TWI512155B - Core-spun yarn, fabric, and method for manufacturing the same - Google Patents

Description

Core yarn, fiber cloth and manufacturing method thereof

The present invention relates to a core yarn for weaving a base fabric of a high frequency printed circuit board, and more particularly to a core yarn having a cyclic olefin polymer fiber and a fiber cloth produced therefrom.

The new generation of consumer electronics will move toward light, thin, short, small and versatile. The printed circuit board (PCB) used in electronic products is also moving towards high density and high aggregation, and the requirements for electrical properties and heat resistance of printed circuit boards are increasing.

The low dielectric constant is required for the electrical properties of printed circuit board materials. The main purpose is to shorten the transmission time of electronic signals in the material medium and to reduce mutual interference and loss of energy when electronic signals are transmitted.

The core material of the printed circuit board is a substrate, and the common substrate is a copper clad laminate (CCL). The substrate fabrication technology has different manufacturing methods depending on the material. At present, the world's highest market share is FR4 (DICY Cured) substrate, but the dielectric constant value of such substrates is between 4.3 and 4.8, and the dielectric constant value is too high, so the material characteristics are more Room for improvement.

Further, the resin materials applied to the substrate of the high-frequency printed circuit board are mainly PTFE (polytetrafluoroethylene) series resin and PPO (Poly phenyl oxide) series resin. Although the PTFE series resin has a very low dielectric constant value, the raw material price is extremely expensive and it is difficult to process and form, which results in a special and expensive substrate process. Therefore, the PTFE series substrate is basically applied to a special demand field of frequencies above 3 GHz, and utilizes PTFE. The printed circuit boards are used in precision instruments or high-priced electronic products, so they are not commonly used. GE, on the other hand, uses the printed circuit board substrate GETEK ^® manufactured by PPO, which has a dielectric constant of about 4.0 and relatively poor material properties.

Further, since the copper foil substrate also has a problem that the glass transition temperature is too low, the heat resistance of the copper foil substrate is insufficient, which causes a risk in use.

Based on the shortcomings of the electrical properties and heat resistance of the above-mentioned substrates, most of the conventional techniques provide an improved means for the resin material in the substrate, but it is still impossible to provide a substrate having a low dielectric constant and high heat resistance.

In addition, a small number of improved substrate fiber cloths and yarns used for the purpose of effectively reducing the dielectric constant and increasing heat resistance have been proposed, and most of the above-mentioned improved techniques use glass fiber cloth as the base fabric of the substrate for use. Reinforcing and insulating materials, but in order to make the substrate more heat resistant, the glass fiber cloth needs to be coupled with the resin through decane coupling treatment to increase the strength of the combination, but also adds a processing procedure and increases its The complexity of the base fabric process.

In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to disclose a core-spun yarn made of a cyclic olefin polymer fiber, and to utilize the package The core yarn is woven into a prefabricated fabric, and then a fiber cloth is replaced by a water washing step to replace the glass fiber cloth as a base fabric of the copper foil substrate. The fiber cloth provided by the invention can reduce the dielectric constant of the copper foil substrate, Electronic tangential loss and increased glass transition temperature to improve heat resistance.

However, since the cyclic olefin polymer fiber has almost no crystal phase, the yarn composed of the cyclic olefin polymer alone has a weak fiber strength and cannot meet the standard of general textile weaving, and cannot be directly woven into a fiber cloth; The invention coats the cyclic olefin polymer fiber as a slurry with a starch and a PVA mixture to form a sizing yarn; or coats the cyclic olefin polymer fiber with a water-soluble fiber as an outer sheath to form a core yarn, using the sizing yarn or The core spun yarn is used as a warp yarn and a weft yarn to weave a prefabricated fabric, and a water washing step is carried out to complete a fiber cloth composed of a cyclic olefin polymer fiber.

