JP2008169101A - Wound glass yarn and method for producing the same, glass cloth, doubled and twisted glass yarn, wound doubled and twisted glass yarn and method for producing the same, doubled and twisted glass yarn cloth and transparent composite composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wound glass yarn prepared by winding a glass yarn not requiring processes of secondary sizing after warping, heat deoiling and a surface treatment after weaving; a method for producing the same; a glass cloth using a glass yarn or a doubled and twisted glass yarn reeled from wound glass yarn; and a transparent composite composition using the glass cloth. <P>SOLUTION: This wound glass yarn is prepared by coating the filament surface of a glass long fiber strand imparted with twisting with a sizing agent containing a silane coupling agent and a polyamine derivative-based lubricating agent, etc. The method for producing the wound glass yarn comprises winding the glass yarn. The doubled and twisted glass yarn is prepared by doubling and twisting a glass yarn reeled from the wound glass yarn. The doubled and twisted yarn wound article is prepared by winding the doubled and twisted glass yarn on a bobbin. The glass cloth is prepared by weaving the glass yarn or the doubled and twisted glass yarn. This transparent composite composition is prepared by combining the glass cloth and a resin having such optical constants that the difference of refractive indices nd between the resin and these glass cloths is within 0.01 and the difference of Abbe's numbers νd between the resin and these glass cloths is within 5. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is woven by a glass yarn wound body having a form in which a glass yarn used for weaving a glass cloth is wound around a bobbin, a manufacturing method thereof, and a glass yarn unwound from the glass yarn wound body. Glass cloth, glass yarn twisted yarn obtained by twisting a glass yarn released from the glass yarn wound body, glass yarn twisted yarn wound body, and glass yarn twisted yarn wound from the glass yarn twisted yarn wound body. The present invention relates to a glass cloth of a twisted yarn and a transparent composite composition obtained by compounding the glass cloth or the glass cloth of a twisted yarn.

  A glass yarn obtained by twisting glass fibers is woven in the form of a glass cloth and used as a material constituting a printed wiring board or various FRP molded bodies. Such a glass yarn is generally manufactured by the following process.

  A glass raw material batch prepared by mixing various inorganic raw materials and glass cullet at a predetermined ratio so as to have a predetermined composition is put into a glass melting furnace, heated to obtain molten glass, and homogeneously melted by a homogenizing operation. After making it into a state, it is pulled out from a bushing having a plurality of platinum nozzles to produce a glass filament. The glass filament is coated with a bundling agent (also called a sizing agent) made of various chemicals for coating the surface by a conventional method, and several tens to thousands of glass filaments are bundled to form a glass strand, and a winding having a winder A semi-finished product called cake or cheese is wound around a tube mounted on a take-up device. The above process is generally called a spinning process, and is one of the basic processes for producing long glass fibers.

  Next, the glass strand wound from the outer layer of the cake is wound on a bobbin or beam fixed to a spindle while twisting while unwinding to obtain a package of a glass yarn wound body. In order to obtain a twisted yarn, a step of taking out the yarn from the glass yarn winding body and twisting it again is required. The process of twisting to form a glass yarn wound body or a glass yarn twisted thread wound body is generally called a twisting process, and strands wound up as a cake are easy to unwind, that is, unraveling the cake. The properties are required to be good.

  In order to produce a composite composition for a specific purpose such as a laminate for a printed wiring board from a package of a glass yarn wound body or a glass yarn twisted yarn wound body, the following steps are required. Become. First, the glass yarn or glass yarn twisted yarn unwound from the package of the glass yarn wound body or glass yarn twisted yarn wound body is warped with a warper, and is secondarily sized by a gluing machine and wound from the beam to the room beam. This is the warp. A package of a glass yarn wound body or a glass yarn twisted yarn wound body is unwound and used as a weft, and a glass cloth is woven using an air jet loom or the like. Organic components adhering to the woven glass cloth are removed by incineration by heating (heat deoiling), immersed in a treatment solution containing a silane coupling agent and dried (surface treatment), and then impregnated with resin. Then, by laminating and curing the resin, a composite composition for a specific purpose such as a laminate for a printed wiring board is produced.

  In recent years, supported by the dramatic development of the electronic component industry, various improvements have been made so that printed wiring boards are lighter and thinner and can be mounted at high density. In such efforts, various demands have been made for glass fibers, which are basic materials constituting printed wiring boards, and various improvements have been made to meet the demands. For example, Patent Document 1 discloses a treatment with a silane coupling agent and ammonium chloride as a method for preventing the generation of voids that are problematic when molding a printed wiring board. Patent Document 2 discloses an invention in which an epoxy resin is used as a primary sizing agent in order to improve warpage, twisting and the like that occur when a printed wiring board is thinned, and it can be dealt with by degreasing and opening treatment by water flow processing. Has been done. Further, Patent Document 3 discloses an invention in which a predetermined amount of a water-soluble urethane resin and / or a water-soluble epoxy resin is adhered to the glass surface in order to improve the change over time in the insulation resistance.

Glass used for plastic substrates for liquid crystal display elements, plastic substrates for organic EL display elements, substrates for solar cells, touch panels, etc. that require high transparency using conventional prepreg manufacturing processes and printed circuit board manufacturing processes. Inventions for producing transparent composite compositions such as composite sheets and substrates reinforced with fibers have also been made. For example, Patent Document 4 discloses a transparent composite composition having an Abbe number of 45 or more using glass fibers. Patent Document 5 discloses a resin sheet that is compounded with an epoxy resin and has a haze value of 10% or less.
JP-A-6-112608 JP-A-9-67757 Japanese Patent Laid-Open No. 9-209233 Japanese Patent No. 3728441 JP 2004-51960 A

  However, only the inventions made so far have high performance, and high yields of glass yarns having excellent quality used when manufacturing various composite compositions such as lightweight and thin printed wiring boards. There are problems to manufacture. In other words, the process yield decreases due to defects such as fuzz due to filament cutting that occurs during continuous production of glass yarn or when performing unwinding operations, etc., so there is ample necessary amount to meet the demand for glass yarn. There is a problem that can not be supplied to.

