CN1304681C - Collecting agent for glass fiber yarn and glass fiber yarn using the same - Google Patents

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 mum 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

Sizing agent for glass fiber yarn and glass fiber yarn using the sizing agent

technical field

The present invention relates to a glass fiber yarn used in a glass cloth, a method for bundling the same, a bundling agent for the bundling, and a glass cloth mainly used as a substrate material of a printed wiring board and the like.

Background technique

Glass fiber yarn is a yarn formed by bundling hundreds to thousands of glass monofilaments with a fiber diameter of several microns into a tow with a sizing agent, and then twisting the tow. The glass fiber yarn is woven into a glass cloth through a weaving process, and the glass cloth can be used as a reinforcing material for fiber plasticized (FRP) products by impregnating the glass cloth with a resin.

In recent years, as the use of this glass cloth, attention has been paid to the use of this glass cloth as a substrate material of a printed wiring board. In the manufacturing process of this printed wiring board, glass cloth is impregnated with a resin such as epoxy to form a prepreg, and thin copper foil or the like is laminated to form the printed wiring board. Therefore, in order not to damage the copper foil, it is required that there are very few defects such as hairiness on the surface of the glass cloth.

On the other hand, as the weaving process of such a glass cloth, the above-mentioned tow is twisted with a ring twister or the like, the glass fiber yarn is wound on a bobbin, and thereafter, the yarn is passed through an air-jet loom. Weaving between warp and weft.

Here, the warp of the glass cloth has a process called a warping process (warping) before the weaving process after the above-mentioned glass fiber yarn is wound into a bobbin. In this warping process, according to the number, length, density and width of the warp yarns determined by the fabric design, the glass fiber yarns are pulled out from the respective bobbins at the same tension and wound onto the warping beam , Like this, warp yarn will be prepared in advance and horizontally neatly arranged, and in next process, this warp warp beam is assembled on the position that loom warp yarn is drawn out.

As the required performance of the warp yarn, firstly, bundling properties for preventing the generation of hairiness in the above-mentioned warping process are required. In the warping process, in order to align hundreds to thousands of warp yarns in the transverse direction, they must pass through multiple yarn guides, and the resulting friction is likely to produce hairiness. Such friction is also prone to hairiness.

In addition, in the above-mentioned warping process, it is also required that the warp yarns have stable running properties. When winding into a warp beam, in order to prevent the warp yarns from hanging and loosening when the loom is drawn out, all the warp yarns must be rolled into bundles with a certain tension. If the tension is not stable, hairiness is likely to occur due to snags or the like, and in the weaving process, crosspieces, slack, etc. are generated in the glass cloth, which is not preferable. Therefore, it is necessary to impart moderate slipperiness to the warp and stabilize the tension to ensure runnability.

In addition, it is also required to prevent powder falling in the warping process. In the warping process, since hundreds to thousands of warp yarns are aligned together, powder falling increases, cleaning frequency increases, operability decreases, and dirt adheres, so it is not ideal. From the perspective of the working environment, it is not ideal.

The sizing properties of such glass fiber yarns, the running properties during warping, and the prevention of dust falling can all be adjusted by the composition of the sizing agent when the glass monofilaments are condensed into a tow.

As such a sizing agent, for example, Japanese Patent Laid-Open Publication No. 2001-240432 discloses the following sizing agent for glass fibers, the sizing agent contains a smoothing agent and a cationic softener, and the smoothing agent is emulsified with an emulsifier including starch, paraffin and Formed as a smooth component of fatty acid triglycerides. As an emulsifier for a smoothing agent, by combining three surfactants with a specific HLB value and setting the amount of starch to cationic softener at a specified ratio, it can prevent hairiness caused by breaking glass single fibers and improve air-jet weaving of weaving. In this embodiment, it is described that hydrogenated vegetable oil is preferably used as fatty acid triglyceride.

In addition, the following chemical starch for glass fiber sizing agent is disclosed in Japanese Patent Laid-Open Publication No. 10-72243 as a chemical starch for glass fiber sizing agent that reduces powder falling or hairiness and can produce yarn with moderate hardness. Starch: 5-95% by weight of all chemical starch, chemical starch with a viscosity of 1-5cps in 60°C, 5% aqueous solution and 95-5% by weight of all chemical starch in 60°C, 5% aqueous solution Composition of chemical starch with a viscosity of 6-50 cps. In this embodiment, it is described that chemical starch is subjected to one or more chemical treatments selected from etherification, esterification, grafting, and cross-linking treatment as required, and the MS value added to indicate the degree of hydroxyalkylation is 0.03 to 0.26, preferably within the range of 0.07 to 0.20.

