WO2004003284A1

WO2004003284A1 - Collecting agent for glass fiber yarn and glass fiber yarn using the same

Info

Publication number: WO2004003284A1
Application number: PCT/JP2003/008139
Authority: WO
Inventors: Yuichi Sugiura; Miki Sakai
Original assignee: Asahi Fiber Glass Company, Limited
Priority date: 2002-06-27
Filing date: 2003-06-26
Publication date: 2004-01-08
Also published as: JP2004026605A; CN1662698A; CN1304681C

Abstract

A collecting agent for use in a glass fiber yarn being prepared by twisting strands each formed by collecting 200 to 800 glass filaments having an average diameter of 5 to 11 μm and being used as a wrap of the glass cloth, characterized in that it comprises a starch, a vegetable oil, a paraffin and an emulsifier, wherein the starch is an etherificated starch having an MS value of 0.001 to 0.025, and the vegetable oil has a saturation degree of 90 % or more. A glass fiber yarn produced by using the collecting agent is used as a warp, and is free from the formation of fluffs in a warping process and excellent in the stability of the tension applied to wraps during warping.

Description

Description Sizing agent for glass fiber yarn and glass fiber yarn using the same

The present invention relates to a glass fiber yarn mainly used for glass cloth used as a substrate material of a printed wiring board, a sizing method therefor, a sizing agent therefor, a glass cloth and the like. Background art

The glass fiber yarn is obtained by bundling hundreds to thousands and hundreds of glass filaments having a fiber diameter of several microns using a sizing agent into a strand, and twisting the strand. The glass fiber yarn is used as a reinforcing material for a fiber reinforced plastic (FRP) product by producing a glass cloth through a weaving process and impregnating the glass cloth with a resin.

In recent years, attention has been focused on the use of this glass cloth, particularly for use as a substrate material for printed wiring boards. In the manufacturing process of this printed wiring board, a glass cloth is impregnated with a resin such as epoxy to form a pre-brig, and further, a thin copper foil or the like is laminated. For this reason, the surface of the glass cloth is required to have very few defects such as fluff so as not to damage the copper foil.

On the other hand, as a manufacturing process of such a glass cloth, the above-mentioned strand is twisted using a ring twisting machine or the like, the glass fiber yarn is wound on a pobin, and then the warp and the weft are wound on a yarn jet loom or the like. Here, in the warp of the glass cloth, a process called a warping process is performed after winding the glass fiber yarn on a pobin and before the weaving process. You. In this warping process, the glass fiber yarn is wound from each pobin into a warping beam with equal tension according to the number, length, density and width of the warps determined by the fabric design. As a result, the warp yarns are prepared in a state in which they are aligned in the width direction in advance, and in the next process, the warping beams are mounted on the warp pay-out position of the loom.

As the performance required for this warp, first, a good bunching property for preventing generation of fluff in the warping step is mentioned. In the warping process, hundreds to thousands of warps need to be aligned in the width direction, so that it is necessary to pass through a plurality of guides, and fluff is liable to be generated due to friction caused by this. Also, when weaving with an air jet, fluff is likely to be generated due to friction with Prov.

Next, in the warping step, stable running properties of the warp are required. When winding onto a warping beam, all warps must be wound onto the beam with a constant tension to prevent hanging and loosening of the warp when unwinding on a loom. If the tension becomes unstable, fluff is generated due to hooking and the like, and it is not preferable because weaving steps and looseness are generated in the glass cloth in the weaving process. Therefore, it is necessary to provide the warp with an appropriate slipperiness to stabilize the tension and secure running property.

Furthermore, prevention of powder dropping during the warping process is required. In the warping process, hundreds to thousands of warp yarns are collectively aligned to increase powder drop, thereby increasing the frequency of cleaning, reducing workability, and causing dirt to adhere. This is not desirable because of the work environment.

The sizing property of the glass fiber yarn, the running property during aging, and the prevention of powder dropping can be adjusted by the composition of the sizing agent when the glass filament is bundled into the strand.