  In addition, when glass yarn is used for various purposes, there is a heat deoiling process and the process is lengthy. Therefore, it is a sizing agent that can be used without heat deoiling the sizing agent adhering to the glass surface. And what can solve the above-mentioned subject is calculated | required.

  Glass used for liquid crystal display element plastic substrates, organic EL display element plastic substrates, solar cell substrates, touch panels, etc. that require high transparency using conventional prepreg manufacturing processes and printed circuit board manufacturing processes. When making a transparent composite composition such as a composite sheet or substrate reinforced with fibers, it is necessary to match the optical constants of the refractive index nd and Abbe number νd of the resin and glass fiber. Since a starch-based sizing agent that does not adhere well to the resin is used, it is necessary to remove the sizing agent of the glass fiber by heat deoiling after weaving. Therefore, it is necessary to adjust the optical constant of the resin used for the transparent composite composition by the thermal history of the glass cloth.

  The present invention is a glass yarn winding obtained by winding a glass yarn capable of realizing high surface performance without going through the secondary oil size after warp warping and the heat deoiling step and surface treatment step of the glass cloth after weaving. Body, a method for producing a glass yarn winding body capable of collecting the glass yarn winding body with a high yield, a glass cloth woven by a glass yarn unwound from the glass yarn winding body, and a released glass yarn. Twisted glass yarn twisted yarn, glass yarn twisted yarn wound body, method for producing the glass yarn twisted yarn wound body, heat deoiling woven from the glass yarn twisted yarn wound from the glass yarn twisted yarn wound body To provide a transparent composite composition produced by using a glass cloth that does not require a process and a surface treatment process, and further using this glass cloth or a glass cloth of a twisted yarn An object of the present invention.

  That is, the glass yarn wound body of the present invention is a glass yarn wound body in which a glass yarn in which a twist is imparted to a strand of long glass fiber is wound on a bobbin, and the filament constituting the strand of the glass yarn The surface is coated with a sizing agent containing an epoxy resin, a silane coupling agent and a polyamine derivative-based lubricant.

  Here, a glass yarn wound body in which a glass yarn in which a twist is applied to a strand of long glass fiber is wound around a bobbin, and the surface of the filament constituting the strand of the glass yarn is an epoxy resin, a silane Coated with a sizing agent containing a coupling agent and a polyamine derivative-based lubricant is a glass yarn provided with a predetermined twist, and an epoxy resin, a silane coupling agent and a polyamine derivative system are provided on the surface of the glass yarn. This shows that a sizing agent containing three kinds of lubricants is coated.

  The twisting of the strands of the glass yarn is carried out because it has an effect of removing excess moisture of the cake by imparting the twisting and further strengthening the binding property of the strands. In order to realize such an effect, it is preferable that a twist of 0.01 to 13 times / inch is imparted to the strand of the long glass fiber.

  As a method for confirming that a predetermined twist is applied to the strand of the long glass fiber, for example, it can be measured by a method described in JIS R3420 (Glass Fiber General Test Method). Specifically, using a tester, confirm by measuring the number of twisted glass yarns while rotating the bobbin so that the number of twisted glass yarns does not change from the side of the bobbin. can do.

  The epoxy resin contained in the sizing agent according to the present invention may be water-soluble or emulsified emulsion, and the epoxy structure may be bisphenol A type or novolac type, but has a structure retaining an epoxy group. It is necessary to become. Epoxy resins are preferred because they have the effect of enhancing strand binding properties and improving resin impregnation properties.

  Moreover, when using ethylene oxide addition bisphenol A as an epoxy resin, it is preferable that ethylene oxide exists in the range of 40-95 mass%, More preferably, it is set as the range of 60 mass% to 90 mass%. . When the amount of ethylene oxide is less than 40% by mass, the water solubility is deteriorated, and when it is more than 95% by mass, the binding property of the strand is decreased, which is not preferable. The addition of ethylene oxide-added bisphenol A is preferable because the fiber bundle improves the lubricity of the strand while maintaining the binding property of the strand, and the unwinding property of the glass yarn wound body is improved. The addition amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 1 part by mass of the epoxy resin.

  The silane coupling agent contained in the sizing agent according to the present invention may be, for example, epoxy silane or amino silane. A silane coupling agent is added because it has an effect of adhering to a resin.

  The polyamine derivative of the polyamine derivative-based lubricant contained in the sizing agent according to the present invention is preferably derived from a fatty acid, and more specifically, stearic acid is preferred.

  Moreover, the glass yarn wound body of the present invention is wound as a yarn while twisting a strand of inorganic glass filaments around a cylindrical shaft body called a bobbin, and its external form is It may be conical type (also called double taper shape), milk bottle shape (also called single taper shape) or flange type shape (also called double square shape), and the strand twist direction is also S twist (The twist direction is a twist in the direction of the left-hand thread) or a Z-twist (the twist direction is a twist in the direction of the right-hand thread).

  In the glass yarn winding body of the present invention, the overall dimensions of the glass yarn winding body, that is, the axial length and diameter are not particularly limited. Also, the bobbin shape is generally a cylindrical shaft body, but may be in other forms as needed, and is not particularly limited.

  Furthermore, as for the material of the glass long fiber constituting the glass yarn wound around the glass yarn winding body of the present invention, any material can be used according to the specification application of the glass yarn winding body. be able to. For example, a material called alkali-free E glass, a material called D glass that realizes a low dielectric constant, a material called C glass that realizes acid resistance, a material called AR glass that realizes alkali resistance, and high elasticity A material called M glass that realizes a high modulus, a material called S glass that realizes high strength and a high elastic modulus, a material called T glass having the same function as S glass, and a H glass having a high dielectric constant. Various glass materials such as materials can be used, and other materials designed to have an optimum function can be used.

