TW202142750A - Glass cloth, prepreg, and printed wiring board - Google Patents

Abstract

Provided is a glass cloth (1) in which glass threads comprising a plurality of glass filaments are constituted as warp and woof, the width (t) of a direction (TD) forming a 90 DEG angle with the warp being 1000 mm or more, wherein the glass cloth has a dielectric constant (Dk) of 5.0 or less and a thickness of 35 [mu]m or less, and when the tensile force in a direction (MD) parallel to the warp is set at 50N, the slack amount (maximum value of x) in a perpendicular direction (z) is 10 mm/m or less.

Description

Glass cloth, prepreg, and printed circuit board

The invention relates to a glass cloth, a prepreg, a printed circuit board and the like.

At present, with the advancement of high-performance and high-speed communication of information terminals such as smart phones, the printed circuit boards used are becoming more dense, ultra-thin, low dielectric constant, and low dielectric loss factor. Significant development.

As the insulating material of the printed circuit board, the following laminated board is widely used, which is a prepreg bulk layer obtained by impregnating a glass cloth in a thermosetting resin such as epoxy resin (hereinafter referred to as "matrix resin") It is made by heat and pressure hardening. The dielectric constant of the matrix resin used for the above-mentioned high-speed communication substrates is about 3, compared to this, the dielectric constant of the usual E glass cloth is about 6.7, which gradually shows the problem of high dielectric constant during lamination. Furthermore, it is known as Edward A. Wolff's formula: Transmission loss∝√ε×tanδ As shown, the smaller the dielectric constant (ε) and dielectric loss factor (tanδ) of the material, the more improved the signal transmission loss. Therefore, a low dielectric constant glass cloth is proposed, which is formed of D glass, NE glass, L glass, etc., which have a glass composition different from E glass (for example, refer to Patent Documents 1 to 4). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 5-170483 [Patent Document 2] Japanese Patent Laid-Open No. 2009-263569 [Patent Document 3] Japanese Patent Laid-Open No. 2009-19150 [Patent Document 4] Japanese Patent Laid-Open No. 2009-263824

[The problem to be solved by the invention]

Previously, in the surface treatment step of glass cloth manufacturing or the resin coating step of prepreg manufacturing, when pressure is applied in the thickness direction of the glass cloth in order to scrape off excess treatment liquid or resin, breakage may occur. Regarding the occurrence of damage, try to reduce the tension in the length direction (MD) of the glass cloth or reduce the pressure in the thickness direction (twisting pressure) due to the surface treatment step.

However, in recent years, as the demand for low-dielectric constant glass cloth or ultra-thin glass cloth with lower strength has increased, the frequency of breakage of the glass cloth has further increased. Even if the MD tension or the pressure in the thickness direction is reduced as before, the glass cloth that is thinner and has a lower dielectric constant cannot be prevented from breaking.

Therefore, the object of the present invention is to suppress the surface of glass cloth with a width of 1000 mm or more in the direction (TD) at 90° to the warp and a relative permittivity (Dk) of 5.0 or less and a thickness of 35 μm or less. Breakage occurs during the processing step and/or the prepreg manufacturing step, and/or the frequency of breakage is reduced. [Technical means to solve the problem]

The inventors conducted intensive research and found that for low-dielectric and extremely thin glass cloth, it is specified that even when the tension of the warp yarn is set to a uniform condition in the width direction, it is used as a glass cloth fabric during production The slack is also generated in a part of the width direction, and the slack is controlled, thereby solving the above-mentioned problems, thereby completing the present invention.

That is, the present invention is as follows. (1) A glass cloth, which is composed of glass yarns containing a plurality of glass filaments as warp yarns and weft yarns, with a width of 1000 mm or more in the direction (TD) at 90° to the warp yarns, and having a width of 5.0 or less Relative permittivity (Dk) and thickness below 35 μm, and when the tension in the direction parallel to the warp (MD) is set to 50 N, the slack in the vertical direction is below 10 mm/m. (2) The glass cloth as described in item (1), wherein the ratio of the warp tension at the center portion to the tension at the end warp yarns (center warp tension/end warp tension) of the glass cloth is 0.8 or more and 1.2 or less. (3) The glass cloth as described in item (1) or (2), wherein in the state where the glass cloth with a width of 1.3 m is wound with 1000 m, the center part and the end part of the glass cloth The winding hardness difference is 10 or less. (4) The glass cloth as described in any one of items (1) to (3), wherein the center and ends of the glass cloth have a difference in the slope of the stress-strain curve in the direction (MD) parallel to the warp yarn Less than 10%. (5) The glass cloth described in any one of items (1) to (4), wherein the weft skew amount of the weft yarn is 10 mm or less. (6) The glass cloth according to any one of items (1) to (5), wherein the thickness of the glass cloth is 25 μm or less. (7) The glass cloth as described in any one of items (1) to (6), wherein the thickness of the glass cloth is 17 μm or less. (8) The glass cloth as described in any one of items (1) to (7), wherein the tensile strength in the direction (MD) parallel to the warp yarn is 150 N/25 mm or less. (9) The glass cloth as described in any one of items (1) to (8), wherein the unit bending rigidity in the direction (TD) at 90° to the warp yarn is 0.03 gf·cm ² /cm or less. (10) The glass cloth according to any one of items (1) to (9), wherein the width of the glass cloth in the direction (TD) at 90° to the warp yarn is 2000 mm or less. (11) The glass cloth as described in any one of items (1) to (10), wherein the amount of slack is 6 mm/m or less. (12) The glass cloth as described in item (11), wherein the amount of slack is 4 mm/m or less. (13) The glass cloth as described in item (12), wherein the amount of slack is 2 mm/m or less. (14) A prepreg comprising: the glass cloth as described in any one of items (1) to (13), and a matrix resin impregnated in the glass cloth. (15) A printed circuit board comprising the prepreg as described in item (14). (16) A glass cloth roll comprising: a core tube and a glass cloth wound around the core tube, the glass cloth being composed of glass yarns including a plurality of glass filaments as warp yarns and weft yarns, and The glass cloth is wound around a core tube made of acrylonitrile-butadiene-styrene copolymer (ABS) with a core tube diameter of 200 mm and a width of 1.3 m. The difference in winding hardness is 10 or less. [Effects of the invention]

According to the present invention, when the low-dielectric and extremely thin glass cloth is supplied to the surface treatment step and/or the prepreg manufacturing step, the glass cloth can be prevented from being damaged or the frequency of damage can be reduced.