In the above-mentioned prior art, since the starch of the sizing agent in the Japanese Patent Laid-Open Publication No. 2001-24043 has no special restrictions on the strength and extensibility of the covering film that greatly affects the sizing, when it is used for the above-mentioned warp application, there is As the above-mentioned starch, gelatinized products of etherified corn starch and high-amylose corn starch can be used alone or in combination.

In addition, the sizing agent in Japanese Patent Laid-Open Publication No. 10-72243 has a problem of insufficient sizing when used as a warp because the MS value of starch is 0.03 to 0.26, and the stretchability of the covering film of starch is insufficient.

Therefore, the object of the present invention is to provide a kind of sizing agent, sizing method and glass fiber yarn etc. of glass fiber yarn, this glass fiber yarn can be used as the warp yarn of the glass cloth for printed wiring board, the warp of warping process. Condensation is good, hairiness can be prevented, and moderate sliding properties obtained by stable running tension can be obtained. Furthermore, the performance of preventing powder falling in the warping process is good, and hairiness caused by friction of reeds, etc. during weaving can be prevented. The resulting performance is good.

Contents of the invention

In order to achieve the above object, the present inventors conducted intensive studies, and as a result, found that: by using starch with a low degree of ether modification as a coating film forming agent, the bundling property can be improved. In addition, by using vegetable oil with a high degree of saturation and paraffin Combining them as an oil agent can maintain the bundle property, and the running property at the time of warping is also good, and the present invention has been completed.

Therefore, the present invention is characterized by having the following points:

1. Sizing agent for glass fiber yarn, which is used to bundle 200 to 800 glass monofilaments with an average diameter of 5 to 11 μm into tows, and then twist them, and use them as glass warp yarns of glass cloth A sizing agent for bundling the aforementioned tows of fiber yarns, wherein the sizing agent contains at least starch, vegetable oil, paraffin, and an emulsifier, the starch is etherified starch with an MS value of 0.001 to 0.025, and the saturated starch of the vegetable oil is degree greater than or equal to 90%.

2. The sizing agent for glass fiber yarn according to the above 1, wherein the compounding ratio of the paraffin wax and the vegetable oil is 30-70:70-30 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 and/or ether ester emulsifier.

4. A glass fiber yarn formed by adhering the sizing agent described in any one of 1 to 3 above.

5. The bundle method of glass fiber yarn, which is to use a bundle agent to bundle 200~800 glass monofilaments with an average diameter of 5~11μm into a bundle, and then twist it, and use it as a warp yarn of glass cloth A method for bundling the above-mentioned tows of glass fiber yarns, wherein the above-mentioned sizing agent contains at least starch, vegetable oil, paraffin, and emulsifier, the above-mentioned starch is an etherified starch with an MS value of 0.001 to 0.025, and the saturation degree of the above-mentioned vegetable oil is Greater than or equal to 90%.

6. The manufacturing method of glass fiber yarn, which is to use a sizing agent to gather 200 to 800 glass monofilaments with an average diameter of 5 to 11 μm into a tow, then twist it, and use it as a warp yarn of glass cloth A method for producing glass fiber yarn, characterized in that the sizing agent contains at least starch, vegetable oil, paraffin, and emulsifier, the starch is etherified starch with a MS value of 0.001 to 0.025, and the degree of saturation of the vegetable oil is greater than or equal to 90%. .

7. Glass cloth, which is made of 200-800 glass monofilaments with an average diameter of 5-11 μm into tows by using a sizing agent, twisted to form glass fiber yarns, and used as warp yarns to weave glass The cloth is characterized in that the sizing agent contains at least starch, vegetable oil, paraffin, and emulsifier, the starch is etherified starch with an MS value of 0.001-0.025, and the saturation degree of the vegetable oil is greater than or equal to 90%.

8. A substrate material for a printed wiring board, wherein the glass cloth described in 7 above is used.

Detailed ways

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.

The purpose of using starch is to bundle monofilaments and protect glass fibers from bending and friction during the process as a coating film forming agent. Therefore, the outstanding feature of this invention is etherified starch whose MS value of starch is 0.001-0.025. In this way, since a high-strength coating film is formed on the glass surface, the bundling property in the warping process can be improved, and the occurrence of hairiness can be suppressed. The cover film strength here refers to the tensile strength when the gelatinized starch is formed into a film.