In order to achieve the above object, the present invention provides a core spun yarn comprising: a core yarn composed of a cyclic olefin polymer fiber; and a plurality of sheath yarns composed of polyvinyl alcohol fibers, and The sheath yarn is wound on the core yarn; wherein the core yarn has a twist coefficient of between 2.3 and 2.5 TPI.

The yarn strength measured by the above-mentioned core yarn was 3.1 g/d or more. Furthermore, the residual torsion measured by the core spun yarn is between 83 and 104 note/m, and the number of hairiness of the core yarn of 0.2 mm or more is less than 100/m. Therefore, the core-spun yarn provided by the present invention can compensate for the disadvantage of insufficient strength of the cyclic olefin polymer fiber, and at the same time achieve a balance between the torsion force and the number of hairiness suitable for weaving.

Further, in the core spun yarn of the embodiment of the invention, the number of the sheath yarns is four.

Further, the core yarn may have a linear density of 150 D, and the core yarn may contain 48 cyclic olefin polymer fibers.

Further, each of the sheath yarns may have a linear density of 40 D, and each of the sheath yarns may contain 12 polyvinyl alcohol fibers.

Another object of the present invention is to provide a method for manufacturing a fiber cloth comprising the steps of: spinning a yarn to form a pre-formed fabric comprising a plurality of warp yarns and a plurality of weft yarns, wherein each of the warp yarns is in the above package a core yarn; and a water washing step, the pre-made fabric is subjected to a water washing treatment to remove the material of the non-cyclic olefin polymer fiber, thereby obtaining a fiber cloth.

Furthermore, the weft yarn of the prefabricated fabric may be a core yarn or a sizing yarn, and when the core yarn is used, the water washing step is for removing polyvinyl alcohol fibers, and when the sizing yarn is used, the water washing step is used for shifting. In addition to polyvinyl alcohol composite slurry.

It will be appreciated that since the core spun yarn of the present invention has a strength of more than 3 g/d, the core spun yarn can be used as a warp yarn or both as a warp yarn and a weft yarn.

Further, in the embodiment of the present invention, the water temperature used in the water washing treatment is 60 ° C or higher, and the higher the water temperature used, the faster the dissolution rate, and the preferred water temperature is 80 ° C.

Still another object of the present invention is to provide a fiber cloth which is produced by the above-described manufacturing method, the fiber cloth comprising a plurality of warp yarns and a plurality of weft yarns, each of which is composed of a cyclic olefin polymer fiber.

Furthermore, in the embodiment of the present invention, the warp and weft of the fiber cloth is 50 × 37 roots / in.

Accordingly, the present invention utilizes polyvinyl alcohol fibers wound around a cyclic olefin polymer fiber to form a core spun yarn, wherein the optimum core-spun yarn twist coefficient is 2.5 TPI, the strength is 3.15, and the residual torque is 104 note/m. . In addition, the core spun yarn can be further woven into a fiber cloth, and the copper foil substrate pressed by the fiber cloth is known by the standard test method of IPC-TM-650, in the electrical properties of the copper foil substrate, when the frequency At 5 GHz, the dielectric constant (D _k ) is 2.7 and the electron tangent loss (D _f ) is 0.025, both of which are lower than the conventional copper foil substrate pressed by the glass fiber cloth. Furthermore, it can be seen from the DSC analysis chart that the copper foil substrate pressed from the fiber cloth of the cyclic olefin polymer has the effect of increasing the glass transition temperature to increase the heat resistance, compared with the conventional copper foil substrate. It is about 25 ° C high.

To fully clarify the objects, features, and advantages of the present invention, those of ordinary skill in the art of the invention can understand the invention and practice the invention. Schematic, a detailed description of the present invention, illustrated as follows:

definition

As used herein, "or" means an "or" or an exclusive "or". For example, the condition "A or B" is satisfied in the following three cases: A is true (or exists) and B is pseudo (or non-existent), A is pseudo (or non-existent), and B is true (or exists) ) and A and B are true (or exist).

In addition, "a" is used to describe the elements and components of the present invention. This usage is provided for convenience only, and is intended to be inclusive of the generality of the invention.

