.

[Glass filament B]
SiO ₂ composition of the glass filaments B is 45 to 60 wt%, preferably from 50 to 60 wt%, more preferably from 51 to 56 wt%. Further, B ₂ O ₃ composition of the glass filaments B is 15 to 30 wt%, preferably from 20 to 30 wt%, more preferably from 21 to 25 wt%. Since the SiO ₂ composition amount is 60% or less and the B ₂ O ₃ composition amount is 15% by mass or more, the glass melt viscosity is lowered and the glass yarn is easily pulled, so that the occurrence of hollow fibers can be suppressed. In addition, the dielectric constant decreases. Further, when the SiO ₂ composition amount is 45% or more and the B ₂ O ₃ composition amount is 30 mass% or less, the moisture absorption resistance is further improved when the surface treatment is performed. On the other hand, when the B ₂ O ₃ composition amount is less than 15% by mass, the number of hollow fibers increases, and the insulation reliability decreases accordingly. Further, when the B ₂ O ₃ composition amount further decreases to the E glass composition amount, the number of hollow fibers tends to decrease, but the dielectric constant increases. On the other hand, if the B ₂ O ₃ composition amount is more than 30% by mass, the moisture absorption amount increases, so that the insulation reliability decreases. The B ₂ O ₃ composition amount can be adjusted according to the amount of raw material used for glass filament preparation.

Further, the glass filament B may have other composition besides SiO ₂ and B ₂ O ₃ . Other compositions are not particularly limited, and examples include Al ₂ O ₃ , CaO, MgO, B ₂ O ₃ , TiO ₂ , Na ₂ O, K ₂ O, Sr ₂ O ₃ , Fe ₂ O _{3 and the} like. It is done.

In the glass filament B, the Al ₂ O ₃ composition amount is preferably 11 to 16% by mass, and more preferably 12 to 16% by mass. When the Al ₂ O ₃ composition amount is within the above range, the productivity of the yarn tends to be further improved.

  In the glass filament B, the CaO composition amount is preferably 4 to 8% by mass, and more preferably 6 to 8% by mass. When the CaO composition amount is within the above range, the yarn productivity tends to be further improved.

[Average filament diameter of glass filament]
The average filament diameter of the glass filaments constituting the warp and the weft is 3 to 10 μm, preferably 6 to 9 μm. When the average filament diameter of the glass filament is within the above range, workability tends to be further improved when the obtained substrate is processed by a mechanical drill. In particular, when the average filament diameter of the glass filament is 6 μm or more, each filament is difficult to cut and the fluffing quality can be improved. Moreover, when the average filament diameter of the glass filament is 9 μm or less, the breakability of the drill tip can be improved when machining with a mechanical drill. When the warp or weft is a glass yarn made of glass filament A or B, the average filament diameter is the average filament diameter of glass filament A or B constituting the glass yarn, and the warp or weft is glass In the case of a glass yarn comprising filaments A and B, the average filament diameter is the average filament diameter of glass filaments A and B constituting the glass yarn.

  Especially the average filament diameter of the glass filament A becomes like this. Preferably it is 4-10 micrometers, More preferably, it is 6-10 micrometers, More preferably, it is 6-9 micrometers. When the average filament diameter of the glass filament A is 4 μm or more, the yarn breakage of the glass filament A is further suppressed, the amount of fluff of the glass cloth is reduced, and the insulation reliability derived from the reduction of fluff tends to be further improved. . Further, since the average filament diameter of the glass filament A is 10 μm or less, the area of contact between the matrix resin and the glass filament per unit volume increases, so that the ignition loss value is 0.2 mass% or more, which will be described later. The effect tends to be expressed more greatly.

  Moreover, the average filament diameter of the glass filament B becomes like this. Preferably it is 3-9 micrometers, More preferably, it is 4-8 micrometers, More preferably, it is 5-7 micrometers. When the average filament diameter of the glass filament B is 3 μm or more, the workability of the obtained substrate tends to be further improved. When the average filament diameter of the glass filament B is 9 μm or less, the area of contact between the matrix resin and the glass filament per unit volume increases, so that the effect described later by setting the ignition loss value to 0.2 mass% or more is obtained. It tends to be expressed more greatly.