As such a sizing agent, for example, Japanese Patent Application Laid-Open No. 2001-240432 discloses a smoothing agent obtained by emulsifying a smoothing component containing starch, paraffin, and fatty acid triglyceride with an emulsifier. And a sizing agent for glass fibers, comprising a cation-based softening agent. Prevention of fluffing due to breakage of single glass fiber by using three surfactants with specific HLB values in combination as emulsifiers for the above-mentioned smoothing agent, and by setting the amount of starch to the cationic softener at a predetermined ratio In addition, weaving properties in jewelry weaving are enhanced. In that embodiment, the fatty acid triglycerides include hydrogenated plants It is stated that oils are preferred.

In addition, for example, Japanese Patent Application Laid-Open No. 10-72243 discloses that a modified starch for a glass fiber sizing agent, which reduces powder loss and fluffing and provides a yarn having appropriate hardness, is used as a total modified starch. On the other hand, 5 to 95% by weight of 60 ° C, 5% aqueous solution has a viscosity of 1 to 5 CPS, and the same as modified starch having 95 to 5% by weight of 60 ° C, 5% aqueous solution of 6 to 50%. A modified starch for a glass fiber sizing agent comprising a modified starch having the viscosity of CPS is disclosed. In the embodiment, the modified starch is subjected to one or more chemical treatments selected from the group consisting of etherification, esterification, grafting, and cross-linking treatment as necessary, and the degree of the hydroxyalkylation is determined by MS. It is described that the value is added so that the value is in the range of 0.03 to 0.26, preferably 0.07 to 0.20.

Among the above prior arts, in the sizing agent disclosed in Japanese Patent Application Laid-Open No. 2001-240432, gelatinized starch of etherified corn starch or high amylose starch is used alone or in combination. Since there is no particular limitation on the coating strength or elongation that greatly affects the sizing property, there is a problem that the sizing property is insufficient when used for the above-mentioned warp applications.

Also, in the sizing agent disclosed in Japanese Patent Application Laid-Open No. H10-72243, since the MS value of the starch is 0.03 to 0.26, the coating elongation of the starch becomes insufficient, and However, when used for warp applications, there is a problem of insufficient sizing.

Thus, an object of the present invention is to use as a warp of a glass cloth used for a printed wiring board, to improve the convergence in the warping step to prevent the generation of fluff, and to obtain a suitable running tension. A glass fiber yarn sizing agent, a sizing method, and a glass fiber yarn, which are excellent in slipperiness, are excellent in powder drop prevention in a warping process, and are excellent in prevention of fluff generation due to friction at a weaving stage during weaving. And so on. Disclosure of the invention

In order to achieve the above object, the present inventors have conducted intensive studies, and have found that The use of starch with a low degree of ether modification improves the sizing properties.Furthermore, by combining a highly saturated vegetable oil with paraffin as an oil agent, the sizing property is maintained, and the running property over time is maintained. And found that the present invention was completed.

Thus, the present invention has the following features.

1. A sizing agent used for tying the strands of glass fiber yarn used as warp of glass cloth by twisting a strand formed by bundling 200 to 800 glass filaments having an average diameter of 5 to 11 m Wherein the sizing agent comprises at least starch, vegetable oil, paraffin, and an emulsifier; the starch is an etherified starch having an MS value of 0.001 to 0.025; and the saturation of the vegetable oil. A sizing agent for glass fiber yarns having a degree of 90% or more.

2. The sizing agent for glass fiber yarn according to 1 above, wherein the mixing ratio of the paraffin and the vegetable oil is 30 to 70:70 to 30 in parts by mass.

3. The sizing agent for glass fiber yarns according to the above 1 or 2, wherein the emulsifier is an ester type and a Z or ether ester type emulsifier.

4. A glass fiber yarn to which the sizing agent described in 1, 2, or 3 above is adhered.

5. A method for bundling the strands of glass fiber yarns used as warps of glass cloth by twisting strands formed by bundling 200 to 800 glass filaments having an average diameter of 5 to 11 m with a sizing agent. Wherein the sizing agent comprises at least starch, vegetable oil, paraffin, and an emulsifier; the starch is an etherified starch having an MS value of 0.001 to 0.025; and A method for tying glass fiber yarns, wherein the degree of union is 90% or more.