  In the glass yarn wound body of the present invention, in addition to the above, as a sizing agent, a primary sizing agent for glass yarn having a pH in the range of 3 to 5.5 was applied to the surface of the filament constituting the strand of the glass yarn. If it is a thing, since appropriate glass intensity | strength can be maintained with time, it is preferable.

  Here, as the sizing agent, the primary sizing agent for glass yarn having a pH in the range of 3 to 5.5 is applied to the surface of the filament constituting the strand of the glass yarn. The value of the hydrogen ion concentration index for the agent prepared as an agent is in the range of 3 to 5.5, and it is uniformly applied to the surface of the filament constituting the strand of the glass yarn. I mean.

  The pH value of the primary sizing agent for glass yarn can be adjusted within the range of 3 to 5.5 by addition of acid, and the types of acids used for this adjustment include acetic acid, formic acid, hydrochloric acid, etc. A known inorganic acid may be used as appropriate. If the pH value is less than 3, the acid reactivity becomes too strong, so that the glass surface is likely to deteriorate and the strength of the glass surface may be weakened. On the other hand, if the pH value is greater than 5.5, the chemical stability of the sizing agent may deteriorate, which is not preferable.

  Further, in the glass yarn wound body of the present invention, in addition to the above, if the mass ratio of the polyamine derivative-based lubricant to the epoxy resin in the sizing agent is in the range of 0.075 to 1.5, a high process yield is obtained. Can be realized.

  Here, the mass ratio of the polyamine derivative-based lubricant to the epoxy resin in the sizing agent is in the range of 0.075 to 1.5 means that the mass content of the polyamine derivative-based lubricant contained in the sizing agent Represents that the value obtained by dividing by the mass content of the epoxy resin is in the range of 0.075 to 1.5.

  If the mass ratio of the polyamine derivative-based lubricant to the epoxy resin in the sizing agent is less than 0.075, it is not preferable because the process yield in producing the glass yarn is lowered. Further, if the mass ratio of the polyamine derivative-based lubricant to the epoxy resin in the sizing agent exceeds 1.5, the yarn quality becomes too soft, or conversely, it becomes too hard and desired adjustment is often difficult. It does not become yarn quality.

  In the glass yarn wound body of the present invention, in addition to the above, the ignition loss of the sizing agent on the filament surface constituting the strand of the glass yarn is in the range of 0.2% by mass to 3% by mass with respect to the mass of the glass yarn. If it exists, it can be set as the state by which moderate surface tension was provided to the glass yarn surface, and can make the frictional force between glass yarns appropriate.

  Here, the ignition loss of the sizing agent on the surface of the filament constituting the strand of the glass yarn is in the range of 0.2% by mass to 3% by mass is fixed to the surface with respect to the mass value of the glass yarn. When the film mass value of the sizing agent is expressed in mass%, it means that it is in the range of 0.2 mass% to 3 mass%.

  The ignition loss of the sizing agent on the filament surface of the glass yarn is preferably in the range of 0.2% by mass to 3% by mass, and the ignition loss on the glass surface of the sizing agent is more than 0.2% by mass. Is too small, the fluff characteristics and runnability of the glass yarn are deteriorated. On the other hand, when the loss on ignition of the sizing agent is more than 3% by mass, the unraveling property of the glass strand from the cake and the unwinding from the glass yarn winding body are reduced. Becomes worse.

  The ignition loss of the sizing agent according to the present invention can be measured according to the ignition loss measurement method according to JIS R3420 (2006).

  Moreover, in order to implement | achieve predetermined | prescribed performance in addition to the above, the glass yarn winding body of this invention does not prevent other chemicals from adhering to the glass fiber surface. If necessary, the glass yarn surface can be coated with an antistatic agent, an antioxidant or the like as a sizing agent to which a plurality of kinds of agents are added in a necessary amount.

  In the method for producing a glass yarn wound body of the present invention, a sizing agent containing an epoxy resin, a silane coupling agent and a polyamine derivative-based lubricant is applied to the surface of a filament spun from a bushing, and a plurality of the filaments are applied. The above-mentioned glass yarn wound body is produced by bundling and forming strands, twisting the strands to form glass yarns, and winding the glass yarns on bobbins.

  Here, a sizing agent containing an epoxy resin, a silane coupling agent and a polyamine derivative-based lubricant is applied to the surface of the filament spun from the bushing, and a plurality of the filaments are converged into a strand, which is then twisted into the strand. To produce a glass yarn wound body by winding the glass yarn around a bobbin, the glass filament drawn from a platinum bushing is used as a primary sizing agent for glass yarn as described above. Apply a sizing agent, wind it around a tube, and then wind it around a bobbin or beam fixed to a spindle while twisting while unwinding the glass strand wound from the outer layer of this cake. It represents manufacturing a glass yarn winding.

  Further, a sizing agent as described in any one of claims 1 to 3 is applied to a glass filament drawn from a platinum bushing as a primary sizing agent for glass yarn, wound around a tube, and then the outer layer of the cake. Winding a glass strand wound from a wire while winding it around a bobbin or beam fixed to a spindle while twisting, to produce any one of the above-mentioned glass yarn windings, platinum having a plurality of nozzles The molten glass having a predetermined glass composition is drawn out from a bushing made into a filament, and a primary sizing agent for glass yarn is applied to the surface of the glass to wind it into a tube, and then the glass strand wound from the outer layer of the cake is unwound. In other words, the glass yarn wound body is formed while twisting.

  As a method for coating the sizing agent as the primary sizing agent for glass yarn, any method can be employed as long as it can uniformly coat the surface of the glass monofilament. For example, a spraying method, a dipping method, a coating method, or the like can be appropriately selected and used. Further, there is no need to particularly limit the glass fiber converging method.