[Number of filaments of glass filament]
The number of glass filaments constituting the warp and the weft is 20 to 300, preferably 20 to 200, independently. When the number of filaments of the glass filament is within the above range, workability tends to be further improved when the resulting substrate is processed with a mechanical drill. When the warp or weft is a glass yarn made of glass filament A or B, the number of filaments is the number of glass filaments A or B constituting the glass yarn, and the warp or weft is glass filament A and In the case of a glass yarn made of B, the number of filaments is the total number of glass filaments A and B constituting the glass yarn.

  In particular, when the warp or weft is a glass yarn comprising glass filament A, the number of filaments of glass filament A is preferably 20 to 250, more preferably 50 to 200, and even more preferably 75. ~ 150. When the number of filaments of the glass filament A is 20 or more, yarn breakage of the glass filament A is further suppressed, the amount of fluff of the glass cloth is reduced, and the insulation reliability derived from the reduction of fuzz tends to be further improved. . Further, when the number of filaments of the glass filament A is 250 or less, there is a tendency that a thinner glass yarn can be realized while suppressing fuzz due to the balance with the filament diameter.

  When the warp or weft is a glass yarn made of glass filament B, the number of filaments of glass filament B is preferably 50 to 300, more preferably 100 to 275, and even more preferably 150. ~ 250. When the number of filaments of the glass filament B is 50 or more, the workability of the obtained substrate tends to be further improved. When the number of filaments of the glass filament B is 300 or less, a thinner glass yarn tends to be realized due to the balance with the filament diameter.

[Pumping density]
The driving density of the warp and weft constituting the glass cloth is independently 20 to 140 yarns / inch, preferably 30 to 130 yarns / inch, and more preferably 40 to 120 yarns / inch.

[Tensile modulus]
The tensile elastic modulus of the glass yarn composed of the glass filament A is preferably 70 GPa or more, more preferably 72 GPa or more, and further preferably 75 GPa or more. Further, the tensile elastic modulus of the glass yarn composed of the glass filament A is preferably 100 GPa or less, more preferably 90 GPa or less, and further preferably 80 GPa or less. When the tensile elastic modulus of the glass yarn made of the glass filament A is 70 GPa or more, the waviness in the horizontal or vertical direction of the glass cloth tends to be improved.

  The tensile elastic modulus of the glass yarn composed of the glass filament B is preferably 50 GPa or more, more preferably 55 GPa or more, and further preferably 60 GPa or more. Moreover, the tensile elastic modulus of the glass yarn consisting of the glass filament B is preferably 80 GPa or less, more preferably 75 GPa or less, and further preferably 70 GPa or less. When the tensile elastic modulus of the glass yarn made of the glass filament B is within the above range, the glass filament is liable to be broken (fluff). Since the fluff becomes a protrusion at the time of the substrate and comes into contact with a conductor portion such as a copper foil, the insulation reliability in the Z direction of the substrate tends to be greatly deteriorated. Therefore, when the tensile elastic modulus is within the above range, the insulation reliability in the Z direction of the obtained substrate tends to be further improved.

  The ratio of the tensile elastic modulus of the glass yarn made of glass filament A to the tensile elastic modulus of the glass yarn made of glass filament B is preferably 1.3 or less, more preferably 1.2 or less. When the ratio of the tensile elastic modulus of the glass yarn consisting of the glass filament A to the tensile elastic modulus of the glass yarn consisting of the glass filament B is 1.3 or less, the anisotropy difference between the vertical and horizontal is reduced, and the warp of the substrate is further increased. It tends to be suppressed.

  The tensile elastic modulus can be measured by the method described in the examples.

〔thickness〕
The thickness of the glass cloth is preferably 5 μm to 100 μm, more preferably 20 μm to 100 μm, and even more preferably 30 to 90 μm.

[Cloth weight (weight)]
The cloth weight (weight per unit area) of the glass cloth is preferably 6 to 100 g / m ² , more preferably 7 to 90 g / m ² .

[Weaving structure]
The woven structure of the glass cloth is not particularly limited, and examples thereof include woven structures such as plain weave, Nanako weave, satin weave, and twill weave. Among these, a plain weave structure is more preferable.

  The skew of the weft and the warp of the glass cloth is preferably 0 to 20 mm, more preferably 0 to 15 mm, and further preferably 0 to 10 mm per meter when one glass yarn is vertical. In the glass cloth of this embodiment, since the physical performances in the warp direction and the weft direction are different, the substrate is likely to warp and the dimensional change rate is increased. Therefore, in this embodiment, the warp amount and the dimensional change rate of the substrate are reduced by manufacturing so that the weft and warp of the glass cloth is 20 mm or less per meter when one glass yarn is vertical. Improve. In order to reduce the skew to 20 mm or less, the standard deviation of flying arrival during weaving is set to 5 or less, the tension of the loom or processing machine is set to 100 N / m or more, and the parallelism of all rolls and all core tubes in the manufacturing process is set. It is effective to set it to 0.1 mm or less per meter. In the present embodiment, “slanting” refers to “a state of a woven fabric in which the weft and the warp are not perpendicular to each other” in JIS R 3410.

