JPH093775A - Production of warp for woven glass fiber fabric and sizing agent used therefor - Google Patents

Abstract

PURPOSE: To produce a woven glass fabric easily splittable after drying, generating little fluffs on the warp and having high quality by applying a sizing agent containing ammonium sulfate compound to glass fiber. CONSTITUTION: The objective sizing agent for glass fiber warp is produced by compounding 0.01-5.0wt.% (based on the solid component of the sizing agent) of an ammonium sulfate compound such as octyl trimethyl ammonium sulfate to a sizing agent composed of a partially saponified polyvinyl alcohol, an etherified high-amylose corn starch, a paraffin emulsion, etc. The sizing agent for warp is applied to warped glass fiber yarn in an amount of 0.1-5.0wt.% (in terms of the solid component of the sizing agent). The treated glass fiber yarn is dried, wound on divided weaving beams and stably woven by a high-speed air jet loom to form a prescribed woven glass fabric.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a glass fiber woven yarn.
The present invention relates to a warp sizing agent used for yarns and a glass fiber yarn to which the sizing agent is attached.

[0002]

2. Description of the Related Art A glass fiber for textiles is made by adhering a starch and a primary sizing agent containing a nonionic lubricant and a cationic lubricant as main components by a roller type applicator when the glass fiber is spun. Then, it is wound into a cake, twisted and wound on a bobbin as a glass fiber yarn. Next, generally, in the step of preparing warp yarns for glass fiber cloth, warp glass fibers wound on a bobbin are warped with equal tension according to the number of warp yarns, length, density and width determined by the fabric design. -Take it around. This glass fiber is put on a sizing machine and pulled out with a constant tension to pass through a sizing agent. As a result, the sizing agent is sufficiently impregnated, and then the sizing agent and the squeezing roll are used to squeeze out the excess sizing agent. Thousands of sheet-shaped glass fiber warps with a sizing agent are dried, and adjacent yarns are divided into upper and lower long rods, which are called dividing rods, and which enter at right angles to the traveling direction of the sheet. The bonded yarns are separated into individual yarns by passing them through a woven beam. Since the adjacent yarns partially adhere to each other during drying due to the sheet-like sizing, the fibers of the strongly adhered part are broken when peeled by the dividing rod, which causes fluff.

This sizing agent is used in the process of weaving glass cloth for the purpose of protecting the glass fiber yarn warp from bending and friction. The components of the sizing agent are usually used in combination with polyvinyl alcohol, starch, lubricant, plasticizer, preservative and the like. Polyvinyl alcohol and starch are used for adhesion and film formation in order to protect the glass fiber of the yarn from any bending or abrasion on the loom. For example, polyvinyl alcohol has a partial saponification degree of 88 ± 2 moles, a viscosity of 5.0 ± 1.0 cps (4%, 20 ° C.), and starch is a starch or a chemically modified product such as ordinary starch. For example, hydroxylalkylated etherified starch, acetylated esterified starch, crosslinked starch reacted with a crosslinking agent such as epichlorohydrin, etc. are used. The lubricant gives the yarn slippage and reduces friction on the loom,
Used to protect glass fibers. Types of lubricants include hydrogenated hydrogenated animal and vegetable oils, paraffin wax, esters of higher saturated fatty acids and higher saturated alcohols, and the like. The plasticizer is a compound having a hydroxyl group, an amino acid or an amide group, such as glycerin or ethylene glycol-
, Urea, etc. are often used.

[0004]

Although such a sizing agent is still used, the glass fiber yarn is easily fluffed by the speeding up of the sizing machine and the loom, and the glass fabric is impregnated with an epoxy resin or the like. Since the electric circuit printed on the copper-clad laminate produced by the above has become more precise, defects due to the fluff of the glass fabric are more likely to occur, and further improvement in quality is required for the glass fiber fabric, and the following problems are solved. Is desired. When one or several thousand glass fiber yarns are drawn out from the warping beam and glued with a sizing agent, a sheet-like form is formed and adjacent yarns are partially bonded during drying. After drying, they are separated one by one with a dividing rod, but if the adhesion between the threads is strong, they will be forcibly divided, and the glass fibers will be partially cut and fluff will occur. 2. Due to the high speed of the loom, the warp yarns are severely rubbed on the loom due to “sacks” and the partially cut portions are further damaged, and fluffing becomes severe. The present invention solves the above-mentioned problems, has a good splittability after sizing, and can obtain a warp with less fluff, and a glass fiber yarn for warp to which this sizing is attached. It is intended to make a glass fiber fabric with less fluff by providing a fluff.