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 to this, and various changes can be made without departing from the spirit thereof.

[Glass cloth] Generally speaking, glass cloth is constructed by weaving glass yarns including a plurality of glass filaments as warp yarns and weft yarns.

In this manual, the machine direction (MD) is the direction parallel to the warp yarns set during the weaving step, the width direction (TD) is the direction where the glass cloth surface is woven at 90° to the MD, and the z direction is perpendicular to the The direction of the glass cloth surface composed of MD and TD.

The glass cloth of this embodiment has a relative permittivity (Dk) of 5.0 or less and a thickness of 35 μm or less. In this specification, the relative permittivity (Dk) refers to the relative permittivity at a frequency of 10 GHz unless otherwise specified. The relative dielectric constant and thickness are measured by the methods described in the examples.

In addition, the relative permittivity of the glass cloth of the present embodiment is preferably 4.7 or less, more preferably 3.8 or less or 3.7 or less. The lower limit of the relative permittivity may exceed zero, for example.

When measuring along the z-direction according to the method described in the examples, the thickness of the glass cloth of this embodiment is 35 μm or less, and from the viewpoint of ultra-thin prepreg and substrate, it is preferably 30 μm or less , More preferably 25 μm or less or 20 μm or less, and still more preferably 17 μm or less or 15 μm or less. In addition, the lower limit of the thickness obviously exceeds 0 μm, and from the viewpoint of suppression of breakage, the diameter of the glass yarn, and the opening step, it may be 1 μm or more.

Regarding the glass cloth of this embodiment, the width of TD is 1000 mm or more, and as shown below, it is characterized by the amount of slack measured under specific conditions. The upper limit of the TD width of the glass cloth can be determined according to the type or size of the weaving machine, for example, it can be under 2000 mm, under 1500 mm, under 1400 mm, under 1300 mm, or under 1200 mm.

[Relaxation] Regarding the glass cloth of this embodiment, the width of the direction (TD) at 90° to the warp yarn is 1000 mm or more, and the slack in the z direction when the tension in the direction (MD) parallel to the warp yarn is set to 50 N is Below 10 mm/m. The amount of relaxation was measured by the method described in the examples with reference to FIG. 1. When focusing on the surface treatment steps and prepreg manufacturing steps in the manufacturing process of glass cloth with a Dk of 5.0 or less and a thickness of 35 μm or less, it was found that there is a tendency that the end (2) of the glass cloth is easier than the center. When slack is generated, if an external force is applied in the thickness (z) direction, wrinkles and breakage will be generated in the slack portion (3). In addition, it has also been found that this tendency is more pronounced in low-dielectric glasses such as L glass and Q glass. Furthermore, the part from both ends to 20% of the total length (t) in the width direction (TD) of the glass cloth is called the glass cloth end (2), and the part of the glass cloth excluding the end is called For the central part. As mentioned above, the width and total length t shown in Figure 1 is 1000 mm or more.

Considering the tendency of breakage described above, it can be seen that by reducing the amount of slack of the glass cloth (1) (the maximum value of x in Fig. 1a), breakage can be suppressed during the surface treatment step and the prepreg manufacturing step. And can reduce the frequency of production. Specifically, if the slack of the glass cloth is adjusted to a range of 10 mm/m or less, the frequency of occurrence can be reduced by about 80% compared with the glass cloth with a slack exceeding 10 mm/m. From this point of view, the slack of the glass cloth is 10 mm/m or less, preferably 6 mm/m or less or 5 mm/m or less, more preferably 4 mm/m or less or 3 mm/m or less, and more preferably It is 2 mm/m or less or 1 mm/m or less.

If gravity is considered, the lower limit of the slack of the glass cloth obviously exceeds 0 mm/m, for example, it can be 0.1 mm/m, or it can be 0.1 mm/m or more. As a method of controlling the amount of slack within the range of 10 mm/m or less, for example, the warp tension in the TD direction can be made uniform. Specifically, the tension of the warp in the center of the glass cloth described above is relative to the end of the glass cloth. The warp tension ratio is set to 1.2 or less or less than 1.2 (specifically, in order to prevent end slack, for example, central warp tension/end warp tension≦1.2 or central warp tension/end warp tension <1.2, which is more Preferably 0.8≦central warp tension/end warp tension≦1.2, more preferably 0.8≦central warp tension/end warp tension<1.2, and more preferably 0.8≦central warp tension/end warp tension≦1.1 )Wait. In addition, by making the warp tension in the TD direction uniform, not only the slack at the end of the glass cloth can be suppressed, but the slack at the center can also be suppressed.

The ratio of the tension of the warp yarns at the center of the glass cloth to the tension of the warp yarns at the ends can be determined by measuring the total warp tensions and finding the difference between the average tension at the ends and the average tension at the center. Specifically, it can be measured by the method described in the examples. As a method of adjusting the ratio of the tension of the warp yarns at the center portion of the glass cloth to the tension of the warp yarns at the end portions within the above-mentioned range, for example, changing the tension of the yarn feeding at the end and the center portion of the glass cloth can be exemplified. In addition, the part from both ends to 20% of the total length (t) of the glass cloth in the width direction (TD) is called the glass cloth end, and the part of the glass cloth excluding the end is called the center part .