  Note that the details of the mechanism for realizing a substrate with a dimensional change rate suppressed by the glass cloth having a skew equal to or less than a certain level are not detailed, but in the substrate production, a threading process, an impregnation process, a pressing process While various external forces applied to the glass cloth in the cooling / curing process etc. are considered to be the cause of expanding the physical performance difference between the warp direction and the weft direction of the glass cloth, the glass cloth with a small amount of bending was subjected to external force. It is presumed that the expansion of the physical performance difference at the time is suppressed, and as a result, the dimensional change rate when the substrate state is reached is suppressed.

〔surface treatment〕
Glass yarn (including glass filaments) of glass cloth is surface-treated with a silane coupling agent, preferably a silane coupling agent having an unsaturated double bond group (hereinafter also simply referred to as “silane coupling agent”). It is preferable that By using a silane coupling agent having an unsaturated double bond group, the reactivity with the matrix resin is further improved, and a hydrophilic functional group is hardly generated after reacting with the matrix resin, and the insulation reliability is further improved. .

Although it does not specifically limit as a silane coupling agent, For example, the compound shown by following General formula (1) is mentioned. By using such a silane coupling agent, moisture absorption resistance is further improved, and as a result, insulation reliability tends to be further improved. In particular, by using a silane coupling agent having an unsaturated double bond group, it is possible to infiltrate the plating solution after drilling a glass cloth having a SiO ₂ composition of 98 to 100% by mass, insulation reliability, and fluffing. Quality can be improved.
X (R) _3-n SiY _n (1)
(In the formula, X is an organic functional group having at least one of an amino group and an unsaturated double bond group, Y is independently an alkoxy group, and n is 1 or more and 3 or less. And each R is independently a group selected from the group consisting of a methyl group, an ethyl group, and a phenyl group.)

  X is an organic functional group having at least one of an amino group and an unsaturated double bond group, more preferably an organic functional group having three or more, and an amino group and an unsaturated double bond group More preferably, it is an organic functional group having at least four of the above. When X is such a functional group, moisture absorption resistance tends to be further improved. The organic functional group having one or more unsaturated double bond groups represented by X is not particularly limited, and examples thereof include a vinyl group, an allyl group, a vinylidene group, an acryloxy group, and a methacryloxy group.

  Any form can be used as the alkoxy group, but an alkoxy group having 5 or less carbon atoms is preferable for stabilizing the glass cloth.

  Specific examples of silane coupling agents that can be used include, but are not limited to, 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, aminopropyltrimethoxysilane, vinyltrimethoxysilane, methacryloxypropyl Trimethoxysilane, methacryloxyoctyltrimethoxysilane, acryloxypropyl Known substances, such as trimethoxysilane and the like. The silane coupling agent tends to be excellent in reactivity with a glass cloth glass fiber (glass filament) and a matrix resin of a substrate, particularly a radical polymerization resin. Therefore, it is possible to suppress a decrease in insulation reliability resulting from the resin and the glass cloth being easily peeled at the interface, and to suppress a decrease in insulation reliability resulting from the plating solution soaking into the glass cloth.

  The molecular weight of the silane coupling agent is preferably 100 to 600, more preferably 150 to 500, and still more preferably 200 to 450. Among these, it is preferable to use a silane coupling agent having two or more types of unsaturated double bond groups having different molecular weights. By treating the glass yarn surface with two or more types of silane coupling agents having different molecular weights, the treatment agent density on the glass surface is increased, and the reactivity with the matrix resin tends to be further improved. In addition, the processing amount by the surface treating agent of glass cloth can be estimated by the following ignition loss value.

[Ignition loss value]
The ignition loss value of the glass cloth is 0.2% by mass or more, preferably 0.25% by mass or more, and more preferably 0.3% by mass or more. Moreover, the upper limit of the ignition loss value of the glass cloth is 1.0% by mass or less, preferably 0.9% by mass or less, more preferably 0.8% by mass or less. When the loss weight loss value of the glass cloth is 0.2% by mass or more, it is possible to improve the plating solution penetration, insulation reliability, and fluffing quality after drilling. Further, the moisture absorption resistance is further improved, and the decrease in insulation reliability due to moisture absorption can be further suppressed. Moreover, when the ignition loss value of the glass cloth is 1.0% by mass or less, the resin permeability to the glass cloth is further improved, and as a result, the insulation reliability is further improved.