  Further, the winding method and the winding device used for the winding method are not particularly limited as long as a stable winding operation can be performed at a predetermined speed.

  The glass cloth of the present invention is obtained by weaving using a glass yarn unwound from the glass yarn winding body according to any one of claims 1 to 3. .

  Here, what is obtained by weaving using a glass yarn unwound from a glass yarn wound body means that the strand surface is coated with a sizing agent containing an epoxy resin, a polyamine derivative-based lubricant and a silane coupling agent. And a glass cloth obtained by fiberizing a glass yarn unwound from a glass yarn winding body obtained by winding a glass yarn of 0.5 to 135 tex provided with a predetermined twist. ing.

  Regarding the weaving method, various known methods can be employed, and it can be used in combination with other materials as necessary. Further, the woven form is not particularly limited. Various weaving forms other than plain weaving can be employed as appropriate.

  The glass yarn twisted yarn of the present invention is characterized in that a plurality of glass yarns unwound from the glass yarn wound body according to any one of claims 1 to 3 are twisted.

  Here, when a plurality of glass yarns unwound from the above-mentioned glass yarn wound body are twisted, the strand surface is coated with a sizing agent containing an epoxy resin, a polyamine derivative-based lubricant and a silane coupling agent. And twisted using a glass yarn unwound from a glass yarn wound body obtained by winding a glass yarn of 0.5 to 135 tex provided with a twist of 0.01 to 13 times / inch. It represents that the glass yarn is a twisted yarn.

  Here, about the glass yarn which comprises a glass yarn intertwisting yarn, what combined together the several glass yarn of this invention as above-mentioned and represents what twisted. In other words, the term “glass yarn” includes a broad sense glass yarn and a narrow sense glass yarn. In a broad sense glass yarn, a definition including a glass yarn twisted yarn and a narrow sense glass yarn is used. In this application, this broad sense glass yarn is used. The glass yarn in a narrow sense and the glass yarn twisted yarn included in the above are distinguished. Therefore, in the present invention, a narrow glass yarn included in a broad glass yarn is simply referred to as a glass yarn.

  As for the twist direction of the glass yarn intertwisted yarn, whether it is S twist (twist direction is a left-handed direction twist) or Z twist (twist direction is a right-handed direction twist), similar to a glass yarn. Good.

  The glass yarn twisted yarn wound body of the present invention is characterized in that the glass yarn twisted yarn according to claim 6 is wound around a bobbin.

  Here, when the glass yarn intertwisted yarn is wound on a bobbin, the strand surface is coated with a sizing agent containing an epoxy resin, a polyamine derivative-based lubricant and a silane coupling agent, and a predetermined twist is imparted. In addition, it is configured by winding a glass yarn twisted using a glass yarn unwound from a glass yarn winding body wound with a glass yarn of 0.5 to 135 tex around a bobbin. Represents.

  About the form of a bobbin, the thing of the material and form similar to the bobbin for glass yarn can be used, and a special change is not required.

  The method for producing a glass yarn twisted yarn wound body of the present invention is characterized in that a glass yarn twisted yarn wound body is produced by winding the glass yarn twisted yarn according to claim 6 on a bobbin.

  Here, manufacturing the glass yarn twisted yarn wound body by winding the glass yarn twisted yarn on a bobbin is a sizing agent in which the strand surface contains an epoxy resin, a polyamine derivative-based lubricant and a silane coupling agent. The above-mentioned glass yarn twisted yarn that has been twisted using a glass yarn unwound from a wound glass yarn wound with a glass yarn of 0.5 to 135 tex coated and coated with a predetermined twist is described above. It shows that a glass yarn twisted yarn wound body is manufactured by continuously winding around such a bobbin.

  The glass cloth of the present invention is woven using a glass yarn twisted yarn unwound from the above-mentioned glass yarn twisted yarn wound body.

  Here, weaving using the glass yarn twisted yarn unwound from the above-mentioned glass yarn twisted yarn wound body means that the strand surface contains an epoxy resin, a polyamine derivative-based lubricant bisphenol A and a silane coupling agent. Glass yarn twisted yarn twisted using a glass yarn unwound from a glass yarn wound body wound with a glass yarn of 0.5 to 135 tex coated with an agent and provided with a predetermined twist It represents a glass cloth obtained by weaving a glass yarn twisted yarn unwound from a wound body.

  About the method of weaving, various well-known methods can be employ | adopted similarly to the case of said glass yarn, and it can also use together with another material as needed. Further, the woven form is not particularly limited. Various weaving forms other than plain weaving can be employed as appropriate.

  The transparent composite composition of the present invention comprises a glass cloth according to claim 5 or a glass cloth of a twisted yarn according to claim 9 and a difference in refractive index nd between 0.01 and Abbe number. It is characterized by being combined with a resin having an optical constant having a difference of νd of 5 or less.

  Here, an optical constant having a refractive index nd of 0.01 or less and a difference of Abbe number νd of ± 5 or less between a glass cloth or a glass cloth of a twisted yarn and a resin is a wavelength 587 by a He light source. The difference between the refractive index of the glass and the cured resin with respect to a spectral light beam (d-line) of .56 nm is within 0.01, and the refractive index of the spectral light beam (F-line) with a wavelength of 486.13 nm by the H light source The value obtained by subtracting the value of the refractive index (nC) of the spectral ray (C-line) having a wavelength of 656.27 nm from the H light source from the value of (nF) is used as the denominator, and the value obtained by subtracting 1 from the refractive index (nd) is used as the numerator. The calculated value, that is, the difference between the glass cloth of the Abbe number value defined as (nd-1) / (nF-nC) or the glass cloth of the twisted yarn and the resin after curing is within 5. .

  If the difference in refractive index nd between the glass cloth and the resin is larger than 0.01, the reflectance at the interface between the glass fiber and the resin increases, and the transparency of the composite composition is impaired, which is not preferable.