6. A method of manufacturing glass fiber yarn used as a warp of glass cloth by twisting a strand formed by bundling 200 to 800 glass filaments having an average diameter of 5 to 11 m with a sizing agent. The sizing agent comprises at least starch, vegetable oil, paraffin, and an emulsifier; the starch is an etherified starch having an MS value of 0.001 to 0.025; and the saturation of the vegetable oil. Is 90% or more. 7. A glass cloth used as a warp is a glass fiber yarn obtained by twisting strands obtained by bundling 200 to 800 glass filaments having an average diameter of 5 to 11 / xm with a sizing agent. Wherein the sizing agent comprises at least starch, a vegetable oil, paraffin, and an emulsifier, wherein the starch is an etherified starch having an MS value of 0.001 to 0.025, and A glass cloth characterized by having a degree of saturation of 90% or more.

8. Substrate material for printed wiring boards using the glass cloth described in 7 above. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The sizing agent for glass fiber yarns of the present invention contains at least starch, vegetable oil, paraffin, and an emulsifier.

Starch is used to bind filaments and as a film former to protect glass fibers from bending and friction during the process. In the present invention, a major feature is that the starch is an etherified starch having an MS value of 0.001 to 0.025. As a result, a high-strength coating film can be formed on the glass surface, so that the convergence in the warping step can be improved, and the generation of fluff can be suppressed. Here, the coating strength is the tensile strength when the gelatinized starch is formed into a film.

There are no particular limitations on the type of starch material, and corn starch, evening starch, wheat starch, sweet potato starch, potato starch, and the like can be used, but corn starch is low in impurities other than starch and is easily available. It is preferably used.

As the starch, etherified starch modified with ether is used. Examples of the etherification include carboxymethylation, hydroxyalkylation, alkylation, benzylation, and cation etheration, with hydroxyalkylation being preferred. As a result, the gelatinization starting temperature is lowered, so that gelatinization is easy and the solution can be stabilized. Furthermore, it can be removed relatively easily even during heating deoiling. Such hydroxyalkylation can be effected on the starch by, for example, ethyleneoxy. , Propylene oxide, 1,2-butylene oxide and the like. The degree of modification of the above-mentioned etherified starch is in the range of 0.001 to 0.025, preferably in the range of 0.05 to 0.02, in terms of MS value. Here, the MS value indicates the degree of hydroxyalkylation and means the number of moles of hydroxyalkyl groups per anhydroglucose residue of starch. If the MS value is less than 0.001, gelatinization becomes difficult, which is not preferable. If the MS value exceeds 0.025, the film strength for suppressing fluff is not obtained, which is not preferable.

By using such a starch having a low degree of ether modification, a particularly high-strength film can be formed on the surface of the glass fiber as described above. Can be suppressed.

Next, the oil agent used in the present invention will be described. Oils are mainly used for imparting lubricity to strands.

The present invention is characterized in that a vegetable oil having a saturation degree of 90% or more and paraffin are used in combination as an oil agent. By adding paraffin, slipperiness can be imparted to improve running stability in the warping process.On the other hand, paraffin alone causes excessive slipperiness and reduces runnability during aging, so vegetable oil is also used. There is a need. Powdering can also be prevented by the combined use of this vegetable oil.

As the vegetable oil, a vegetable oil having a degree of saturation of 90% or more is preferably used, and a vegetable oil having a degree of saturation of 99% or more is preferably used. Thereby, the smoothness of the yarn surface is improved, the convergence is improved, and the generation of fluff can be prevented. When a vegetable oil having a degree of saturation of less than 90% is used, the smoothness of the yarn surface is reduced and fluff is likely to occur.