[0005]

In order to achieve the above object, the present inventors have attached a sizing agent containing at least one or more kinds of ammonium sulfate compounds to a glass fiber warp wound on a warping beam. When the sheet-like material is dried and then wound on a woven beam, it is separated into glass fiber yarns one by one, but there is no partial cutting of the glass fiber which causes fuzz. Furthermore, they have found that they can be easily divided by a dividing rod, and have completed the present invention based on this finding.
The components of the sizing agent used in the present invention are those normally used for sizing agents for glass fibers such as adhesive and film-forming agents, lubricants, surfactants and preservatives, and their general formulation examples are as follows. However, the present invention is not limited to this, and it is sufficient if there is no problem in compatibility with the ammonium sulfate-based compound.
Adhesive and film-forming agents bond hundreds of glass fibers together into a single strand, which is then processed into yarn and woven into a cloth to protect the glass fibers from all mechanical bending and friction during the process. It is used for the purpose of forming a film to eliminate the cause of fluff. Specific examples include high-amylose type starch, normal type starch, chemically modified products of these starches, for example, hydroxyalkylated ether compounds, acetylated ester compounds, and cross-linking agents such as epichlorohydrin. There is a cross-linked product that has been reacted, and the compounding amount in the sizing agent is about 3% by weight to about 7% by weight. In addition, polyvinyl alcohol, partially saponified polyvinyl alcohol,
There are water-soluble epoxy resins, etc., which are used in combination.

Lubricants are used to lubricate the strands, reduce friction during processing and protect glass fibers. Examples of the lubricant used include hydrogenated hydrogenated oils of animal and vegetable oils, paraffin wax, and synthetic oils such as condensation products of higher fatty acids and higher alcohols. The compounding amount in the sizing agent is about 0.5% by weight. The surfactant is often used for emulsifying these lubricants, and for example, polyoxyethylene polyalkyl ether, polyoxyethylene alkyl ether, etc. are used. Formalin is often used as the preservative. The compounding amount in the sizing agent is about 0.1% by weight.

The ammonium sulfate compound that can be used in the present invention is represented by the formula (1).

Embedded image In the above (1), R1 is ammonium or a group containing ammonium, and R2 is ammonium or a group containing ammonium, or an organic group other than these. Examples of the group having an ammonium in R1 and R2 include triethylammonium, octyltrimethylammonium, oleylamidopropyldimethylethylammonium, stearyldihydrooxyethylmethylammonium, stearyldiacetylmethylammonium and the like. As R2, those having other functional groups are also effective, and examples thereof include an alkyl group, an alkylarene group, an aryl group, an alkenyl group, and an alkynyl group, provided that they do not impair the water solubility of the ammonium sulfate-based compound. Any group is applicable. Ammonium sulfate compounds used in the present invention from the combination of these groups are, for example, ammonium sulfate,
Trimethylammonium sulfate, triethylammonium sulfate, tributylammonium sulfate, octyltrimethylammonium ethosulfate, lauryltrimethylammonium ethosulfate, laurylamidopropyltrimethylammonium methosulfate,
Stearyl amide dihydrooxyethyl methyl ammonium methosulfate, stearyl diacetyl methyl ammonium methosulfate, etc. can be illustrated.

The content of the ammonium sulfate type compound with respect to the total solid content of the sizing agent of the present invention is 0.002-20.0% by weight, preferably 0.01-5.0% by weight, more preferably It is 0.05-1.0% by weight. 0.00
If it is 2% by weight or less, there is no effect in improving the dividability, and
When it is 0% by weight or more, the decomposition products of the ammonium sulfate-based compound after thermal deoiling increase, and when the resin is impregnated into a laminated plate, the physical properties are adversely affected, which is not preferable. A sizing agent containing the ammonium sulfate-based compound of the present invention,
It is attached to a warped yarn, dried and wound up on a woven beam, but the yarn is limited in glass composition, glass fiber diameter, cross-sectional shape, number of filaments constituting a strand, number of twists, etc. However, it can be applied to any warped yarn. The amount of solid content of the sizing agent containing the ammonium sulfate compound of the present invention to be attached to the yarn is 0.001-1.
5.0% by weight, preferably 0.1-5.0% by weight,
More preferably, it is 0.5-2.0% by weight. If the adhered amount of the sizing agent is 0.001% by weight or less, the effect as a sizing agent does not appear, and if it is 15% by weight or more, the adhesive strength becomes too strong and the dividability deteriorates.

[0009]

The glass fiber for warp used in the present invention has the primary sizing agent already attached when the molten glass is drawn out from the platinum nozzle, spun and wound. The sizing agent of the present invention is attached on the glass fiber sizing agent. A sizing agent containing an ammonium sulfate-based compound has little tackiness when wet. Therefore, it is easy to control the adhered amount by the mangle and easily separate from the adjoining glass fiber yarn due to the vibration during drying, etc., and the adhesiveness of the sizing agent existing between them is low even in the adhered state. Therefore, it is considered that the particles tend to move toward the yarn during drying, and the amount of the sizing agent between the adjacent yarns decreases, resulting in a good splittability that cannot be obtained by the conventional sizing agent.

[0010]

The present invention will be described in more detail with reference to the following examples. The test results obtained are shown in Table 1.