  The “ignition loss value” mentioned here can be measured according to the method described in JIS R3420. That is, first, the glass cloth is placed in a dryer at 110 ° C. and dried for 60 minutes. After drying, the glass cloth is transferred to a desiccator, left for 20 minutes, and allowed to cool to room temperature. After standing to cool, the glass cloth is weighed in units of 0.1 mg or less. Next, the glass cloth is heated in a muffle furnace at 625 ° C. for 20 minutes. After heating in the muffle furnace, the glass cloth is transferred to a desiccator, left for 20 minutes, and allowed to cool to room temperature. After standing to cool, the glass cloth is weighed in units of 0.1 mg or less. The amount of silane coupling agent treated with glass cloth is defined by the ignition loss value obtained by the above measurement method.

[Dielectric constant of glass cloth]
The dielectric constant of the glass cloth is 4, 4 or less, preferably more than 3.8 and less than 4.4, and more preferably more than 3.8 and less than 4.2. The dielectric constant of the glass cloth can be measured by the method described in the examples.

[Glass cloth manufacturing method]
The manufacturing method of the glass cloth of the present embodiment is not particularly limited, but for example, conditions such as flying arrival standard deviation at the time of weaving, tension of the loom and processing machine, parallelism of all rolls and all core tubes in the manufacturing process, etc. The method of adjusting and adjusting so that the curvature of the printed wiring board obtained may be 10 mm or less is mentioned. In addition, when the surface of the glass yarn is surface-treated with a silane coupling agent, a coating step of almost completely covering the surface of the glass filament with the silane coupling agent with a treatment liquid having a concentration of 0.1 to 3.0% by mass; By fixing the silane coupling agent to the surface of the glass filament by heat drying and washing at least part of the silane coupling agent fixed to the surface of the glass filament with high-pressure spray water or the like, the ignition loss value is reduced. And a preparation step of adjusting the adhesion amount of the silane coupling agent so as to be 0.2 to 1.0% by mass.

  As the solvent for dissolving or dispersing the silane coupling agent, either water or an organic solvent can be used, but water is preferably used as the main solvent from the viewpoint of safety and protection of the global environment. As a method for obtaining a treatment liquid containing water as a main solvent, a method in which a silane coupling agent is directly added to water, an organic solvent solution is prepared by dissolving the silane coupling agent in a water-soluble organic solvent, and then the organic solvent solution is used. Any one of the methods of adding to water is preferable. In order to improve the water dispersibility and stability of the silane coupling agent in the treatment liquid, a surfactant may be used in combination.

  The covering step, the fixing step, and the preparation step are preferably performed on the glass cloth after the weaving step. Furthermore, you may have the fiber opening process which opens the glass yarn of a glass cloth after a weaving process as needed. In addition, when performing a preparation process after a weaving process, an adjustment process may serve as a fiber opening process. In addition, the composition of the glass cloth does not usually change before and after opening.

  It is considered that the silane coupling agent layer can be formed almost completely and uniformly on the entire surface of each glass filament constituting the glass yarn by the above production method.

  As a method of applying the treatment liquid to the glass cloth, (a) a method of storing the treatment liquid in a bath and immersing and passing the glass cloth (hereinafter referred to as “immersion method”), (b) a roll coater, a die coater, Or the method of apply | coating a process liquid directly to glass cloth with a gravure coater etc. is possible. When applying by the immersion method (a), the immersion time of the glass cloth in the treatment liquid is preferably selected to be 0.5 seconds or more and 1 minute or less.

  In addition, examples of the method for heating and drying the solvent after applying the treatment liquid to the glass cloth include known methods such as hot air and electromagnetic waves.

  The heating and drying temperature is preferably 90 ° C. or higher, and more preferably 100 ° C. or higher so that the reaction between the silane coupling agent and glass is sufficiently performed. Moreover, in order to prevent deterioration of the organic functional group which a silane coupling agent has, 300 degrees C or less is preferable, and if it is 200 degrees C or less, it is more preferable.