In the present invention, the degree of saturation refers to the total amount of hydrocarbons contained in the vegetable oil (calculated excluding the substituents when hydrogen bonded to carbon atoms of hydrocarbons is substituted). Hydrocarbons that do not contain double bonds contained in the vegetable oil, that is, the total amount of saturated hydrocarbons (calculated excluding the substituents when the hydrogen bonded to the carbon atom of the hydrocarbon is substituted) Means the ratio of

As such a vegetable oil having a degree of saturation of 90% or more, a glyceride containing a saturated fatty acid may be used in advance. It may be obtained as a petroleum oil.

The vegetable oil is not particularly limited, and includes coconut oil, palm oil, palm kernel oil, corn oil, cottonseed oil and the like. These may be used alone or as a mixture of two or more. In the present invention, as the vegetable oil, animal and plant oils in combination with animal oils such as lard can be used. When animal and vegetable oils are used, the amount of vegetable oil described below refers to the amount of animal and vegetable oils.

On the other hand, the paraffin used in the present invention is not particularly limited, and conventionally known paraffin wax and the like can be used.

As the content of the above oil agent, the total amount of the paraffin and the vegetable oil is preferably 10 to 50 parts by mass, particularly preferably 20 to 50 parts by mass, based on the starch of 100 parts by mass. It is 40 parts by mass. If the above total content is less than 10 parts by mass, slipperiness cannot be obtained, and the running property decreases, which is not preferable.If the total content is more than 50 parts by mass, slipping is excessive, and running stability is secured. It is not preferable because it becomes impossible. The mixing ratio of paraffin to vegetable oil is preferably 30 to 70:70 to 30, particularly preferably 40 to 60:60 to 40 in parts by mass. . With this blending ratio, vegetable oil can suppress excessive slippage while preventing slippage while imparting lubricity with paraffin, and a sizing agent that is particularly excellent in both sizing properties and running properties can be obtained. If the blending ratio of the above paraffin is less than 30% by mass, sufficient slipperiness cannot be obtained, and the running property is unfavorably lowered. It is not preferable because the stability is lowered.

In the present invention, an emulsifier for emulsifying the above oil agent is further contained. The emulsifier is not particularly limited, and a conventionally known nonionic surfactant can be used. As the nonionic surfactant, an ester, ether, or ester ester emulsifier can be used. Among them, an ester and / or ether ester emulsifier can be used. preferable.

Specifically, examples of the ester emulsifier include polyoxyxethylene monoalkyl esters such as polyoxyethylene monolaurate, polyoxyethylene monostearate, and polyoxyethylene monooleate; Evening Monolau Sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, and other sorbitan esters; Fatty acid dalycerin esters such as polyglycerin stearate can be used. Of these, sorbitan esters are preferred. Examples of the ether emulsifier include, for example, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxetylene stearyl ether, and polyoxyethylene oleyl ether. Examples thereof include phenyl ether type emulsifiers such as polyalkylene xylylene ether, polyalkylene xylylene nonylphenyl ether, and polyoxylethylenoctyl phenyl ether.

Further, examples of the ether ester-based emulsifier include sorbitan ester ether-type emulsifiers such as polyoxyethylene sorbitan ethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate.

These emulsifiers may be used alone or in combination of two or more. The content of the above emulsifier is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total amount of paraffin and vegetable oil. The sizing agent of the present invention may contain other components in addition to the above components. Such components include, for example, cationic lubricants, fungicides, silane coupling agents, and other various additives.

The sizing agent of the present invention can be produced by a conventionally known method by adding an emulsion obtained by emulsifying an oil agent to starch, and further mixing other components. Next, the glass fiber yarn and glass cloth of the present invention obtained by using the above sizing agent will be described. The sizing agent of the present invention obtains strands by bundling 200 to 800 glass filaments having an average diameter of 5 to llm, preferably 5 to 10 m, particularly preferably 8 to 10 m. At that time, it is attached as a sizing agent. As a strand having such an average fiber diameter and the number of bundles, for example, ll ~ 270 tex Hand strands.

As a method of adhering the sizing agent to the glass fiber, the sizing agent can be applied using a roll applicator or the like. The amount of the sizing agent adhered is preferably from 0.3 to 2% by mass, particularly preferably from 0.5 to 1.5% by mass, based on the mass of the glass fiber strand after the sizing agent is adhered. A range is preferred. In addition, the sizing agent may be attached at any time after the fiberization, but it is preferable that the sizing agent is attached immediately after the fiberization for efficient attachment.