There are no special restrictions on the type of starch raw material, and cornstarch, tapioca starch, wheat starch, sweet potato starch, potato starch, etc. can be used, but from the perspective of less impurities other than starch and easy purchase, cornstarch is better.

As the starch, ether-modified etherified starch is used. Etherification means carboxymethylation, hydroxyalkylation, alkylation, benzylation, cationic etherification, etc. Among them, hydroxyalkylation is preferred. Thereby, since the gelatinization initiation temperature falls, gelatinization becomes easy, and a solution can also be stabilized. In addition, even when degreasing by heating, it is relatively easy to remove.

Such hydroxyalkylation can be obtained by, for example, ethylene oxidation, propylene oxidation, 1,2-butene oxidation, etc., on the aforementioned starch.

Moreover, the modification degree of the said etherified starch is 0.001-0.025 represented by MS value, Preferably it exists in the range of 0.005-0.02. The MS value here indicates the degree of hydroxyalkylation, which 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 it exceeds 0.025, the film strength for suppressing hairiness cannot be obtained, so it is not preferable.

By using such a starch with a small degree of ether modification, as described above, an extremely high-strength coating film can be formed on the surface of the glass fiber, and when used in warp yarns, the bundling property can be improved and the occurrence of hairiness can be suppressed.

The oil agent used in the present invention will be described below. The main purpose of using a finish is to impart lubricity to the tow.

In the present invention, the oil agent is characterized in that vegetable oil having a saturation degree of 90% or more and paraffin wax are used in combination. In addition, paraffin wax is added to impart slidability to improve running stability in the warping process. However, if only paraffin wax is contained, the slidability will be excessive and the running performance during warping will be reduced. Therefore, it must be used in combination with vegetable oil. Combining with this vegetable oil also prevents dusting.

As the vegetable oil, a vegetable oil with a saturation degree of 90% or more can be used, preferably a vegetable oil with a saturation degree of 99% or more. In this way, the smoothness of the yarn surface is improved, the bundling property is improved, and the occurrence of hairiness can be prevented. If a vegetable oil with a saturation of less than 90% is used, the smoothness of the yarn surface will decrease, and hairiness will easily occur.

The degree of saturation in the present invention means: relative to the total amount of hydrocarbon contained in the vegetable oil (calculated by removing the substituent when the hydrogen bonded to the carbon atom of the hydrocarbon is substituted), does not contain the hydrocarbon contained in the above-mentioned vegetable oil. Hydrocarbons containing double bonds, that is, the ratio of the total amount of saturated hydrocarbons (calculated by removing the substituents when the hydrogen bonded to the carbon atoms of the hydrocarbons is substituted).

Such a vegetable oil having a degree of saturation of 90% or more may be glyceride containing saturated fatty acid in advance, or a so-called hardened oil obtained by hydrogenating and saturating unsaturated fatty acid.

The vegetable oil is not particularly limited, and coconut oil, palm oil, palm kernel oil, corn oil, cotton oil and the like can be used. These may be used individually or in mixture of 2 or more types. As the vegetable oil of the present invention, animal and vegetable oils obtained by combining animal oils such as lard can be used. When animal and vegetable oils are used, the amount of vegetable oils mentioned 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 paraffins and the like can be used.

The content of the above-mentioned oil agent is preferably from 10 to 50 parts by mass, particularly preferably from 20 to 40 parts by mass, based on 100 parts by mass of the above-mentioned starch, the total content of the above-mentioned paraffin and the above-mentioned vegetable oil as the total amount of the oil agent. If the above-mentioned total content is less than 10 parts by mass, slidability cannot be obtained and the running property is low, which is not preferable; on the contrary, if it exceeds 50 parts by mass, the slidability is excessive and running stability cannot be ensured, which is not preferable.

The compounding ratio of paraffin:vegetable oil is preferably 30-70:70-30, particularly preferably 40-60:60-40, expressed in parts by mass. With this compounding ratio, paraffin wax imparts slipperiness, vegetable oil suppresses excessive slipperiness, prevents hairiness, and provides a sizing agent with excellent sizing and running properties. If the compounding ratio of the above paraffin wax is less than 30% by mass, sufficient slidability cannot be obtained and the running property is low, which is not preferable; on the contrary, if it exceeds 70% by mass, the slidability is excessive and the stability is low, which is not preferable.

In the present invention, an emulsifier for emulsifying the above oil agent may also be contained.