  Further, when the difference in Abbe number νd is greater than 5, the reflection loss at the glass fiber / resin interface with visible light having a wavelength other than 587.56 nm increases, and the composite composition has a blue, red, or purple color. Since coloring occurs, it is not preferable.

  In order to adjust the difference in the refractive index nd between the glass cloth or the glass cloth of the twisted yarn and the resin to be within 0.01 and the difference in the Abbe number νd to be within 5, the surface of the filament as described above. The sizing agent containing an epoxy resin, a silane coupling agent, and a polyamine derivative-based lubricant may be appropriately adjusted so that the sizing agent is covered with a glass cloth. That is, the epoxy resin, the silane coupling agent, and the polyamine derivative-based lubricant are the same as described above with respect to more preferable conditions, and in addition, pay attention to the optical constant.

  JIS K 7142 (1996) is a means for confirming that the optical constant is such that the difference in refractive index nd between the glass cloth or the glass cloth of the twisted yarn and the resin is within 0.01 and the difference in Abbe number νd is within 5. ) It can be measured by the method using the Abe Abbe refractometer described in "Method for measuring refractive index of plastic" and the Becke line method of B method.

  In addition to the above, the transparent composite composition of the present invention can be used as a substrate material for optical applications, optical devices, or various high-functional structural materials. Such as durability and excellent electrical performance can be sufficiently exhibited in various applications.

  (1) As described above, the glass yarn winding body of the present invention is a glass yarn winding body in which a glass yarn in which a twist is applied to a strand of glass long fiber is wound on a bobbin, and the glass Since the surface of the filament constituting the yarn strand is coated with a sizing agent containing an epoxy resin, a silane coupling agent and a polyamine derivative-based lubricant, when the glass cloth is woven, The next size and the heat deoiling step and the surface treatment step of the glass cloth after weaving can be omitted, and an inexpensive glass cloth can be produced.

  (2) Moreover, if the mass ratio of the polyamine derivative-type lubricant with respect to the epoxy resin is within the range of 0.075 to 1.5, the glass yarn wound body of the present invention is applied to the surface of the glass yarn. The coated sizing agent film can exhibit stable surface performance over a long period of time without deteriorating over time.

  (3) Furthermore, the glass yarn wound body of the present invention has the properties of the surface of the glass yarn as long as the adhesion rate of the sizing agent to the mass of the glass yarn is in the range of 0.2 mass% to 3 mass%. By setting the predetermined range, it is possible to perform a stable operation without changing various condition settings in a winding operation, a weaving operation, or the like.

  (4) In the method for producing a glass yarn wound body according to the present invention, a sizing agent containing an epoxy resin, a silane coupling agent and a polyamine derivative-based lubricant is applied to the surface of a filament spun from a bushing. The filament is bundled into a strand, the strand is twisted into a glass yarn, and the glass yarn wound body is manufactured by winding the glass yarn around a bobbin. By using various types of equipment that have been developed in the past, it is possible to minimize defects that occur during production by an efficient production method, and to obtain a high-quality glass yarn winding body. Is.

  (5) Since the glass cloth of the present invention is obtained by weaving using the glass yarn unwound from the above-mentioned glass yarn winding body, it is a homogeneous glass cloth with few defects, and is a printed wiring. Even in applications that require high-density mounting such as substrates, stable performance can be exhibited.

  (6) Since the glass yarn intertwisted yarn of the present invention is formed by twisting a plurality of glass yarns unwound from the above-mentioned glass yarn wound body, there are few defects such as fuzz, and the quality is stable for a long time. It is a simple twisted yarn and can exhibit stable performance even in applications that require stringing, weaving, and braiding processes.

  (7) The glass yarn twisted yarn wound body of the present invention is suitable for abundantly supplying glass yarn twisted yarn having a stable quality since the glass yarn twisted yarn described above is wound around a bobbin. .

  (8) The manufacturing method of the glass yarn twisted yarn wound body of the present invention is a method for manufacturing a glass yarn twisted yarn wound body by winding the above-mentioned glass yarn twisted yarn around a bobbin. It is possible to obtain various types of glass yarn twisted and wound yarns of excellent quality and meet customer demands.

  (9) Since the glass cloth of the twisted yarn of the present invention is woven using the glass yarn twisted yarn unwound from the above-mentioned glass yarn twisted yarn wound body, it is homogeneous with various defects suppressed. This is a stable glass cloth, and can exhibit stable performance even in applications that require high-density mounting such as printed wiring boards.

  (10) The transparent composite composition of the present invention has an optical constant having a difference in refractive index nd of 0.01 or less and an Abbe number νd of 5 or less between the glass cloth or the glass cloth of the twisted yarn. Unlike glass cloth using glass yarn that uses general starch-based sizing agents, it is necessary to remove the glass fiber sizing agent by heat deoiling after weaving. In addition, the optical constant of the refractive index nd and Abbe number νd of the glass cloth is not changed in the manufacturing process, and the frequency of adjusting the optical constant of the resin used in the transparent composite composition can be reduced. For this reason, the transparent composite composition of the outstanding performance can also be manufactured efficiently.

  EXAMPLES The glass yarn winding body of the present invention, a method for producing the same, a glass cloth using the glass yarn winding body, and a transparent composite composition will be described below based on examples.

  [Example 1] First, a glass raw material adjusted to have an E glass composition was heated and melted and homogenized, and then drawn out from a bushing having a platinum nozzle so as to form a glass filament having a diameter of 9.2 µm. And the primary sizing agent for glass yarn is apply | coated to the surface as a sizing agent adjusted beforehand.