[Winding characteristics] Regarding the glass cloth of the present embodiment, it is preferable that the difference in the winding hardness between the center part and the end part of the glass cloth is 10 or less in a state where the glass cloth is wound with a width of 1.3 m in a 1000 m roll. The winding hardness difference is measured by the method described in the examples.

If the winding hardness difference is within the range of 10 or less, the glass cloth breakage in the surface treatment step and the prepreg manufacturing step tends to decrease in frequency. From this viewpoint, the difference in winding hardness is more preferably 8 or less, and still more preferably 6 or less. The lower limit of the winding hardness difference obviously exceeds 0, for example, it may be 1 or more or 2 or more.

The winding hardness difference can be adjusted to a range of 10 or less, for example, by making the warp binding yarn of the loom thinner than the warp yarn used, specifically, so that the TEX of the warp yarn is relatively Weaving is performed in such a way that the ratio of the TEX of the ground warp binding yarn exceeds 1 (that is, the warp yarn TEX/the ground warp binding yarn TEX>1).

[S-S curve characteristics] It is preferable that the center part and the end part of the glass cloth of this embodiment have a slope difference of the stress-strain curve (S-S curve) in the direction (MD) parallel to the warp yarns of 10% or less. The MD S-S curve and slope of the glass cloth were measured by the method described in the examples.

In the SS curve of the MD of the glass cloth, if the difference between the slope of the center of the glass cloth and the slope of the end of the glass cloth is less than 10%, there is a frequency of breakage of the glass cloth in the surface treatment step and the prepreg manufacturing step The tendency to decrease. From this viewpoint, the slope difference of the S-S curve of MD is more preferably 5% or less, still more preferably 3% or less, and still more preferably 1% or less. The lower limit of the slope difference of the S-S curve of MD obviously exceeds 0%.

The slope difference of the S-S curve of MD can be adjusted to be within a range of 10% or less by, for example, spreading the glass cloth uniformly along TD during the spreading step to reduce the line width difference between the center and the end of the glass cloth. Specifically, in the opening step, the ratio of the water pressure at the center of the glass cloth to the water pressure at the ends of the glass cloth can be adjusted to less than 1.2 (that is, the water pressure at the center/end opening water Pressure <1.2).

The components of the glass cloth of this embodiment are as follows.

[Glass Type] As long as the slack of the obtained glass cloth is within the numerical range described above, the glass type of the glass filaments constituting the glass yarn is selected from D glass, NE glass, L glass, NL glass, L2 glass, and Q glass. At least one of the groups is sufficient. From the viewpoint of low dielectric constant, slack, and suppression of breakage, it is preferable to use L glass, NL glass, L2 glass, or Q glass.

[Glass filament composition] The glass filament may have a _{composition of SiO 2} , may have a _{composition other than SiO 2} , or may have a composition other _{than SiO 2.} The other composition is not particularly limited, and examples thereof 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. The composition amount can be adjusted by the amount of raw materials used to make the glass filament. From the viewpoint of adjusting the CTE (coefficient of thermal expansion, coefficient of thermal expansion) to be lower, the SiO ₂ content is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% or more, and still more It is preferably more than 95%, particularly preferably more than 99%.

[Average diameter of glass filament] The average filament diameter of the glass filaments constituting the glass yarn is preferably 2 μm to 10 μm, more preferably 3.5 μm to 8 μm, and still more preferably 4 μm to 6 μm. By making the average fiber diameter of the glass filaments 2 μm or more, even for the tension or processing pressure applied to the glass filaments in the weaving step, the water washing step, and the fiber opening step, it is not easy to cause breakage, and the fluffing can be suppressed. In addition, by adjusting the average wire diameter of the warp and weft to 10 μm or less, the thickness of the glass cloth can be reduced, and a thinner substrate can be obtained. It can suppress the tension or processing pressure in the weaving step, washing step, fiber opening step, suppress fluffing, and realize a thinner glass cloth. In particular, by adjusting the average diameter of the glass filaments within the range of 4 μm to 6 μm, the deviation of the thickness of the glass cloth can be suppressed.

[Number of glass filaments] The number of glass filaments constituting the glass filaments of the glass yarn is preferably 30 to 200, and more preferably 40 to 100. By setting the number of glass filaments within the above range, tension or processing pressure can be suppressed during the weaving step, water washing step, or fiber opening step, and fluffing can be suppressed.

[Weft skew amount] The weft yarn constituting the glass cloth of this embodiment preferably has a weft skew amount of (15÷1000)=0.015 mm/width (mm) or less than 0.015 mm/width (mm). In this specification, the weft skew amount refers to the largest value among _{Z N} (Z ₀ , Z ₁ , and Z _{2) defined by the following formula (I).} Z _N =|(Y _N+1 −Y _N )/(X _N+1 −X _N )| (I) {where, N is 0～2, and the value of _{X N+1} −X _{N is 0} In this case, Z _N is 0}

In formula (I), X ₀ ～X ₃ and Y ₀ ～Y _{3 are} based on (X ₀ ,Y ₀ ), (X ₁ ,Y ₁ ), (X ₂ ,Y ₂ ), and (X ₃ ,Y ₃ The combination performance of) is defined as follows. A glass cloth, prepreg or printed circuit board containing a plurality of warp yarns and a plurality of weft yarns is used as the tested sample, the warp direction of the tested sample is set to the Y direction, and the direction perpendicular to the Y direction is set to the X direction, Regarding the weft yarns extending from the first warp yarn to the second warp yarn among the first and second warp yarns located at the two ends of the tested sample, the point of contact between the first warp yarn and the above weft yarn is defined as the origin (0,0), namely ( X ₀ ,Y ₀ ) Y axis and X axis. Furthermore, taking the contact point between the second warp yarn and the weft yarn as the end point (X ₃ , Y ₃ ), the coordinate Y of the weft yarn on the X axis and the Y axis takes one of the maximum and minimum points as (X ₁ ,Y ₁ ), the other is set to (X ₂ ,Y ₂ ), in this case, (X ₀ ,Y ₀ ), (X ₁ ,Y ₁ ), (X ₂ ,Y ₂ ), And (X ₃ , Y ₃ ) are arranged on the weft yarn in this order.