The emulsifier is not particularly limited, and conventionally known nonionic surfactants and the like can be used. As the nonionic surfactant, ester, ether, and ether ester emulsifiers can be used, and among them, ester and/or ether ester emulsifiers are preferably used.

Specifically, as an emulsifier of esters, for example, polyoxyethylene monoalkyl esters of polyoxyethylene monolaurate, polyoxyethylene monostearate, and polyoxyethylene monooleate; Monolaurate, Sorbitan Monostearate, Sorbitan Monopalmitate, Sorbitan Monooleate, Sorbitan Sesquioleate, Sorbitan Trioleate Sorbitan esters such as esters; fatty acid glycerides such as polyglyceryl oleate, polyglyceryl laurate, and polyglyceryl stearate, among which sorbitan esters are preferably used.

As ether emulsifiers, for example, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl Ether and other polyoxyethylene alkyl ethers; polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether and other phenyl ether emulsifiers.

As an emulsifier for ether esters, for example, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan Emulsifiers of sorbitan ester ethers such as sorbitan monooleate, etc.

These emulsifiers may be used alone or in combination of two or more. The content of the emulsifier is preferably from 5 to 40% by mass, particularly preferably from 10 to 30% by mass, based on the total amount of paraffin wax and vegetable oil.

The sizing agent of the present invention may contain other components other than the above-mentioned components. Such components include, for example, cationic emulsifiers, antifungal agents, organosilane coupling agents, and other various additives.

The sizing agent of the present invention can be produced by adding an emulsion emulsified by an oil agent to starch and then mixing other components by a conventionally known method.

Next, the glass fiber yarn and glass cloth of the present invention produced using the above-mentioned sizing agent will be described. The sizing agent of the present invention is attached as a sizing agent when 200 to 800 glass monofilaments with an average diameter of 5 to 11 μm, preferably 5 to 10 μm, particularly preferably 8 to 10 μm are bundled to obtain a tow. As the tow having such an average fiber diameter and a bundle count, for example, a tow having a count of 11 to 270 tex can be used.

As a method of adhering the sizing agent to the glass fibers, a method of coating with a feed roll or the like can be used. The adhesion amount of the sizing agent is based on the mass of the glass fiber strands to which the sizing agent is attached, expressed as the amount of solid content, and is 0.3 to 2% by mass, particularly preferably in the range of 0.5 to 1.5% by mass. In addition, the timing of attaching the sizing agent may be performed after fibrillation, but it is preferable to attach it immediately after fibrillation for effective adhesion.

The tow to which the above-mentioned sizing agent is adhered is further twisted to form a glass fiber yarn, which is wound on a bobbin as a glass cloth warp. For the twisted yarn here, a conventionally known ring twister or the like can be used. The degree of twist is not particularly limited, but is preferably 0.1 to 2.0 twists/25mm, particularly preferably 0.5 to 1.0 twists/25mm.

As a typical type of glass fiber yarn produced in this way, for example, glass filaments of ECG75 (75 means 1/100 of a yard per pound) in JIS-R3413 can be used.

The above-mentioned glass fiber yarn is subjected to a warping process before being supplied to a loom as a warp yarn of glass cloth. In the warping process, "creel loading" is performed to align the bobbins wound with glass fiber yarn one by one according to the number, length, density, width, etc. designed according to the fabric. "Operation, and then, these multiple yarns are pulled out, arranged in parallel, while giving the same tension, while winding into a warp beam. Thus, the warp yarns required for weaving are finished. There is no limit to the method of warping, and partial warping may also be used.

Then, since the glass fiber yarns using the sizing agent of the present invention are excellent in sizing properties, there is little hairiness in the warping process. In addition, since the running tension is stable, excellent running properties can be obtained during warping. In addition, there is less dust falling during warping.

Thereafter, the warp warp beam is assembled on the side pulled out of the loom, and is woven into glass cloth by the weaving process. The loom is preferably an air-jet loom capable of high-speed weaving.

As the above-mentioned weaving conditions, conventionally known conditions can be used without limitation. In addition, there are no particular limitations on the texture of the fabric. For example, when used as a substrate material of a printed wiring board, a plain weave is preferably used.

The above-mentioned glass cloth obtained in this way has very few defects such as surface hairiness, and is mainly used for printed wiring boards.