  This primary sizing agent for glass yarn is 1.0% by mass of a water-soluble epoxy modified product, 2.0% by mass of ethylene oxide added with bisphenol A, and 0.3% of an epoxy silane coupling agent in terms of solid content. %, 0.5% by mass of polyamine derivative and 0.05% by mass of acetic acid, with the remainder being a sizing agent made of water. When the pH of this sizing agent was measured, the value was 4.5.

  Next, a strand obtained by bundling 400 glass filaments (69 tex) of E glass having a diameter of 9.2 μm coated with a primary sizing agent for glass yarn was wound into a tube to obtain a cake, and then the strand was unwound from the cake. Twisting was performed while applying a twist of 1 turn / inch in the Z direction (hereinafter referred to as 1Z) to produce a glass yarn, which was wound around a glass yarn bobbin to form a glass yarn wound body. The loss on ignition of the sizing agent with respect to the glass fiber was 0.40%. The mass ratio of the polyamine derivative-based lubricant to the epoxy resin coating the filament surface was 0.5.

  Further, the glass yarn was warped with a warper to obtain a warp without performing the secondary size, and the glass yarn was used as a weft to plain weave with a high-speed air jet loom to weave a glass cloth.

Table 1 summarizes the performance of the glass yarn wound around the glass yarn winding body obtained in the above process and the performance of the obtained glass cloth. In this table, regarding the unwinding property of the glass yarn winding body, “good”, unraveling is obtained by unwinding the glass yarn from the glass yarn winding body and twisting it without causing problems such as yarn breakage. Those that could not be twisted due to yarn breakage or the like in the inside are indicated as “bad”.

  Table 1 summarizes the performance of the glass yarn wound around the glass yarn winding body obtained in the above process and the performance of the obtained glass cloth. In this table, regarding the unwinding property of the glass yarn winding body, “good”, unraveling is obtained by unwinding the glass yarn from the glass yarn winding body and twisting it without causing problems such as yarn breakage. Those that could not be twisted due to yarn breakage or the like in the inside are indicated as “bad”.

  As for flying performance, the air jet loom (ZA) manufactured by Tsudakoma Kogyo Co., Ltd. was used, and “○” indicates that weaving defects such as shorts did not occur. What occurred was displayed as "x".

  As for the fluff properties, “GOOD” indicates that no yarn breakage or fluff was generated after the strand was unwound at a speed of 100 m / min and passed through the tension bar. The one with the "BAD". The above results are summarized in Table 1 as yarn performance.

  Furthermore, Table 2 summarizes the performance of the glass cloth after weaving this glass yarn into a glass cloth. Regarding the tensile strength in this table, the tensile strength of the glass cloth obtained by weaving the yarn into a plain weave was measured by a measuring method in accordance with JIS, and the value was compared with the following comparative example created by the prior art. Sample No. 1 shown in FIG. It represents as a relative value when the tensile strength about 3 glass cloth is set to 100.

  Further, this glass cloth was impregnated with an FR-4 type epoxy resin varnish according to JIS standard without subjecting it to a heat deoiling step and a surface treatment step, and press cured to produce a prepreg test piece. About this prepreg test piece, by using a pressure cooker test apparatus, by measuring the water absorption after 72 hours in a high temperature and high pressure environment, that is, holding at 133 ° C. and 2 atm, and visually observing the whitening phenomenon, Those having no problem in appearance are indicated as “OK” in the “Water absorption and whitening” column, and those having a high water absorption rate are indicated as “Whitening”. This result is also shown in Table 2.

  In addition, with respect to the process time in this table, the sample No. 3 represents the time required from the glass strand for 3 to the completion of the glass cloth, that is, the relative time when the process time is 100.

  As can be seen from Table 1, with respect to Example 1, the unwinding property of the glass yarn wound body is good because no yarn breakage is observed, and there is no problem with the air jet loom. Further, yarn breakage and fluff did not occur even after passing through the tension bar, and the product had good quality.

  Furthermore, as for the performance after weaving this glass yarn into a glass cloth, Example 1, which is the glass cloth of the present invention, showed "water absorption and whitening" as shown in Table 2 as a result of the evaluation described above. There was no problem with this item, and the process processing time could be shortened to 70% of the conventional process.

  [Example 2] Next, as Example 2, the same E glass filament as in Example 1 was used, and a primary sizing agent for glass yarn was applied to the surface thereof. In terms of solid content, 1.0% by mass of water-soluble epoxy-modified product, 2.0% by mass of ethylene oxide added with bisphenol A, 0.3% by mass of epoxy silane coupling agent, 0.5% by mass of polyamine derivative %, 0.5% by mass of paraffin wax and 0.05% by mass of acetic acid, with the remainder being prepared as a sizing agent consisting of water. When the pH of this sizing agent was measured, the value was 4.5. The mass ratio of the polyamine derivative-based lubricant to the epoxy resin coating the filament surface was 0.5.

  The obtained glass yarn was warped with a warper to obtain a warp without performing secondary sizing, and the glass yarn was used as a weft to plain weave with a high-speed air jet loom to obtain a glass cloth. The unwinding property of the glass yarn wound body, the flying property of the yarn during weaving, and the fluff properties are summarized in Table 1, as in Example 1.

  Table 2 shows the same evaluation results as in Example 1 for the tensile strength of the glass cloth. Further, this glass cloth was impregnated with an FR-4 type epoxy resin varnish according to JIS standards without being subjected to a heat deoiling step and a surface treatment step, and press cured to obtain a prepreg test piece. The results of confirming the water absorption rate and the whitening phenomenon under the same conditions as in Example 1 for this prepreg test piece are also shown in the column of “Water absorption and whitening” in Table 2. Table 2 shows the relative values of the process processing time as in Example 1.

  As is apparent from the results of Tables 1 and 2, the sample Nos. With regard to 2 as well, the unwinding property of the glass yarn winding body is good because yarn breakage is not observed, and its flying performance is not a problem in the air jet loom, even after passing through the tension bar. It was confirmed that thread breakage and fluff did not occur and the product had good quality.