Hereinafter, referring to Figs. 2 to 4, the calculation methods of _{Z 0} , Z ₁ , and Z _{2 are shown by way of example.} Figures 2 to 4 are schematic diagrams showing one form of the weft yarn. The shape of the weft yarn in this embodiment is not limited to the shape of the weft yarn in FIGS. 2 to 4.

In Figure 2, the origin (X ₀ ,Y ₀ ), the point where the maximum value of Y is taken (X ₁ , Y ₁ ), the point where the minimum value of Y is taken (X ₂ , Y ₂ ), and the end point (X ₃ , Y ₃ ) is arranged on the weft yarn in this order. Z ₀ is calculated by substituting two adjacent points (X ₀ , Y ₀ ) and (X ₁ , Y ₁ ) into the above formula (I), and Z ₁ is calculated by substituting two adjacent points (X ₁ , Y ₁₎ ) And (X ₂ , Y ₂ ) are substituted into the above formula (I) and calculated, Z ₂ is calculated by substituting two adjacent points (X ₂ , Y ₂ ) and (X ₃ , Y ₃ ) into the above formula (I) Figure out.

In Figure 3, the origin (X ₀ ,Y ₀ ), the point where the maximum value of Y is taken (X ₁ , Y ₁ ), the point where the minimum value of Y is taken (X ₂ , Y ₂ ), and the end point (X ₃ , Y ₃ ) is arranged on the weft yarn in this order. Here, (X ₂ , Y ₂ ) and (X ₃ , Y ₃ ) represent the same coordinate. Z ₀ , Z ₁ , and Z ₂ can be calculated in the same manner as in the description of Fig. 2 above. Furthermore, since (X ₂ , Y ₂ ) and (X ₃ , Y ₃ ) represent the same coordinate, Z ₂ takes a value of 0 in the above formula (I).

In Figure 4, the origin (X ₀ ,Y ₀ ), the point where the maximum value of Y is taken (X ₁ , Y ₁ ), the point where the minimum value of Y is taken (X ₂ , Y ₂ ), and the end point (X ₃ , Y ₃ ) are arranged on the weft yarn in this order, where (X ₀ ,Y ₀ ) and (X ₁ ,Y ₁ ) represent the same coordinate, and (X ₂ ,Y ₂ ) and (X ₃ ,Y ₃ ) represent The same coordinates, Z ₀ , Z ₁ , and Z ₂ can be calculated in the same way as in the description of Fig. 2 above. Furthermore, since (X ₀ ,Y ₀ ) and (X ₁ ,Y ₁ ) represent the same coordinate, Z ₀ takes the value of 0 in the above formula (I), and Z ₂ also takes the value of 0.

In this specification, the maximum value of the measured value of the weft skew amount is set as the weft skew amount in this embodiment. The amount of weft skew is measured by the method described in the examples in accordance with JIS L1096.

If the weft skew amount of the weft yarn is within the range of 15 mm or less, even if the glass cloth has a Dk of 5.0 or less and a thickness of 35 μm or less, it is possible to suppress or prevent breakage during the surface treatment step and the prepreg manufacturing step. From this viewpoint, the weft skew amount of the weft yarn is more preferably 10 mm or less, still more preferably 5 mm or less, and still more preferably 3 mm or less. In addition, the lower limit of the weft skew amount of the weft can be 0 mm or more or more than 0 mm.

The weft skew amount of the weft can be adjusted to a range of 15 mm or less by, for example, increasing the opening tension in the opening step of glass cloth manufacturing, specifically, so that the opening tension of the glass cloth is relatively Spreading is performed in a way where the ratio of tensile strength exceeds 0.1 (that is, the opening tension/tensile strength>0.1).

[Tensile Strength] The tensile strength of the glass cloth is preferably 150 N/25 mm or less in the direction parallel to the warp (MD). If the MD tensile strength is in the range of 150 N/25 mm or less, it is usually easy to be damaged in the surface treatment step and the prepreg manufacturing step, but by setting the above-mentioned relaxation amount to 10 mm/m or less, it can be significantly Suppress or prevent breakage. From this viewpoint, the MD tensile strength is more preferably 100 N/25 mm or less, and still more preferably 50 N/25 mm or less.

The lower limit of the MD tensile strength of the glass cloth obviously exceeds 0 N/25 mm. From the viewpoint of improving the insulation reliability in the thickness (T) direction of the substrate containing the glass cloth, it is preferably 20 N/25 mm or more . Furthermore, the tensile strength of the glass cloth can be measured in accordance with JIS R3420, item 7.4.

[Unit Bending Rigidity (Hand Feel)] The unit bending rigidity of the glass cloth in the direction (TD) at 90° to the warp yarn is preferably 0.03 gf·cm ² /cm or less. Bending rigidity is to model the movement of the hand that bends the formed body such as glass cloth and use it as an indicator of the hand feeling. In the technical field, the bending rigidity sometimes reflects the plasticity in the hand feeling of the glass cloth.

If the unit bending rigidity of the glass cloth is in ^{the range of 0.03 gf·cm 2} /cm or less, it is usually easy to be damaged in the surface treatment step and the prepreg manufacturing step, but by setting the above-mentioned relaxation amount to 10 mm/m Below, damage can be significantly suppressed or prevented. From this viewpoint, the unit bending rigidity is more preferably 0.02 gf·cm ² /cm or less, and more preferably 0.01 gf·cm ² /cm or less. In addition, the unit bending rigidity can be arbitrarily set according to the dimensional stability of the glass cloth, for example, it can exceed 0 gf·cm ² /cm. Furthermore, the unit bending rigidity (feel) of the glass cloth was measured by the method described in the examples.