The strand to which the sizing agent is attached is further twisted into a glass fiber yarn and wound around a pobin as a warp of glass cloth. Here, a conventionally known ring twisting machine or the like can be used for twisting. Although the number of twists is not particularly limited, it is preferably 0.1 to 2.0 times 5 mm, particularly preferably 0.5 to 1.0 times / 25 mm.

Typical types of glass fiber yarn obtained in this way include, for example, ECG 75 (75 represents 1/100 of yards per pound) in JIS-R3 4 13 A glass thread can be exemplified.

The above-mentioned glass fiber yarn is subjected to a warping step before being supplied to a loom as a warp of glass cloth. In the warping process, creel wrapping is a process for aligning one by one from multiple pobins wound with glass fiber yarn according to the number, length, density, width, etc. based on the fabric design. After the operation, these yarns are drawn out, arranged in parallel, and wound on a warping beam while applying uniform tension. This prepares the warp necessary for weaving. The warping method is not limited, and partial warping may be used.

Since the glass fiber yarn using the sizing agent of the present invention has excellent sizing properties, the generation of fluff in the warping step is small. In addition, since the running tension is stable, excellent running properties can be obtained during aging. In addition, there is little powder loss during aging.

After that, the warping beam is mounted on the unwinding side of the loom, and the glass cloth is manufactured by the weaving process. Air jet loom is used because weaving can be performed at high speed. Is preferred.

As the above-mentioned weaving conditions, conventionally known conditions can be used and are not particularly limited. The woven structure is not particularly limited. For example, when used as a substrate material for a printed wiring board, a plain woven is preferably used.

The glass cloth thus obtained has very few defects such as fluff on the surface, and can be suitably used mainly for a printed wiring board.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In addition, in the following Examples and Comparative Examples, the blending amounts of the respective components are percentages when the entire sizing agent including the finally obtained medium is 100% by mass, that is, as shown in Table 1 below. As described above, the value is expressed as a percentage value in the composition of the whole sizing agent including the finally obtained aqueous medium.

Example 1

Preparation of gelatinized starch paste>

Hydroxypropyl corn starch, which is an etheric starch (MS value = 0.01) 4.4 mass% (as described above, the percentage value in the composition of the entire sizing agent containing the finally obtained aqueous medium, also Was dispersed in water, heated, and gelatinized at 95 ° C for 30 minutes to obtain a gelatinized liquid.

0.6% by mass of paraffin wax, 0.6% by mass of vegetable oil having a saturation of 99.7% composed of coconut oil and palm oil, and 0.0 of solpitan monostearate as an emulsifier

%, Melted and mixed, and emulsified with hot water at 80 ° C. to obtain an oil emulsion.

Preparation of other additive components

It was dispersed in hot water so that 0.2% by mass of a cationic lubricant composed of tetraethylenepentamine (TEP A) and stearic acid condensate acetate and 0.01% by mass of a fungicide were added.

<Preparation of sizing agent> The starch gelatinizing solution, the oil agent emulsion, the cationic lubricant and the fungicide were mixed, and warm water was added to obtain the sizing agent of Example 1 shown in Table 1 (solid content).

Example 2

Table 1 (solid content) was prepared in the same manner as in Example 1, except that hydroxypropyl corn starch having an MS value of 0.022 was used as the esterified starch in Example 1. A sizing agent of Example 2 was obtained.

Example 3

In Example 1, except that a vegetable oil composed of coconut oil and palm oil having a saturation of 92% was used as the vegetable oil, the same adjustment method as in Example 1 was used, and Example 3 shown in Table 1 (solid content) was used. Was obtained.

Example 4

Example 1 is the same as Example 1 except that 0.36% by mass of paraffin wax and 0.84% by mass of vegetable oil having a saturation degree of 99.7% consisting of coconut oil and palm oil were used. By the adjusting method, the sizing agent of Example 4 shown in Table 1 (solid content) was obtained.