  [Comparative Example 1] Next, as a comparative example of the present invention, an E glass filament similar to that in Example 1 was used, and a primary sizing agent for glass yarn was applied as a sizing agent to the surface of the filament. This primary sizing agent for glass yarn is, in terms of solid content, 4.00% by mass of hydroxypropylated high amylose corn starch, 1.00% by mass of hydroxypropylated normal corn starch, and 0.8% by mass of vegetable oil emulsion. The imidazole derivative was prepared so as to contain a sizing agent containing 0.80% by mass of paraffin wax and 0.8% by mass of paraffin wax, and the rest being warm water.

  As described above, the prepared bundling agent was applied to 400 glass filaments (69 tex) of E glass having a diameter of 9.2 μm, and the bundled strand was wound around a paper tube to form a cake. Then, as described above, the yarn was twisted under the condition of 1Z to produce a glass yarn, which was wound around a glass yarn bobbin. The adhesion amount of the sizing agent to the glass fiber was 1.0% by mass. Next, the spun cake was rewound while twisting 1Z with a twisting machine to produce a glass yarn. The measured value of pH was 4.8.

  This glass yarn was warped with a warper and glued with a gluing machine to obtain a warp. The glass yarn was weaved using a high-speed air jet loom as a weft to obtain a green glass cloth. The unwinding property of the glass yarn wound body, the flying property of the yarn during weaving, and the fluff properties were evaluated in the same manner as in the Examples, and the results are shown in Table 1. Table 2 shows the tensile strength of the glass cloth after heat deoiling and surface treatment of the resulting green glass cloth as 100. Next, this glass cloth was impregnated with an FR-4 type epoxy resin varnish according to JIS standards, and press cured to obtain a prepreg. Table 2 also shows the results of confirming the water absorption rate and the whitening phenomenon of the prepreg test piece prepared from this glass cloth. Further, Table 2 shows the process processing time.

  As is clear from Tables 1 and 2, the sample No. 3 can achieve a certain level of performance, but since it is necessary to go through processes such as heat deoiling and surface treatment, it must be a process that takes a long time compared to the embodiment as a process treatment time. For this reason, it is difficult to carry out efficient production, which is accompanied by an increase in production costs.

  [Comparative Example 2] As still another comparative example, the same sizing agent as in Example 1 was prepared except that a water-soluble epoxy-modified product was not added as a primary sizing agent for glass yarn. The pH of this sizing agent was 4.7 when measured. The sizing agent thus prepared is applied to 400 glass filaments (69 tex) of E glass having a diameter of 9.2 μm, and the bundled strand is wound around a paper tube to form a cake, and then the strand is unwound from the cake. Twisting was performed under the conditions of 1Z to produce a glass yarn, and wound around a glass yarn bobbin to obtain a wound body. The ignition loss of the sizing agent with respect to the glass fiber of this glass yarn was 0.35 mass%. Next, the glass yarn was warped with a warper to obtain a warp without performing secondary sizing, and the glass yarn was used as a weft to plain weave with a high-speed air jet loom to obtain a glass cloth. Table 1 shows the unwinding property of the glass yarn wound body, the flying property of the yarn during weaving, and the fluff characteristics.

  As is clear from the results in Tables 1 and 2, the sample No. As for No. 4, there was no problem with the unwinding and flying properties of the glass yarn wound body, but fluff and thread breakage occurred frequently after passing through the tension bar, and the quality of the product deteriorated during actual use. Turned out to be.

  [Comparative Example 3] Further, as Comparative Example 3, for the primary sizing agent for glass yarn, the same sizing agent as in Example 1 was prepared and prepared except that no polyamine derivative was added. The pH of this sizing agent was measured and found to be 4. Then, a sizing agent was applied to 400 glass filaments (69 tex) of E glass having a diameter of 9.2 μm by the same procedure as in the example, and the bundled strand was wound around a paper tube to obtain a cake. The amount of sizing agent attached to the glass fiber thus obtained was 0.35% by mass. This sample No. The evaluation results of 5 are summarized in Tables 1 and 2 as before.

  As is clear from the results in Tables 1 and 2, the sample No. Regarding No. 5, it was found that the unwindability of the glass yarn wound body was poor, and there was a problem in use in actual use, and the quality of the product was lowered.

  [Comparative Example 4] Next, the glass yarn produced under the same conditions as in Example 1 except that the ignition loss of the sizing agent with respect to the glass fiber was as low as 0.19% by mass. Similar evaluations were made. This glass yarn was used, warped with a warper, used as warp without secondary sizing, and the glass yarn was used as a weft to plain weave with a high-speed air jet loom to obtain a glass cloth. Table 1 shows the unwinding property of the glass yarn wound body, the flying property of the yarn during weaving, and the fluff characteristics.

  Sample No. of Comparative Example 4 In No. 6, the unwinding property of the glass yarn wound body was good, but the flying property was found to have a defect such as a short circuit. Moreover, thread breakage and fluff frequently occur after passing through the tension bar, and the quality of the glass strand was not good.

  [Comparative Example 5] As Comparative Example 5, Sample No. For No. 7, the same sizing agent as in Example 1 was prepared except that no epoxy silane coupling agent was added as the sizing agent. The pH of this sizing agent was 4.7.

  The prepared sizing agent was applied to 400 E glass filaments (69 tex) in the same manner as in the Examples. The bundled strands were wound around a paper tube to form a cake, and then the strands were unwound from the cake, twisted under the conditions of 1Z to produce a glass yarn, and wound around a glass yarn bobbin. For this glass yarn, the loss on ignition of the sizing agent with respect to the glass fiber was 0.45% by mass.

  The glass yarn was also warped with a warper in the same manner as described above to obtain a glass cloth by plain weaving with a high-speed air jet loom using the glass yarn as a weft without performing secondary sizing. Table 1 shows the evaluation results of the unwinding property of the glass yarn wound body, the flying property of the yarn during weaving, and the fluff properties. In addition, Table 2 shows the relative values of the tensile strength of the obtained glass cloth.