[Weaving Density] The weaving density of the warp yarns and weft yarns constituting the glass cloth is independently preferably 50-140 yarns/inch, and more preferably 80-130 yarns/inch.

[Cloth weight (unit area weight)] The cloth weight (unit area weight) of the glass cloth is preferably 4 to 200 g/m ² , more preferably 10 to 100 g/m ² , and still more preferably 10 to 60 g/ m ² .

[Fabric Structure] The fabric structure of the glass cloth is not particularly limited, and examples thereof include fabric structures such as plain weave fabrics, box fabrics, satin weave fabrics, and twill weave fabrics. Among them, a plain weave structure is preferred.

[Surface treatment] The glass yarn (including glass filament) of the glass cloth is preferably surface-treated with a silane coupling agent, preferably a silane coupling agent with an unsaturated double bond group (hereinafter also referred to as "silane coupling agent"). If a silane coupling agent with an unsaturated double bond group is used, the reactivity with the matrix resin is further improved, and the hydrophilic functional group is less likely to be generated after the reaction with the matrix resin, and the insulation reliability is further improved.

The silane coupling agent having an unsaturated double bond group is not particularly limited, and examples thereof include compounds represented by the following general formula (1). By using this silane coupling agent, the moisture absorption resistance is further improved, and as a result, the insulation reliability tends to be further improved. Especially by using a silane coupling agent with unsaturated double bond groups, the penetration of plating solution, insulation reliability, and raising quality of glass cloth with a _{SiO 2 composition of 98-100% by mass after drilling can be improved} . _{X (R) 3-n SiY} n · · · (1) ( wherein, X is a group having an unsaturated double bond group and at least one of any of the one or more organic functional groups, Y are each independently an alkoxy Group, n is an integer of 1 to 3, and R is each independently a group selected from the group consisting of methyl, ethyl and phenyl)

In the general formula (1), X is an organic functional group having at least one of an amine group and an unsaturated double bond group, more preferably an organic functional group having 3 or more, and more preferably an amine group And at least any one of the unsaturated double bond groups with 4 or more organic functional groups. When X is such a functional group, there is a tendency for the moisture absorption resistance 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 vinylene group, an acryloxy group, and a methacryloxy group.

As the alkoxy group in the above general formula (1), any form can be used, but in order to stabilize the glass cloth, it is preferably an alkoxy group with a carbon number of 5 or less.

Specifically, the silane coupling agent that can be used is not particularly limited. For example, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane and its Hydrochloride, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropylmethyldimethoxysilane and its hydrochloride, N-β-(N-di(ethylene (Benzyl) aminoethyl)-γ-aminopropyl trimethoxysilane and its hydrochloride, N-β-(N-bis(vinylbenzyl)aminoethyl)-N-γ- (N-vinylbenzyl)-γ-aminopropyltrimethoxysilane and its hydrochloride, aminopropyltrimethoxysilane, vinyltrimethoxysilane, methacryloxypropyltrimethyl Well-known substances such as oxysilane, methacryloxy octyl trimethoxy silane, acryloxy propyl trimethoxy silane. The above-mentioned silane coupling agent tends to have excellent reactivity with the glass yarn (glass filament) of the glass cloth or the matrix resin of the substrate, especially the radical polymerization resin. Therefore, the above-mentioned silane coupling agent has the following tendency: it can suppress the decrease of the insulation reliability caused by the easy peeling of the resin and the glass cloth at the interface, and also can suppress the insulation reliability caused by the penetration of the plating solution into the glass cloth It is lowered.

[count] From the viewpoint of making the glass cloth thinner and the viewpoint of controlling the difference in the winding hardness between the central part and the end part, the counts of the warp and weft yarns (hereinafter also referred to as Tex) constituting the glass cloth are independently preferably 0.2 g /1000 m or more and 20.0 g/1000 m or less, more preferably 0.5 g/1000 m or more and 10.0 g/1000 m or less. The Tex of the glass cloth can be calculated using the following formula. Tex=m/l×1000 {In the formula, Tex: count m: the mass of the test piece (g) l: length of test piece (m)}

[Manufacturing method of glass cloth] The manufacturing method of the glass cloth of the present embodiment is not particularly limited. For example, a method including the following steps can be mentioned: a coating step in which the surface of the glass filament is almost completely covered by a treatment solution with a concentration of 0.1% to 3.0% by weight The silane coupling agent is covered; and the step of fixing is to make the silane coupling agent adhere to the surface of the glass filament by heating and drying. In addition, the manufacturing method of the glass cloth of this embodiment may also include an adjustment step: it uses high-pressure water spraying to clean at least a part of the silane coupling agent adhered to the surface of the glass filament, thereby adjusting the adhesion of the silane coupling agent quantity.

As a solvent for dissolving or dispersing the silane coupling agent, either water or an organic solvent can be used, but from the viewpoint of safety and protection of the global environment, water is preferably used as the main solvent. As a method for obtaining a treatment solution with water as the main solvent, any one of the following methods is preferred: directly throwing the silane coupling agent into water; dissolving the silane coupling agent in a water-soluble organic solvent to prepare an organic solvent solution , The organic solvent solution was poured into water. In order to improve the water dispersibility and stability of the silane coupling agent in the treatment liquid, a surfactant can also be used in combination.

The coating step, the bonding step, and the adjustment step are preferably performed on the glass cloth after the weaving step. Furthermore, if necessary, after the weaving step, an opening step of opening the glass yarn of the glass cloth may be included. Furthermore, when the adjustment step is performed after the weaving step, the adjustment step can also serve as the fiber opening step. Furthermore, the composition of the glass cloth before and after opening is usually unchanged.