In addition, the opening method in the opening step is not particularly limited, and examples thereof include a method of opening a glass cloth with spray water (high-pressure water opening), vibrowasher, ultrasonic water, mangle and the like. . In the fiber opening process, in the case of a glass cloth having a SiO ₂ composition amount of 98 to 100% by mass, fuzz is likely to occur. On the other hand, the ignition loss value of the glass cloth of the present embodiment is 0.12% by mass or more, whereby fuzz can be suppressed. Further, in order to suppress a decrease in the tensile strength of the glass cloth due to the fiber opening process, it is preferable to take measures such as reducing friction of the contact member when weaving the glass yarn, optimizing the sizing agent and increasing the amount of adhesion. . There is a tendency that the air permeability can be further reduced by lowering the tension applied to the glass cloth during the opening process.

  Even after the opening process, an optional process may be included. Although it does not specifically limit as an arbitrary process, For example, a slit process process is mentioned.

  After the glass cloth is surface-treated, a matrix resin is applied to manufacture a prepreg. The storage period between the surface treatment of the glass cloth and the application of the matrix resin is preferably within 2 years. Moreover, it is preferable that storage temperature shall be 10-40 degreeC. When the storage temperature is 30 ° C. or lower, the deactivation of unsaturated double bond groups of the silane coupling agent on the surface of the glass cloth can be suppressed, and the reactivity with the matrix resin tends to be maintained. Moreover, it exists in the tendency which can suppress that the silane coupling agent reacts with the water adhering to the glass surface, and the convergence property of a glass filament bundle increases because storage period is less than two years. This tends to improve the permeability of the matrix resin.

[Prepreg]
The prepreg of this embodiment has the glass cloth and a matrix resin impregnated in the glass cloth. Accordingly, it is possible to provide a prepreg that is thin, has a low dielectric constant, and has improved insulation reliability and improved moisture absorption resistance related to the above reasons.

  As the matrix resin, either a thermosetting resin or a thermoplastic resin can be used. The thermosetting resin is not particularly limited. For example, a) a compound having an epoxy group and an amino group, a phenol group, an acid anhydride group, a hydrazide group, an isocyanate group, a cyanate group, and a hydroxyl group that react with the epoxy group. An epoxy that is cured by reacting with a compound having at least one of the above, without a catalyst, or by adding a catalyst having a reaction catalytic ability such as an imidazole compound, a tertiary amine compound, a urea compound, or a phosphorus compound. A resin; b) a radical polymerization curable resin in which a compound having at least one of an allyl group, a methacryl group, and an acryl group is cured using a thermal decomposition catalyst or a photodecomposition catalyst as a reaction initiator; c D) a maleimide triazine resin cured by reacting a compound having a cyanate group with a compound having a maleimide group; Imide compounds, thermosetting polyimide resin is cured by reacting an amine compound, a; benzoxazine resin to crosslink cured by thermal polymerization of a compound having e) benzoxazine ring are exemplified.

  The thermoplastic resin is not particularly limited. For example, polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyarylate, aromatic polyamide, polyether ether ketone, thermoplastic polyimide, insoluble polyimide, Examples include polyamide imide and fluororesin. Moreover, you may use together a thermosetting resin and a thermoplastic resin.

[Printed wiring board]
The printed wiring board of this embodiment has the prepreg. Thereby, a printed wiring board having a low dielectric constant and improved insulation reliability can be provided.

  Next, the present invention will be described in more detail with reference to examples and comparative examples. The present invention is not limited in any way by the following examples.

Example 1
Weft made of glass filaments with a SiO ₂ composition of 99.9% by mass (average filament diameter of glass filament 9 μm, number of filaments 100, implantation density 54 / inch), SiO ₂ composition 53% by mass, B ₂ O ₃ Glass warp (thickness 78 μm, fabric weight 70 g / m ² ) using warp (glass filament average filament diameter 6 μm, number of filaments 200, implantation density 61 / inch) composed of glass filaments with a composition amount of 23% by mass Was woven. The obtained glass cloth was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Toray Dow Corning Co., Ltd .; Z6032) dispersed in water. Immersion and heat drying. Next, high-pressure water opening was carried out by spraying and heat drying to obtain a product. The loss on ignition value of the glass cloth was 0.32% by mass. The skew of the weft of the glass cloth was 5 mm.