  This glass cloth was impregnated with an FR-4 type epoxy resin varnish according to JIS standards without subjecting it to a heat deoiling step and a surface treatment step to obtain a prepreg test piece. Table 2 shows the results of confirming the water absorption rate and the whitening phenomenon after holding this prepreg test piece under the same conditions as described above, that is, at a pressure cooker test apparatus of 133 at 2 ° C. for 2 hours. The process processing time is expressed as a relative value in Table 2 as described above.

  As can be seen from Tables 1 and 2, this test no. Regarding No. 7, the unwinding property, flying property, and fluff property of the glass yarn wound body were good. And although the tensile strength was low, it showed a numerical value equivalent to the conventional one. However, when a pressure cooker test using a prepreg test piece was performed, it was found that the water absorption was high, and as a result, the whitening phenomenon was remarkably observed and the performance was low.

  [Example 3] Further, the glass yarns of Examples 1 and 2 described above were used for twisting, and the obtained glass yarn twisted yarn was wound around a bobbin to obtain a glass yarn twisted yarn wound body. The strand of the strand of the glass yarn twisted yarn constituting this glass yarn twisted yarn wound body was 4.4 turns / inch in the Z direction. A cloth woven by using the glass yarn twisted yarn unwound from the glass yarn twisted yarn wound body was impregnated with an FR-4 type epoxy resin varnish according to JIS standard to obtain a prepreg test piece. This prepreg test piece was held for 72 hours in the same conditions as described above, that is, a pressure cooker test apparatus at 133 ° C. and 2 atm, and the result of confirming the water absorption rate and the whitening phenomenon was the same as that shown in the above examples of Table 2. Results were obtained.

[Example 4] Next Example _{4, SiO 2 51.0%, Al} 2 O 3 2.0%, B 2 O 3 1.0%, MgO 3.0%, SrO 4.2%, BaO Except that the glass is composed of 10.0%, ZnO 4.0%, Li ₂ O 2.6%, Na ₂ O 5.2%, K ₂ O 8.0%, the same as in Example 1. A glass cloth was produced by this method. When the refractive index and Abbe number of the glass cloth were measured in accordance with JIS K 7142 (1996), the Abbe number νd was 45. This glass cloth is impregnated with an epoxy resin having a refractive index nd of 1.596 and an Abbe number νd of 44 after curing in a normal prepreg manufacturing process without performing a heat deoiling process and a surface treatment process. A composition was prepared. Since the epoxy resin having an optical constant having a refractive index nd difference of 0.01 or less and an Abbe number νd difference of 5 or less with a glass cloth is combined, the obtained transparent composite composition is also colored. There was no transparency.

  Here, epoxy resin was used as the resin, but other appropriate resins can be selected according to the application, and various methods suitable for compounding glass cloth and resin can be adopted. Needless to say. In addition, it is also possible to add a plurality of other materials, auxiliaries and the like to the resin that can be used to improve specific performance, improve the properties of the resin, or facilitate complexing. This can be done arbitrarily as long as the function of the object is not impaired. Even when using a glass cloth of a twisted yarn instead of a glass cloth, it is possible to confirm that the same result as described above, that is, the obtained transparent composite composition is not colored and has good transparency. did it.

  As shown above, the glass yarn wound body of the present invention omits the secondary oil size after warp warping using the glass yarn and the heat deoiling step and surface treatment step of the glass cloth after weaving. It is possible to prevent a reduction in strength of the glass cloth that occurs in the heat deoiling step, and to realize a glass cloth having high surface performance. Further, it has become clear that the heat deoiling step and the surface treatment step can be omitted, thereby making it possible to shorten the glass cloth manufacturing process treatment time. Moreover, since the fluctuation | variation of the refractive index of the glass cloth used when manufacturing a transparent resin composite_body | complex is small, adjustment of the optical constant of resin to be used can be decreased.

Claims (10)

A glass yarn wound body in which a glass yarn having a twist applied to a strand of long glass fiber is wound around a bobbin,
The glass yarn wound body, wherein the surface of the filament constituting the strand of the glass yarn is coated with a sizing agent containing an epoxy resin, a silane coupling agent and a polyamine derivative-based lubricant.   The glass yarn wound body according to claim 1, wherein the mass ratio of the polyamine derivative-based lubricant to the epoxy resin in the sizing agent is in the range of 0.075 to 1.5.   The glass yarn wound body according to claim 1 or 2, wherein an ignition loss of the sizing agent with respect to the mass of the glass yarn is in a range of 0.2 mass% to 3 mass%.   A sizing agent containing an epoxy resin, a silane coupling agent and a polyamine derivative-based lubricant is applied to the surface of the filament spun from the bushing. A glass yarn winding body according to any one of claims 1 to 3, wherein the glass yarn winding body is produced by winding the glass yarn around a bobbin.   A glass cloth obtained by weaving using a glass yarn unwound from the glass yarn winding body according to any one of claims 1 to 3.   A glass yarn twisted yarn comprising a plurality of glass yarns unwound from the glass yarn wound body according to any one of claims 1 to 3.   A glass yarn twisted yarn wound body comprising the glass yarn twisted yarn according to claim 6 wound around a bobbin.   A glass yarn twisted yarn wound body is produced by winding the glass yarn twisted yarn according to claim 6 around a bobbin.   A glass cloth of a twisted yarn, which is woven using the glass yarn twisted yarn unwound from the glass yarn twisted yarn wound body according to claim 7.   The glass cloth according to claim 5 or the glass cloth of the twisted yarn according to claim 9 and an optical constant having a difference in refractive index nd of 0.01 or less and an Abbe number νd of 5 or less. A transparent composite composition characterized by being combined with a resin.