Example 5

Example 1 is the same as Example 1 except that 0.84% by mass of paraffin wax and 0.36% by mass of vegetable oil having a saturation degree of 99.7% consisting of coconut oil-palm oil were used. By the adjusting method, the sizing agent of Example 5 shown in Table 1 (solid content) was obtained.

Example 6

Example 1 was repeated except that polyoxyethylene disorbitan monostearate was not used as an emulsifier and only 0.18% by mass of sorbitan monostearate was used. (Solid content) was obtained as the sizing agent of Example 6.

Example 7

Example 1 was repeated except that sorbitan monostearate was not used as the emulsifier and only 0.18% by mass of polyoxyethylene disorbinone monostearate was used. The sizing agent of Example 7 shown in Table 1 (solid content) was obtained. Comparative Example 1

Comparative Example 1 shown in Table 1 (solid content) was prepared in the same manner as in Example 1 except that hydroxypropylated corn starch having an MS value of 0.08 was used as the etherified starch. Was obtained.

Comparative Example 2

Example 1 was repeated except that vegetable oil was not used as the oil agent and only paraffin wax was used in an amount of 1.2% by mass. The preparation method was the same as in Example 1 except that Comparative Example 2 shown in Table 1 (solid content) was used. A sizing agent was obtained.

Comparative Example 3

The sizing agent of Comparative Example 3 shown in Table 1 (solid content) was prepared in the same manner as in Example 1 except that paraffin was not used as the oil agent and only vegetable oil was used in an amount of 1.2% by mass. Got.

Comparative Example 4

Table 1 (solid fraction) was prepared in the same manner as in Example 1 except that a vegetable oil of palm oil / corn oil having a saturation degree of 41% and 0.6% by mass was used as the vegetable oil in Example 1. The sizing agent of Comparative Example 4 shown in the following was obtained.

table 1

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Starch 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4

MS value 0.01 0.022 0.01 0.01 0.01 0.01 0.01 0.08 0.01 0.01 0.01 Harafffin wax 0.6 0.6 0.6 0.36 0.84 0.6 0.6 0.6 1.2 0 0.6 Vegetable oil 0.6 0.6 0.6 0.84 0.36 0.6 0.6 0.6 0 1.2 0.6 Saturation 99.7 99.7 92 99.7 99.7 99.7 99.7 99.7 99.7 41 Sorbitan monostearate 0.09 0.09 0.09 0.09 0.09 0.18 0 0.09 0.09 0.09 0.09 e. Lithylene'zosorbitan 0.09 0.09 0.09 0.09 0.09 0 0.18 0.09 0.09 0.09 0.09 monosparate

Cationic lubricant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Fungicide 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Total solids 5.99 5.99 5.99 5.99 5.99 5.99 5.99 5.99 5.99 5.99 5.99 Water 94.01 94.01 94.01 94.01 94.01 94.01 94.01 94.01 94.01 94.01 94.01

Test example

Using the sizing agents of Examples 1 to 7 and Comparative Examples 1 to 4, a glass fiber yarn was manufactured and warped, and the running tension in the warping process, the number of fluffs, and the powder loss during aging were examined. .

The production and warping of the glass fiber yarn were performed under the following conditions.

First, a strand is manufactured by bundling 400 glass filaments having an average diameter of 9 m, and the above-mentioned sizing agent is used as a solid content of 1.0% by mass based on the mass of the glass fiber strand to which the sizing agent is attached. Immediately after fiberization.

The strand was twisted using a ring twisting machine to obtain a glass fiber yarn of ECG751 / 0.7Z in JIS-R334.

600 glass fiber yarns were set, aligned and warped, and wound around a warping beam.

The running property in the warping step was measured by measuring the tension (g) of the glass fiber yarn during running using a tension meter.

The number of fluffs was measured by using a fluff detector.

The powder drop is visually evaluated for the amount of the sizing agent that has fallen with a Prize guide or the like during aging. 1: very small, 2: small, 3: normal, 4: large, 5: very large, 5 It was evaluated on a scale.