Example

The present invention will be described in more detail below through examples, but the present invention is not limited by the examples. The compounding amount of each component of the following examples and comparative examples is the percentage when the total amount of the finally prepared medium-containing sizing agent is set as 100% by mass, that is, as shown in the following Table 1, to account for the total amount of the final prepared medium-containing sizing agent The percentage value of the obtained aqueous medium in the overall composition of the sizing agent is recorded.

Example 1

(Preparation of starch gelatinization solution)

Hydroxypropylated cornstarch (MS value = 0.01) of etherified starch of 4.4% by mass (as described above, the percentage value in the total composition of the sizing agent of the finally prepared aqueous medium, the same below) was dispersed in Heat in water, and conduct gelatinization at 95°C for 30 minutes to obtain a gelatinized liquid.

(Preparation of oil emulsion)

0.6% by mass of paraffin, 0.6% by mass of vegetable oil with a saturation degree of 99.7% consisting of coconut oil and palm oil, 0.09% by mass of emulsifier, namely sorbitan monostearate and 0.09% by mass of poly Oxyethylene sorbitan monostearate was melted and mixed together, and emulsified in hot water at 80°C to obtain an oil emulsion.

(modulation of other added ingredients)

It was prepared by dispersing 0.2% by mass of a cationic lubricant composed of tetraethylenepentylamine (TEPA) and stearic acid condensate acetate and 0.01% by mass of an antifungal agent in hot water.

(Preparation of stimulant)

Mix above-mentioned starch gelatinization liquid, oil emulsion, cationic lubricant and antifungal agent together, add warm water and make the sizing agent of embodiment 1 as shown in Table 1 (solid composition).

Example 2

In Example 1, except that the hydroxypropylated cornstarch with MS value=0.022 was used as the etherified starch, the bundle of Example 2 shown in Table 1 (solid content) was obtained by the same adjustment method as in Example 1. agent.

Example 3

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

Example 4

In embodiment 1, except adopting the paraffin wax of 0.36 mass %, the vegetable oil that the saturation degree that is made of coconut oil and palm oil is 99.7% except adopting 0.36 mass %, table 1 (solid form Component) the sizing agent of Example 4 shown.

Example 5

In embodiment 1, except adopting the paraffin wax of 0.84 mass %, the vegetable oil that the saturation degree that is made of coconut oil and palm oil of 0.36 mass % is 99.7%, with the same adjustment method as embodiment 1, table 1 (solid Component) the sizing agent of Example 5 shown.

Example 6

In Example 1, except that polyoxyethylene disorbitan monostearate is not used, but only 0.18% by mass of sorbitan monostearate is used as an emulsifier, the same The sizing agent of Example 6 shown in Table 1 (solid content) was prepared by the adjustment method.

Example 7

In Example 1, except not using sorbitan monostearate, but only using 0.18% by mass of polyoxyethylene disorbitan monostearate as an emulsifier, the same as in Example 1 The sizing agent of Example 7 shown in Table 1 (solid content) was prepared by the adjustment method.

Comparative example 1

In Example 1, except that hydroxypropylated cornstarch with MS value = 0.08 was used as the etherified starch, the bundle of Comparative Example 1 shown in Table 1 (solid content) was obtained by the same adjustment method as in Example 1. agent.

Comparative example 2

In Example 1, the sizing agent of Comparative Example 2 shown in Table 1 (solid content) was prepared by the same adjustment method as in Example 1, except that no vegetable oil was used and only 1.2% by mass of paraffin was used as the oil agent.

Comparative example 3

In Example 1, the sizing agent of Comparative Example 3 shown in Table 1 (solid content) was prepared by the same adjustment method as in Example 1, except that no paraffin was used and only 1.2% by mass of vegetable oil was used as an oil agent.

Comparative example 4

In Example 1, in addition to adopting 0.6% by mass of vegetable oil composed of palm oil and corn oil with a saturation degree of 41% as vegetable oil, the same adjustment method as in Example 1 was used to obtain the mixture shown in Table 1 (solid content). The sizing agent of Comparative Example 4.

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 MS value 0.01 0.022 0.01 0.01 0.01 0.01 0.01 0.08 0.01 0.01 0.01 paraffin 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 Polyethylene disorbitan monostearate 0.09 0.09 0.09 0.09 0.09 0 0.18 0.09 0.09 0.09 0.09 cationic lubricant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 antifungal agent 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 case

Production and warping of glass fiber yarns were performed using the sizing agents of Examples 1 to 7 and Comparative Examples 1 to 4, and the running tension in the warping process, the number of hairiness, and powder fall during warping were investigated. Production and warping of glass fiber yarns were carried out under the following conditions.