Where a quantity, a concentration, or other value or parameter is expressed by a range, a preferred range, or a series of upper and lower limits, it is understood to be a specific disclosure of the upper or lower value of any range or the lower limit of any range or All ranges of preferred values are constructed regardless of whether such ranges are disclosed separately. In addition, when a range of values is recited herein, unless otherwise stated, the range shall include its endpoints and all integers and fractions within the range.

In the present invention, before the object can be attained, the numerical value should be understood as having the accuracy of the number of significant digits. For example, the number 40 should be understood to cover the range from 35.0 to 44.9, while the number 40.0 should be understood to cover the range from 39.50 to 40.49.

Raw materials and measuring instruments

The cyclic olefin copolymer (COC) fiber used in the present invention has a specification of 150 D/48 F, a strength of 1.41 g/d, and an elongation of 57.4%; polyvinyl alcohol (PVA, polyvinyl alcohol) fiber. The specification is 40 D/12 F, the strength is 4.31 g/d, and the elongation is 21.7%.

In addition, in the measuring instrument used in the present invention, the solution viscosity is measured in No. 3 and No. 4 Ford cups; the fiber strength and elongation are measured by a German Textechno Statimat ME type instrument; the thermal properties are measured by SETARAM DSC131. Measurement.

Yarn [core yarn]

Referring to FIG. 1A and FIG. 1B, in the embodiment of the present invention, the core spun yarn 1 comprises a core yarn 11 and a four-strand sheath yarn 12, wherein the core yarn 11 is formed by using a plurality of bundles of COC fibers, and each of the core yarns 11 is formed by a plurality of bundles of COC fibers. Sheath 12 series using multiple bundles Formed by PVA fibers. The arrow in Fig. 1B indicates the direction of the sheath yarn. Since the strength of the COC fiber itself is low, and the yarn is generated by the friction with the hollow spindle of the apparatus when the fiber cloth is woven, thereby reducing the weaving efficiency, it is necessary to use PVA fiber wound on the COC fiber to increase the strength.

Further, in the present invention, the enthalpy coefficient is used to evaluate the degree of cohesion between fibers. In general, the twist factor of the yarn must be greater than 2.3 TPI (twist per inch) to make it stronger than 370 gf, which is used for the weaving of woven fabrics, and the number of hairiness with the increase of the twist factor of the yarn The length of the hairiness will be reduced. However, if the twist factor of the yarn is too high, the residual torque is too high to smoothly weave the yarn. Table 1 below shows the data measured by COC fibers being wound by PVA fibers at different twist coefficients to form core spun yarns.

The data in Table 1 shows that when the twist coefficient of the core yarn reaches 2.3 TPI or more, the phenomenon that the COC fiber produces the yarn can be effectively improved and the yarn is smoothly discharged. However, when the twist factor exceeds 2.5 TPI, the torsion of the yarn residual is too high, which is disadvantageous for weaving. According to the measurement results of Table 1, it can be understood that the core yarn of the present invention has a twist coefficient of between 2.3 and 2.5 TPI to achieve the strength required for weaving, and at the same time, the number of hairiness exceeding 0.2 mm is lower than 100 to meet the standard of yarn output.

Further, Table 2 below is the yarn strength corresponding to the core yarn of the present invention at different twist coefficients.

In general, the warp yarn used for the fiber cloth has a higher strength than the weft yarn, and the strength of the yarn must be 3 g/d or more to be used as a warp yarn, and the yarn strength can be observed in Table 2 with the core. The yarn twist coefficient increases and increases. When the twist coefficient reaches 2.1 TPI, the yarn strength reaches 3.04 g/d, which has met the standard as warp yarn. The core yarn of the present invention has the main reason for the high yarn strength, and the first is to use the winding system of the sheath yarn to make the COC fibers in the single-strand core yarns more closely bond, thereby improving the strength of the yarn; The sheath yarn itself has a high strength (4.31 g/d), which increases the strength of the overall core yarn.