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

As a method of applying the treatment liquid to the glass cloth, the following methods can be used: (A) The method of storing the treatment liquid in a bath, immersing the glass cloth, and passing it through (hereinafter referred to as "dipping method"); (B) A method of directly coating the treatment liquid on the glass cloth using a roll coater, die nozzle coater, or gravure coater. In the case of coating by the dipping method of (A) above, it is preferable to select the immersion time of the glass cloth in the treatment liquid to be 0.5 second or more and 1 minute or less.

In addition, as a method of heating and drying the solvent after applying the treatment liquid to the glass cloth, known methods such as hot air and electromagnetic waves can be cited.

In order to allow the silane coupling agent to fully react with the glass, the heating and drying temperature is preferably 90°C or higher, more preferably 100°C or higher. In addition, in order to prevent deterioration of the organic functional group possessed by the silane coupling agent, the heating and drying temperature is preferably 300°C or less, more preferably 200°C or less.

In addition, the opening method of the opening step is not particularly limited. For example, a method of opening the glass cloth by spraying water (high-pressure water opening), vibrating washer, ultrasonic water, rolling machine, etc. . In order to suppress the decrease in the tensile strength of the glass cloth caused by the opening process, it is preferable to implement the following countermeasures: low friction of the contact member when weaving the glass yarn, or optimization of the sizing agent and high adhesion. During the fiber-opening process, by reducing the tension applied to the glass cloth, there is a tendency to further reduce the air permeability.

The manufacturing method of the glass cloth may also include any steps after the opening step. The arbitrary step is not particularly limited, and for example, a slit processing step can be cited.

After surface treatment of the glass cloth, a matrix resin is applied to produce a prepreg. The storage time after the surface treatment of the glass cloth until the matrix resin is applied is preferably within 2 years. In addition, the storage temperature is preferably set to 10°C to 40°C. When the storage temperature is below 40°C or below 30°C, there is a tendency to suppress the inactivation of the unsaturated double bond groups of the silane coupling agent on the surface of the glass cloth and maintain the reactivity with the matrix resin. In addition, when the storage time is within 2 years, there is a tendency to prevent the silane coupling agent from reacting with each other due to the water adhering to the glass surface, which results in the improvement of the bundling of the glass filament bundle. By this, there is a tendency to increase the permeability of the matrix resin.

[Glass cloth roll] In another embodiment of the present invention, the following glass cloth roll can be formed, which comprises: a core tube made of acrylonitrile-butadiene-styrene copolymer (ABS) with a core tube diameter of 200 mm, and a core tube wound around the core Tube of glass cloth. The glass cloth in the roll is preferably in a state where the core tube is wound with a width of 1.3 m for 1000 m, and the winding hardness difference between the center part and the end part of the glass cloth is 10 or less. If the winding hardness difference between the center part and the end part of the glass cloth in the roll state is 10 or less, when the glass cloth roll is supplied to the prepreg manufacturing step, the occurrence of breakage can be suppressed or the frequency of occurrence of breakage can be reduced.

The glass cloth constituting the glass cloth roll is as described above as an embodiment of the glass cloth.

[Prepreg] The prepreg of this embodiment has the above-mentioned glass cloth and a matrix resin impregnated in the glass cloth. Thereby, a thinner, lower dielectric constant, and improved insulation reliability of the prepreg can be provided.

As the matrix resin, any of thermosetting resin and thermoplastic resin can be used. The thermosetting resin is not particularly limited. For example, a) a compound having an epoxy group and an amine group, a phenol group, an acid anhydride group, a hydrazine group, an isocyanate group, A compound of at least one of the cyano group and hydroxyl group, the ring hardened by the reaction without a catalyst or by adding imidazole compounds, tertiary amine compounds, urea compounds, phosphorus compounds and other catalysts with reaction catalyst functions Oxygen resin; b) using a thermal decomposition catalyst or a photodecomposition catalyst as a reaction initiator to harden a compound having at least one of an allyl group, a methacryl group, and an acrylic group Polymeric hardening resin; c) a maleimide tri-resin cured by reacting a compound having a cyanamide group and a compound having a maleimide group; d) a maleimide compound and an amine compound Thermosetting polyimide resin that undergoes a reaction to harden; e) Benzo resin, etc., which is crosslinked and hardened by a compound having a benzoxane ring by heating and polymerizing.

In addition, the thermoplastic resin is not particularly limited, and examples thereof include polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polysulfide, polyether sulfide, polyarylate, aromatic polyamide, and polyether ether. Ketone, thermoplastic polyimide, insoluble polyimide, polyimide, fluororesin, etc. Moreover, a thermoplastic resin and a thermosetting resin can also be used together.

[A printed circuit board] The printed circuit board of this embodiment has the above-mentioned prepreg. Thereby, a printed circuit board with a lower dielectric constant and improved insulation reliability can be provided. The prepreg in the printed circuit board of this embodiment may also be a laminate including two or more layers. [Example]

Next, the present invention will be further described in detail with examples and comparative examples. The present invention is not limited to the following embodiments at all.

(Example 1) As shown in Table 1, glass yarns containing L glass are woven to form a glass cloth, which is immersed in N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane The hydrochloride salt (manufactured by Toray Dow Corning Co., Ltd.; Z6032) is dispersed in water and heated and dried. Next, use a sprayer to perform high-pressure water opening, heat and dry, and obtain a glass cloth product for evaluation.

(Examples 2-12, Comparative Examples 1-6) As shown in Table 1, the glass cloth product for evaluation was obtained in the same manner as in Example 1, except that the thickness of the glass cloth, the glass type, the dielectric constant, the relaxation characteristic, the winding characteristic, etc. were changed.

＜Method of evaluating the thickness of glass cloth＞ According to 7.10 of JIS R 3420, use a micrometer to slowly rotate the shaft so that it is parallel to the measurement surface and lightly touches it. Read the scale after the ratchet makes three sounds.