First, 400 glass monofilaments with an average diameter of 9 μm are bundled to form a bundle, and a sizing agent is attached immediately after fiberization. The above-mentioned sizing agent is based on the quality of the glass fiber bundle after the sizing agent is attached, and its solid content is 1.0% by mass.

Then, the tow was twisted using a ring twisting machine to obtain a glass fiber yarn of ECG75 1/0 0.7Z of JIS-R3413.

The glass fiber yarns are warped with a width density of 600, and rolled into a warp beam.

For the runnability in the warping process, the tension (g) of the glass fiber yarn running was measured with a tensiometer.

The number of hairiness is determined by measuring the number of hairiness of each warping beam with a hairiness detector.

The falling powder is determined by visually evaluating the shedding amount of the sizing agent of the reed or guide rail during warping, with 1: very little; 2: little; 3: general; 4: many; 5: very much 5 grades Make an evaluation.

The above measurement results are summarized in Table 2.

Table 2 Walking tension (g) Hairiness falling powder Example 1 25 10 2 Example 2 25 12 2 Example 3 26 13 2 Example 4 28 15 1 Example 5 twenty one 12 3 Example 6 25 11 2 Example 7 25 11 2 Comparative example 1 twenty four twenty one 2 Comparative example 2 11 14 5 Comparative example 3 48 33 1 Comparative example 4 31 twenty four 2

From the results in Table 2, it can be known that in Examples 1-7 of the present invention, the running tension was 21-28 g, and the running property during warping was good. In addition, the number of hairiness and powder fall are also small.

On the other hand, in Comparative Example 1 using cornstarch with an MS value of 0.08, the number of fluffs in the warping process increased because the bundling property was insufficient. In Comparative Example 2, which did not contain vegetable oil but contained only paraffin as an oil agent, the slipperiness was excessive, the tension decreased conversely, the running performance was poor, and powder falling was even worse. In addition, in Comparative Example 3, which did not contain paraffin and contained only vegetable oil as an oil agent, the sliding properties were insufficient, the running tension was greatly increased, and the number of hairiness was also increased. Also, in Comparative Example 4 using a vegetable oil with a saturation degree of 41% exceeding the specified range of the present invention, the sliding property was insufficient, resulting in an increase in running tension and an increase in the number of hairiness.

Possibility of industrial use

The sizing agent of the present invention has good sizing properties even in the warping process of glass fiber yarns used as warp yarns of glass cloth, and thus can effectively prevent the occurrence of hairiness. In addition, due to the moderate sliding property, the tension in the warping process is constant, and the running property is excellent, and the hanging and loosening of the warp yarn in the air-jet weaving can be prevented. Therefore, the glass fiber yarn using this sizing agent can be suitably used for the glass cloth used for a printed wiring board.

Claims (7)

1. glass fiber yarn collecting agent, described glass fiber yarn is by being that the glass monofilament boundling of 5～11 μ m is a tow with 200～800 average root diameters, again its twisting is formed, warp thread as glass cloth, it is characterized in that, above-mentioned collecting agent contains starch, vegetable oil, paraffin, emulsifying agent at least, and above-mentioned starch is that the degree of hydroxy alkylated is 0.01～0.025 etherification starch, and the saturation degree of above-mentioned vegetable oil is more than or equal to 90%.

2. glass fiber yarn collecting agent according to claim 1 is characterized in that, the cooperation ratio of above-mentioned paraffin and above-mentioned vegetable oil is expressed as 30～70 with parts by mass: 70～30.

3. glass fiber yarn collecting agent according to claim 1 and 2 is characterized in that, mentioned emulsifier is ester class and/or ether-ether class emulsifying agent.

4. glass fiber yarn is characterized in that, described glass fiber yarn is by adhering to the glass fiber yarn that each described collecting agent forms in the claim 1～3.

5. the manufacture method of glass fiber yarn is characterized in that, it comprises that be that the glass monofilament boundling of 5～11 μ m is a tow with the described collecting agent of claim 1 with 200～800 average root diameters, its twisting is formed, as the warp thread of glass cloth again.

6. glass cloth is characterized in that, it is to be after the glass monofilament boundling of 5～11 μ m is tow with the described collecting agent of claim 1 with 200～800 average root diameters, and twisting forms glass fiber yarn, is made into used as warp thread.

7. the printed wiring board-use baseplate material is characterized in that, has used the described glass cloth of claim 6.