Table 2 summarizes the above measurement results.

Table 2

From the results in Table 2, in Examples 1 to 7 of the present invention, the running tension was 21 to 28 g, and the running property after aging was good. In addition, the number of fluff and powder fall was small.

On the other hand, in Comparative Example 1 using corn starch having an MS value of 0.08, the number of fluffs in the warping step increased due to insufficient convergence. Also, in Comparative Example 2 which contained only paraffin as the oil agent and did not contain vegetable oil, the slipperiness was excessive, the tension was reduced, the running property was worsened, and the powder drop was further worsened. Further, in Comparative Example 3, which was a vegetable oil-only oil and did not contain paraffin, the running tension was significantly increased and the number of fluff was increased due to lack of slipperiness. In Comparative Example 4 using a vegetable oil having a saturation degree of 41%, in which the saturation degree of the vegetable oil is out of the specified range of the present invention, the running tension is increased due to the lack of slipperiness, and the number of fluff is also reduced. Increased. Industrial applicability

ADVANTAGE OF THE INVENTION According to the sizing agent of this invention, since the sizing property is excellent also in the warping process of the glass fiber yarn used as a warp of a glass cloth, generation | occurrence | production of fluff can be prevented effectively. . In addition, since a moderate slip property is imparted, the tension in the warping process is constant and the running property is excellent, and the hanging and loosening of the warp in the weaving of weaving can be prevented. Therefore, the glass fiber yarn using this sizing agent can be suitably used for a glass cloth used for a printed wiring board.

Claims

: Hata WO 2004/003284 PCT / JP2003 / 008139 17 Scope of request

1. A sizing agent used to bundle glass fiber yarns, which are used as glass fiber warp yarns, by twisting strands formed by bundling 200 to 800 glass filaments having an average diameter of 5 to 11 m. Wherein the sizing agent comprises at least starch, vegetable oil, paraffin, and an emulsifier, wherein the starch is an etherified starch having an MS value of 0.001 to 0.025, and a saturation of the vegetable oil. A sizing agent for glass fiber yarns having a degree of 90% or more.

2. The sizing agent for glass fiber yarn according to claim 1, wherein the mixing ratio of the paraffin and the vegetable oil is 30 to 70:70 to 30 by mass.

3. The sizing agent for glass fiber yarns according to claim 1, wherein the emulsifier is an ester type and a Z or ether ester type emulsifier.

4. A glass fiber yarn having the sizing agent according to claim 1, 2 or 3 attached thereto.

5. 200 to 800 glass filaments with an average diameter of 5 to 11 m are bundled with a sizing agent and twisted into strands, and the strands of glass fiber yarn used as warps of glass cloth are bundled. The method, wherein the sizing agent comprises at least starch, a vegetable oil, a paraffin, and an emulsifier, wherein the starch is an etherified starch having an MS value of 0.001 to 0.025, and A method for focusing glass fiber yarns, wherein the degree of saturation is 90% or more.

6. A method for producing a glass fiber yarn used as a warp of glass cloth by twisting a strand formed by bundling 200 to 800 glass filaments having an average diameter of 5 to 11 m with a sizing agent. Wherein the sizing agent comprises at least starch, vegetable oil, paraffin, and an emulsifier; the starch is an etherified starch having an MS value of 0.001-10.025; and the saturation of the vegetable oil is A method for producing glass fiber yarn, characterized in that it is at least 90%.

7. A glass cloth used as a warp, wherein a glass fiber yarn obtained by twisting a strand formed by bundling 200 to 800 glass filaments having an average diameter of 5 to 11 / _tm with a sizing agent is used as the warp, and But starch and vegetable oil and paraffin : Rui

WO 2004/003284 PCT / JP2003 / 008139

A glass cloth containing at least 18 and an emulsifier, wherein the starch is an etherified starch having an MS value of 0.001 to 0.025, and the vegetable oil has a saturation of 90% or more. .

8. Substrate material for printed wiring boards, wherein the glass cloth according to claim 7 is used.