(Example 2)
Weft made of glass filaments with a SiO ₂ composition of 99.9% by mass (average filament diameter of glass filament 9 μm, number of filaments 100, implantation density 54 / inch), SiO ₂ composition 53% by mass, B ₂ O ₃ Glass warp (thickness 78 μm, fabric weight 70 g / m ² ) using warp (glass filament average filament diameter 6 μm, number of filaments 200, implantation density 61 / inch) composed of glass filaments with a composition amount of 23% by mass Was woven. The obtained glass cloth was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Toray Dow Corning Co., Ltd .; Z6032) dispersed in water. Immersion and heat drying. Next, high-pressure water opening was carried out by spraying and heat drying to obtain a product. The loss on ignition value of the glass cloth was 0.32% by mass. The skew of the weft of the glass cloth was 10 mm.

(Example 3)
Weft made of glass filaments with a SiO ₂ composition of 99.9% by mass (average filament diameter of glass filament 9 μm, number of filaments 100, implantation density 54 / inch), SiO ₂ composition 53% by mass, B ₂ O ₃ Glass warp (thickness 78 μm, fabric weight 70 g / m ² ) using warp (glass filament average filament diameter 6 μm, number of filaments 200, implantation density 61 / inch) composed of glass filaments with a composition amount of 23% by mass Was woven. The obtained glass cloth was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Toray Dow Corning Co., Ltd .; Z6032) dispersed in water. Immersion and heat drying. Next, high-pressure water opening was carried out by spraying and heat drying to obtain a product. The loss on ignition value of the glass cloth was 0.32% by mass. The skew of the weft of the glass cloth was 18 mm.

Example 4
Weft made of glass filaments having a SiO ₂ composition of 99.9% by mass (average filament diameter of glass filament 9 μm, number of filaments 100, implantation density 54 / inch), SiO ₂ composition of 59% by mass, B ₂ O ₃ Glass warp (thickness 78 μm, fabric weight 70 g / m ² ) using warps (glass filament average filament diameter 6 μm, number of filaments 200, implantation density 61 / inch) composed of glass filaments with a composition amount of 16% by mass Was woven. The obtained glass cloth was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Toray Dow Corning Co., Ltd .; Z6032) dispersed in water. Immersion and heat drying. Next, high-pressure water opening was carried out by spraying and heat drying to obtain a product. The loss on ignition value of the glass cloth was 0.32% by mass. The skew of the weft of the glass cloth was 10 mm.

(Example 5)
Wefts composed of glass filaments with a SiO ₂ composition of 99.9% by mass (average filament diameter of glass filament 9 μm, number of filaments 100, implantation density 54 / inch) and glass filaments with a SiO ₂ composition of 99.9% by mass A glass cloth (thickness 78 μm, cloth weight 69 g / m ² ) was woven using warps (average filament diameter of glass filament 9 μm, number of filaments 100, implantation density 54 / inch). The obtained glass cloth was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Toray Dow Corning Co., Ltd .; Z6032) dispersed in water. Immersion and heat drying. Next, high-pressure water opening was carried out by spraying and heat drying to obtain a product. The loss on ignition value of the glass cloth was 0.24% by mass. The skew of the weft of the glass cloth was 10 mm.

(Comparative Example 1)
Weft made of glass filaments with a SiO ₂ composition of 99.9% by mass (average filament diameter of glass filament 9 μm, number of filaments 100, implantation density 54 / inch), SiO ₂ composition 53% by mass, B ₂ O ₃ Glass warp (thickness 78 μm, fabric weight 70 g / m ² ) using warp (glass filament average filament diameter 6 μm, number of filaments 200, implantation density 61 / inch) composed of glass filaments with a composition amount of 23% by mass Was woven. The obtained glass cloth was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Toray Dow Corning Co., Ltd .; Z6032) dispersed in water. Immersion and heat drying. Next, high-pressure water opening was carried out by spraying and heat drying to obtain a product. The loss on ignition value of the glass cloth was 0.32% by mass. The skew of the weft of the glass cloth was 22 mm.

(Comparative Example 2)
Weft made of glass filaments with a SiO ₂ composition of 99.9% by mass (average filament diameter of glass filament 9 μm, number of filaments 100, implantation density 54 / inch), SiO ₂ composition 53% by mass, B ₂ O ₃ Glass warp (thickness 78 μm, fabric weight 70 g / m ² ) using warp (glass filament average filament diameter 6 μm, number of filaments 200, implantation density 61 / inch) composed of glass filaments with a composition amount of 23% by mass Was woven. The obtained glass cloth was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Toray Dow Corning Co., Ltd .; Z6032) dispersed in water. Immersion and heat drying. Next, high-pressure water opening was carried out by spraying and heat drying to obtain a product. The loss on ignition value of the glass cloth was 0.32% by mass. The skew of the weft of the glass cloth was 30 mm.