<Production method of substrate> The glass cloth obtained in the above examples and comparative examples was impregnated with polyphenylene ether resin varnish (modified polyphenylene ether resin 30 parts by mass, triallyl isocyanurate 10 parts by mass, toluene 60 parts). A mixture of 0.1 parts by mass and 0.1 parts by mass of the catalyst) was dried at 120°C for 2 minutes to obtain a prepreg. The resin content of the prepreg was adjusted to 60% by volume. The prepreg was stacked, and copper foils with a thickness of 12 μm were further stacked on top and bottom of the prepreg, and ^{heated and pressed at 200° C. at 40 kg/cm 2 for} 60 minutes to obtain a substrate.

＜Method of measuring and calculating dielectric constant＞ As described above, the substrate was fabricated so that the resin content per 100% by volume of the prepreg became 60% by volume, and the copper foil was removed to obtain a sample for permittivity evaluation. An impedance analyzer (manufactured by Agilent Technologies) was used to measure the dielectric constant of the obtained sample at a frequency of 10 GHz. According to the obtained substrate dielectric constant, based on the volume fraction of the glass cloth and the resin dielectric constant of 2.5, the relative dielectric constant (Dk) of the glass cloth at 10 GHz is calculated.

＜Measuring method of center warp tension/end warp tension＞ In the above weaving step, the low-load digital tension meter (ZEF-100) manufactured by Schmidt was used to measure the tension of each warp yarn when the warp yarns were straightened, until it reached 0.1 cN unit. Calculate the average warp tension of the part from both ends to 20% (end) and the part except the end (central part), and find the warp tension at the center/end warp.

<Measurement of slack> As shown in Figure 1, the glass cloth (1) with a width and total length t of 1000 mm is horizontally spread on the two rollers (4, 4) with a distance between the rollers of 1 m. When holding the glass cloth (1), the MD When the glass cloth (1) is stretched at the end (end 2 in Figure 1b) with a tension of 50 N in the MD direction, visually judge the most recessed part of the cloth and use the laser displacement meter ( LK-G5000) is measured to a unit of 1 mm, and the amount of depression in the vertical direction (z direction) of the loose part (3) of the glass cloth is measured as the amount of looseness (x). Furthermore, the so-called recessed amount refers to the distance from the plane obtained by connecting the upper surfaces of the two rollers (4, 4) in a straight line to the farthest part of the glass cloth (1) from the plane.

＜Winding test＞ On a core tube made of ABS with a core tube diameter of 200 mm (hardness ≧90), the glass cloth is wound with a width of 1.3 m for 1000 m to make a roll. The winding hardness tester "GS-701N" manufactured by TECLOCK was used to measure the winding hardness difference between the center part and the end part of the winding body in accordance with JIS K 7312. In addition, using the auto-stereograph "AGS-J5kN" manufactured by Shimadzu Corporation, the slope difference of the stress-strain curve in the direction (MD) parallel to the warp of the glass cloth was measured at the center and the end of the winding body.

＜Weft skew amount＞ According to JIS L1096, refer to Figures 2 to 4 to measure the weft skew amount of the sample. Specifically, visually observe 1 weft in a glass cloth with a width of 1000 mm spread on a pair of rollers, measure the displacement from the reference line with the TD connection between the roller and the cloth as the reference line, and calculate the maximum displacement The difference between the value and the minimum value is used as the weft skew amount, and this operation is performed 5 times to calculate the average value.

＜Tensile strength＞ The tensile strength of the glass cloth is measured in accordance with JIS R3420, item 7.4.

<Unit Bending Rigidity (Hand Feel)> Using the "KES-FB2-A" manufactured by Kato Technology Co., Ltd. as a bending tester, the unit bending rigidity (gf·cm ² /cm) of the glass cloth was measured.

＜Frequency of damage in the surface treatment step of glass cloth＞ In the Examples and Comparative Examples, as described above, the glass cloth was immersed in the hydrochloride of N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane Manufactured by Toray Dow Corning Co., Ltd.; Z6032) is dispersed in water to form a silane coupling agent treatment solution. In order to scrape off the excess silane coupling agent, two pairs of rollers apply force in the Z direction of the glass cloth and observe the glass Whether the cloth is damaged, calculate the frequency of damage (%) relative to the N number of the glass cloth.

＜Frequency of breakage in prepreg manufacturing steps＞ The glass cloth obtained in the Examples and Comparative Examples was impregnated in the polyphenylene ether resin varnish as described in the above-mentioned "Method of Making Substrate", and the glass cloth was passed through two pairs of rollers on the glass cloth in order to scrape off the excess PPE resin. When force is applied in the Z direction, observe whether the prepreg is damaged, and calculate the frequency of damage (%) relative to the N number of the prepreg.

Table 1 summarizes the evaluation results of the glass cloths shown in the examples and comparative examples.