[sizing]

In the embodiment of the present invention, a sizing yarn formed by a PVA slurry and a COC fiber is further provided, wherein the slurry is prepared by mixing the PVA slurry and the starch slurry with hot water of 40 ° C or higher, and then using the Ford Cup. Test the viscosity of the composite slurry so that the viscosity of the slurry is between 20 and 30 cps, and finally COC The fiber is impregnated and dried to form a sizing, wherein the impregnation rate of the slurry is between 20 and 30%.

The strength of the above sizing yarn is only 2.12 g/d, which is the strength (3 g/d) required for the warp yarn of a general woven fabric, and can only be used as a weft yarn.

COC fiber cloth and its process

In the embodiment of the present invention, for the weaving process of the COC fiber cloth, a core yarn made of PVA fiber and COC fiber is used as a warp yarn, and the above-mentioned sizing yarn is used as a weft yarn, followed by warping and beating, Weaving a weave of plain weave. The woven fabric is used as a pre-formed fabric for subsequent processing, and has a warp and weft density of 50 × 37 / in. and a cloth thickness of 0.2 mm.

Thereafter, the pre-formed fabric is further subjected to a water washing treatment, since the PVA fibers wound on the core spun yarn and the PVA slurry coated on the sizing yarn are composed of water-soluble PVA material, and when the PVA is in contact with water, It can be dissolved to remove it from the prefabricated cloth to form a COC fiber cloth having only a plain weave of COC fibers.

In the present embodiment, the water washing treatment was performed by using hot water of 80 ° C for about 20 minutes to remove the PVA.

It should be understood that although sizing is used as the weft of the fiber cloth in the embodiment of the present invention, it should be understood by those of ordinary skill in the art that the strength of the core yarn of the present invention is stronger than the sizing. Therefore, the core-spun yarn can replace the sizing yarn as the weft yarn of the fiber cloth. In other words, in the other equivalent embodiment of the present invention, the core-spun yarn can be used only as a warp yarn or as a warp yarn and a weft yarn. .

Measurement and comparison of electrical properties of COC fiber

One of the main objects of the present invention is to replace the base fabric of the glass fiber in the copper foil substrate with a base fabric made of COC fibers to provide a low dielectric constant (D _k , permitivity) and low electron tangent loss (D _{f ).} , loss tangent), therefore, in the examples, the copper foil substrate made of the COC fiber cloth of the present invention was used to measure electrical properties to prove the excellent efficacy of the present invention.

In general, the copper foil substrate contains a resin, a base fabric, and a copper foil. In the copper foil substrates of the examples and comparative examples of the present invention, the blending ratio of the resin is determined depending on the specific platen conditions.

Table 3 below shows the blending ratio of the tested resin. The platen conditions of the copper foil substrate are fixed at hot pressing pressure: 3 kg/cm ² , hot pressing temperature: 185 ° C, and hot pressing time: 2 hours to find a suitable formula. proportion.

Among them, NPEB-475A70 is a product type of a mixture of various brominated epoxy resins, which is soluble in acetone, 70% solids, which can be purchased from general commercial sources; 2-MI stands for 2-methyl imidazole ), which is a hardening accelerator in an amount of 0.05 PHR; Dicy represents dicyandiamide; and DMF represents dimethylformamide.

According to the pressing process of the copper foil substrate, the optimum hardening time is 180 seconds. It can be seen from Table 3 that the gelation time of the formulation 1 is closest to 180 seconds, so that the resin formulation for pressing the copper foil substrate is Formulation 1.

Next, in the copper foil substrate of the embodiment of the present invention, a COC fiber cloth was used as the base fabric, and the copper foil substrate of the comparative example was a glass cloth (the specification is shown in Table 4) as a base fabric.

Next, the base fabric of the above examples and comparative examples were impregnated into the resin of the formulation 1 by using 2/3 of the gelation time as the inclusion time, and then dried at 165 ° C by a hot air circulation bellows to make the resin Some of the components are polymerized to obtain an adhesive prepreg, which is then laminated with a 1 oz copper foil. The copper foil substrate is obtained by thermosetting and bonding at 175 to 200 ° C.