(Comparative Example 3)
Wefts composed of glass filaments with a SiO ₂ composition of 53% by mass and a B ₂ O ₃ composition of 23% by mass (average filament diameter of glass filament 6 μm, number of filaments 200, implantation density 60 / inch) and SiO ₂ composition Glass warp (thickness 78 μm) using warp (glass filament average filament diameter 6 μm, number of filaments 200, driving density 61 / inch) consisting of 53% by mass and B ₂ O ₃ composition 23% by mass glass filaments Woven fabric weight 72 g / m ² ). The obtained glass cloth was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Toray Dow Corning Co., Ltd .; Z6032) dispersed in water. Immersion and heat drying. Next, high-pressure water opening was carried out by spraying and heat drying to obtain a product. The loss on ignition value of the glass cloth was 0.32% by mass. The skew of the weft of the glass cloth was 22 mm.

(Comparative Example 4)
Wefts composed of glass filaments with a SiO ₂ composition of 99.9% by mass (average filament diameter of glass filament 9 μm, number of filaments 100, implantation density 54 / inch) and glass filaments with a SiO ₂ composition of 99.9% by mass A glass cloth (thickness 78 μm, cloth weight 69 g / m ² ) was woven using warps (average filament diameter of glass filament 9 μm, number of filaments 100, implantation density 54 / inch). The obtained glass cloth was treated with N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Toray Dow Corning Co., Ltd .; Z6032) dispersed in water. Immersion and heat drying. Next, high-pressure water opening was carried out by spraying and heat drying to obtain a product. The loss on ignition value of the glass cloth was 0.24% by mass. The skew of the weft of the glass cloth was 21 mm.

<Evaluation method of ignition loss value of glass cloth>
The ignition loss value was measured according to the method described in JIS R3420. Specifically, the glass cloth was placed in a dryer at 105 ° C. ± 5 ° C. and dried for at least 30 minutes. After drying, the glass cloth was transferred to a desiccator and allowed to cool to room temperature. After standing to cool, the weight of the glass cloth was measured in units of 0.1 mg or less. Next, the glass cloth was heated in a muffle furnace at about 625 ° C. for 20 minutes. After heating in the muffle furnace, the glass cloth was transferred to a desiccator and allowed to cool to room temperature. After standing to cool, the weight of the glass cloth was measured in units of 0.1 mg or less. The change in weight before and after heating of the muffle furnace was measured, and the ignition loss value was calculated as the amount of treatment agent attached.

<Measuring method of skew>
The weft and warp skew was measured according to the method described in JISL1096.

<Evaluation method of glass cloth thickness>
According to JIS R 3420 7.10, using a micrometer, the spindle was gently rotated to lightly contact the measurement surface in parallel. The scale after the ratchet made three sounds was read.

<Evaluation of fluff of prepreg (flexibility evaluation)>
Polyphenylene ether resin varnish (mixture of modified polyphenylene ether resin 30 parts by mass, triallyl isocyanurate 10 parts by mass, toluene 60 parts by mass, catalyst 0.1 part by mass) is added to the glass cloth obtained in the above-mentioned examples and comparative examples. A prepreg was obtained after impregnation and drying at 120 ° C. for 2 minutes. The resin content of this prepreg was adjusted to 50% by mass. Next, a small sample of 100 mm × 100 mm at an arbitrary location was cut out, and the number of protrusions was determined visually.

<Evaluation method of dielectric constant of substrate and glass cloth>
A substrate was prepared as described above so that the resin content per 100% by mass of the prepreg was 60% by mass, and the copper foil was removed to obtain a sample for dielectric constant evaluation. The dielectric constant of the obtained sample at a frequency of 1 GHz was measured using an impedance analyzer (manufactured by Agilent Technologies). From the obtained substrate dielectric constant, the dielectric constant of the glass cloth was calculated based on the volume fraction of the glass cloth and the resin dielectric constant of 2.5.

<Manufacturing method of substrate>
Epoxy resin varnish (low brominated bisphenol A type epoxy resin (DIC, 1121N-80M) 40 parts by mass, o-cresol type novolac epoxy resin (DIC) N680-75M) impregnated with 10 parts by mass, 50 parts by mass of 2-methoxyethanol, 1 part by mass of dicyandiamide, and 0.1 parts by mass of 2-ethyl-4-methylimidazole) and dried at 120 ° C. for 2 minutes. A prepreg was obtained. This prepreg was stacked, a copper foil having a thickness of 12 μm was stacked on the top and bottom, and heated and pressed at 200 ° C. and 40 kg / cm ² for 60 minutes to obtain a substrate.