[Table 1-1] Example ① Example ② Example ③ Example ④ Example ⑤ Example ⑥ Example ⑦ Example ⑧ Example ⑨ Example ⑩ Example ⑪ Example⑫ Glass cloth Thickness [μm] 30 30 30 30 30 30 30 20 15 30 30 30 Glass type L glass NL glass L2 glass Q glass L glass L glass L glass L glass L glass L glass L glass L glass Dk@10 GHz 4.7 4.7 4.4 3.8 4.7 4.7 4.7 4.7 4.7 4.7 4.7 4.7 Central warp tension/end warp tension [-] 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Relaxation [mm] 8 8 8 8 8 8 8 8 8 3 1 0 Poor winding hardness [-] 15 15 15 15 8 8 8 8 8 15 15 15 Difference of slope of stress-strain curve [%] 15 15 15 15 15 8 8 8 8 15 15 15 Weft skew amount [mm] 15 15 15 15 15 15 8 8 8 15 15 15 Tensile strength in warp direction [N/25 mm] 100 100 100 70 100 100 100 70 60 100 100 100 Feel [gf·cm ² /cm] 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.02 0.01 0.04 0.04 0.04 Frequency of damage in the surface treatment step [%] 10 10 10 10 5 3 0 0 0 5 3 0 Frequency of breakage during prepreg manufacturing steps [%] 10 10 10 10 5 3 0 0 0 5 3 0 [Table 1-2] Comparative example① Comparative example ② Comparative example ③ Comparative example ④ Comparative example ⑤ Comparative example ⑥ Glass cloth Thickness [μm] 30 30 30 30 20 15 Glass type L glass NL glass L2 glass Q glass L glass L glass Dk@10 GHz 4.7 4.7 4.4 3.8 4.7 4.7 Central warp tension/end warp tension [-] 1.3 1.3 1.3 1.3 1.3 1.3 Relaxation [mm] 15 15 15 15 15 15 Poor winding hardness [-] 15 15 15 15 15 15 Difference of slope of stress-strain curve [%] 15 15 15 15 15 15 Weft skew amount [mm] 15 15 15 15 15 15 Tensile strength in warp direction [N/25 mm] 100 100 100 100 70 60 Feel [gf·cm ² /cm] 0.04 0.04 0.04 0.04 0.02 0.01 Frequency of damage in the surface treatment step [%] 50 50 60 70 80 100 Frequency of breakage during prepreg manufacturing steps [%] 50 50 60 70 80 100

From the comparison between Examples 8-9 and Comparative Examples 5-6, it can be seen that in the comparative example, the thinner the glass cloth is, the more likely it is to be damaged. However, in Examples 8-9, even under the condition that the glass cloth is easily broken, The effect of the present invention can be significantly exerted by controlling the amount of slack.

1: Glass cloth 2: Glass cloth end 3: Glass cloth slack 4: Roll MD: Direction parallel to the warp t: Width and full length TD: Direction 90° to the warp x: Slack X: X axis (X ₀ ,Y ₀ ): Origin (X ₁ , Y ₁ ): The point where the maximum value of Y is taken (X ₂ , Y ₂ ): The point where the minimum value of Y is taken (X ₃ , Y ₃ ): End point Y: Y axis z: vertical direction

Fig. 1 is a schematic diagram for explaining the method of measuring the amount of slack, including a side view (a) and a top view (b) of the glass cloth set on a pair of rollers. Fig. 2 is a schematic diagram showing a form of the glass cloth in the measurement of the amount of weft, and a diagram showing a form of the weft yarn. Fig. 3 is a schematic diagram showing a form of the glass cloth in the measurement of the weft skew amount, and a diagram showing a form of the weft yarn. Fig. 4 is a schematic diagram showing a form of the glass cloth in the measurement of the weft skew amount, and a diagram showing a form of the weft yarn.

1: glass cloth

2: Glass cloth end

3: Slack part of glass cloth

4: Kun

MD: The direction parallel to the warp

t: width full length

TD: 90° to the warp

x: slack

z: vertical direction

Claims (16)

A glass cloth, which is composed of glass yarns containing a plurality of glass filaments as warp and weft, and the width of the direction (TD) at 90° to the above warp is 1000 mm or more, and has a relative dielectric of 5.0 or less Constant (Dk) and thickness of 35 μm or less, and when the tension in the direction parallel to the warp yarn (MD) is set to 50 N, the slack in the vertical direction is 10 mm/m or less. The glass cloth of claim 1, wherein the ratio of the central warp tension to the end warp tension of the glass cloth (central warp tension/end warp tension) is 0.8 or more and 1.2 or less. The glass cloth of claim 1 or 2, wherein the winding hardness difference between the center part and the end part of the glass cloth is 10 or less in the state of the winding body obtained by winding 1000 m of the above glass cloth with a width of 1.3 m . The glass cloth according to any one of claims 1 to 3, wherein the difference in the slope of the stress-strain curve of the center part and the end part of the glass cloth in the direction parallel to the warp yarn (MD) is 10% or less. Such as the glass cloth of any one of claims 1 to 4, wherein the weft skew amount of the weft yarn is 10 mm or less. The glass cloth of any one of claims 1 to 5, wherein the thickness of the glass cloth is 25 μm or less. The glass cloth according to any one of claims 1 to 6, wherein the thickness of the glass cloth is 17 μm or less. The glass cloth according to any one of claims 1 to 7, wherein the tensile strength in the direction (MD) parallel to the warp yarn is 150 N/25 mm or less. The glass cloth according to any one of claims 1 to 8, wherein the unit bending rigidity in the direction (TD) at 90° to the warp yarn is 0.03 gf·cm ² /cm or less. The glass cloth according to any one of claims 1 to 9, wherein the width of the glass cloth in the direction (TD) at 90° to the warp yarn is 2000 mm or less. The glass cloth of any one of claims 1 to 10, wherein the above-mentioned slack is 6 mm/m or less. Such as the glass cloth of claim 11, wherein the above-mentioned slack is 4 mm/m or less. Such as the glass cloth of claim 12, in which the above-mentioned slack is less than 2 mm/m. A prepreg, which contains: Such as the glass cloth of any one of claims 1 to 13, and The matrix resin impregnated in the above-mentioned glass cloth. A printed circuit board comprising the prepreg as claimed in claim 14. A glass cloth roller, which comprises: Core tube, and The glass cloth wound around the above core tube, The glass cloth is composed of glass yarns containing a plurality of glass filaments as warp yarns and weft yarns, and In the state where the above glass cloth is wound around a core tube made of acrylonitrile-butadiene-styrene copolymer (ABS) with a core tube diameter of 200 mm and a width of 1.3 m, the center and ends of the glass cloth The winding hardness difference of the part is 10 or less.

Images