Table 5 below shows the electrical property analysis data of the copper foil substrate.

The data of the dielectric constant of the copper foil substrate (Example) pressed with the COC fiber cloth of Table 5 and the copper foil substrate (Comparative Example) pressed with the glass fiber cloth was tested according to IPC-TM-650. Obtained by standard methods. In the data, the dielectric constant of the copper foil substrate of the example is lower than the dielectric constant of the copper foil substrate of the comparative example at a frequency from 1 MHz to 5 GHz, and the maximum difference of the dielectric constants The value reached 2.1.

Furthermore, the data listed in Table 5 also shows that the copper foil substrate of the embodiment has a lower electron tangent loss, and the difference is more pronounced under the condition of higher frequency, and the maximum difference is 0.01.

Further, Fig. 2 and Fig. 3 are sequentially DSC analysis views of the copper foil substrates of the examples and the comparative examples. It can be observed from Fig. 2 that the glass transition temperature of the copper foil substrate of the embodiment is 175 ° C, and it can be observed from Fig. 3 that the glass transition temperature of the copper foil substrate of the comparative example is 150 ° C, thereby demonstrating The COC fiber cloth has an effect of increasing the glass transition temperature of the copper foil substrate pressed therefrom, thereby improving the heat resistance of the copper foil substrate.

Accordingly, the present invention has been disclosed above in the preferred embodiments, It is to be understood by those skilled in the art that the present invention is not intended to limit the scope of the invention. It should be noted that variations and permutations equivalent to those of the embodiments are intended to be included within the scope of the present invention. Therefore, the scope of protection of the present invention is defined by the scope of the patent application.

1‧‧‧core yarn

11‧‧‧core yarn

12‧‧‧sheath

Fig. 1A is a schematic view of a core spun yarn according to an embodiment of the present invention.

Fig. 1B is a cross-sectional view of the core yarn of Fig. 1A taken along line A-A.

Fig. 2 is a DSC analysis diagram of the copper foil substrate of the example.

Fig. 3 is a DSC analysis chart of a copper foil substrate of a comparative example.

1‧‧‧core yarn

11‧‧‧core yarn

12‧‧‧sheath

Claims (9)

A core spun yarn comprising: a core yarn composed of a cyclic olefin polymer fiber; and a plurality of sheath yarns composed of polyvinyl alcohol fibers, and the sheath yarns are wound on the core yarn Wherein the core yarn has a twist coefficient between 2.3 and 2.5 TPI. The core-spun yarn according to claim 1, wherein the number of the sheath yarns is four. The core-spun yarn according to claim 1, wherein the core yarn has a linear density of 150 D, and the core yarn comprises 48 cyclic olefin polymer fibers. The core-spun yarn according to claim 1, wherein each of the sheath yarns has a linear density of 40D, and each of the sheath yarns comprises 12 polyvinyl alcohol fibers. A method for manufacturing a fiber cloth, comprising the steps of: spinning a yarn to form a prefabricated fabric comprising a plurality of warp yarns and a plurality of weft yarns, wherein each of the warp yarns is in the first to fourth aspects of the patent application scope. A core yarn according to any one of the invention; and a water washing step, which is subjected to a water washing treatment to remove polyvinyl alcohol fibers to obtain a fiber cloth. The manufacturing method according to claim 5, wherein each of the weft yarns is a core yarn or a sizing yarn. The manufacturing method according to claim 5, wherein the water temperature used in the water washing treatment is 60 ° C or higher. A fiber cloth produced by the manufacturing method according to claim 5, wherein the fiber cloth comprises a plurality of warp yarns and a plurality of weft yarns, each of which is The yarn and the weft are composed of a cyclic olefin polymer fiber. The fiber cloth according to item 8 of the patent application has a warp and weft density of 50 × 37 roots / in.