<Evaluation method of substrate warpage>
As described above, a substrate was prepared so that the resin content per 100% by mass of the prepreg was 60% by mass, and the copper foil was removed to obtain a sample for warpage evaluation. The obtained sample was cut into a size of 50 mm × 200 mm, heated at 200 ° C. for 30 minutes, placed on a flat desk, cooled to room temperature, and the warp height of four pieces of the sample was measured. The maximum value of the four pieces was determined as the substrate warpage.

<Evaluation method of dimensional change of substrate>
The substrate was prepared as described above so that the resin content per 100% by mass of the prepreg was 60% by mass, and was cut into 350 mm × 350 mm to obtain a sample for dimensional evaluation. The obtained sample was processed with nine holes of 100 mm with a 0.5 mmφ drill, and the position (A) was measured with a three-dimensional measuring machine (manufactured by NIKON; VM-500N). Further, the copper foil of the sample was removed, heated at 200 ° C. for 30 minutes, cooled to room temperature, and the positions (B) of nine through holes were measured. The maximum value of the rate of change between the position (A) and the position (B) was obtained as the substrate dimension change.

  The evaluation results of the glass cloth shown in Examples and Comparative Examples are summarized in Table 1.

  It was found that the substrate obtained by using the glass cloth of the example had a low dielectric constant and was very excellent in substrate warpage and dimensional change.

  The glass cloth of the present invention has industrial applicability as a base material used for a printed wiring board used in the electronic / electric field.

Claims (12)

A glass cloth formed by weaving glass yarns composed of a plurality of glass filaments as warps and wefts,
The average filament diameters of the glass filaments constituting the warp and the weft are each independently 3 to 10 μm,
The number of filaments of the warp and the weft are each independently 20 to 300,
The driving density of the warp and the weft is 20 to 140 pieces / inch independently of each other,
The dielectric constant of the glass cloth is 4.4 or less,
The warp of the printed wiring board composed of the glass cloth is 10 mm or less,
Glass cloth. One of the warp and the weft is a glass yarn containing a glass filament whose SiO ₂ composition is 98 to 100% by mass,
The other of the warp and the weft is a glass yarn including a glass filament having a SiO ₂ composition amount of 45 to 60% by mass and a B ₂ O ₃ composition amount of 15 to 30% by mass,
The dielectric constant of the glass cloth is more than 3.8 and less than 4.4.
The glass cloth according to claim 1. The average filament diameter of the glass filament whose SiO ₂ composition is 98 to 100% by mass is 6 to 9 μm.
The glass cloth according to claim 1 or 2. The thickness is 30 to 90 μm.
The glass cloth of any one of Claims 1-3. The tensile elastic modulus of the glass yarn composed of the glass filament with the SiO ₂ composition amount of 98 to 100% by mass is 70 GPa or more,
The SiO ₂ composition amount is 45 to 60 wt%, relative to the tensile modulus of the glass fiber in which the B ₂ O ₃ composition amount is made of the glass filaments is 15 to 30 wt%, the SiO ₂ composition weight 98 to The ratio of the tensile elastic modulus of the glass yarn comprising the glass filament that is 100% by mass is 1.3 or less,
The glass cloth of any one of Claims 1-4. One of the warp and the weft is a glass yarn containing a glass filament whose SiO ₂ composition is 98 to 99.95% by mass,
The glass cloth of any one of Claims 1-5. The other of the warp and the weft is a glass yarn containing a glass filament whose SiO ₂ composition is 50 to 60% by mass and whose B ₂ O ₃ composition is 20 to 30% by mass,
The glass cloth of any one of Claims 1-6. The ignition loss value of the glass cloth is 0.2% by mass or more and 1.0% by mass or less.
The glass cloth according to any one of claims 1 to 7. The skew of the weft and the warp of the glass cloth is 0 to 20 mm per meter when one glass yarn is vertical.
The glass cloth according to any one of claims 1 to 8. The surface of the glass yarn was treated with a silane coupling agent,
The glass cloth of any one of Claims 1-9. The glass cloth according to any one of claims 1 to 10,
A matrix resin impregnated in the glass cloth,
Prepreg. The prepreg according to claim 11.
Printed wiring board.