Example 1 5 kg of partially saponified polyvinyl alcohol (manufactured by Nippon Gohsei Co., Ltd., product number GL-5) and 1 kg of high amylose type corn etherified starch are dispersed in 70 kg of water and heated to 90 ° C. After stirring and holding for 10 minutes, it is cooled to 65 ° C. (Liquid A). In a separate container, 500 g of paraffin emulsion (solid content 30% by weight) (B
Liquid), formalin 100 g (liquid C), and octyltrimethylammonium ethosulfate (trade name: Cationogen ESO, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 300 gr (D
Prepare) Solution B, solution C, and solution D are sequentially added to solution A, and then water is added to adjust the total weight to 100 kg and the mixture is kept at 60 ° C. This paste was mixed with warped G75 O. 7Z Yard
(Filament number 400, twist number 0.7 times / 25
mm) using a sizing machine (manufactured by SUCKER) to adhere 1.22% by weight of solids, dried, divided and wound on a weaving beam, and woven by a high-speed air jet loom (manufactured by Tsuda Koma Kogyo). Density 44 warps / 25 mm, weft 32 threads / 25 m
m glass fabric. Table 1 shows various evaluation results described below. 1. To evaluate the splittability, after the warp threads are glued and dried, the adjacent yarns are split up and down with the split rods, and the length from the split rods to the place where the warp threads are actually split is measured. However, there are 7 categories. 1 is the longest, 7 is the shortest, and the longer the length, the easier it is to divide.
It can withstand normal use. 2. The evaluation of fluff was performed by weaving with a loom, counting the number of fluffs on the surface of the woven fabric, and classifying them into 7 ranks, with 1 being the least and 7 being the most, showing 2-3 or less. It can withstand normal use.

[0011]

Example 2 Partially saponified polyvinyl alcohol 4.8% by weight High amylose corn etherified starch 1.5% by weight Hydrogenated cottonseed oil 1.0% by weight Polyoxyethylene ether 0.1% by weight % Formalin 0.1% by weight Ammonium sulfate 0.3% by weight Water 92.2% by weight E255 1.0Z (200 filaments, prepared by preparing a sizing agent having the above composition in the same manner as in Example 1)
A gluing machine (SUC) for yarns with 1.0 twist / 25 mm
1.30% by weight was made to adhere by using an ER), and a woven fabric having a weaving density of 60 warps / 25 mm and wefts 58/25 mm was formed using a high-speed air jet loom (made by Tsudakoma Kogyo Co., Ltd.).

[0012]

Example 3 Partially saponified polyvinyl alcohol 5.4% by weight High amylose corn etherified starch 1.3% by weight Paraffin emulsion (solid content 30% by weight) 1.0% by weight Formalin 0.1 Wt% triethylammonium sulfate 0.3 wt% (manufactured by Koizumi Chemical Co., Ltd.) water 91.9 wt% E2551.0Z (200 filaments) prepared by preparing a sizing agent having the above composition in the same manner as in Example 1. Using a sizing machine (made by SUCER), 1.30% by weight is attached to a yarn with a twist of 1 twist / 25 mm), and a high-speed air jet loom (made by Tsudakoma Kogyo Co., Ltd.) gives a warp density. A glass fabric having 60 yarns / 25 mm and weft yarns 58 yarns / 25 mm was used.

[0013]

Example 4 Partially saponified polyvinyl alcohol 3.5% by weight High amylose type corn etherified starch 2.0% by weight Paraffin emulsion (solid content 45% by weight) 0.4% by weight Formalin 0.1 % Octyl trimethylammonium 0.3% by weight Ethosulfate water 93.7% by weight A sizing agent having the above composition was prepared in the same manner as in Example 1, and warped G75 0.7Z (number of filaments 400, twisted) Adhesive machine (SUCE) for several 0.7 times / 25 mm yarn
(Made by R Co., Ltd.), 1.05% by weight is attached, and a high-speed air jet loom (made by Tsudakoma Kogyo Co., Ltd.) has a weaving density of 4 warps.
It was made into a glass fabric of 4 threads / 25 mm and weft threads of 32 threads / 25 mm.

[0014]

Comparative Example 1 A glass fabric was prepared in the same manner as in Example 1 except that water was added instead of 0.5% by weight of octyltrimethylammonium ethosulfate. The test results obtained are shown in Table 1.

[0015]

Comparative Example 2 A glass fabric was prepared in the same manner as in Example 2 except that water was added instead of 0.3% by weight of ammonium sulfate.

[0016]

As described above, since the glass fiber warp glued with the sizing agent according to the present invention can be easily divided after drying, the occurrence of fluff of the warp is small. Further, since it has excellent abrasion resistance, the glass fabric using this warp has an extremely small amount of fluff as compared with the conventional products.

[0017]

[Table-1]

Claims (3)

[Claims] 1. A method for producing a warp for a glass fiber woven fabric, which comprises treating a glass fiber yarn with a sizing agent containing an ammonium sulfate compound. 2. A sizing agent for warp yarns of a glass fiber woven fabric, wherein the solid content of an sizing agent contains an ammonium sulfate compound in an amount of 0.01% by weight to 5.0% by weight. 3. A warp yarn for a glass fiber woven fabric, comprising the sizing agent according to claim 2 attached to a glass fiber yarn in a solid content of 0.1% by weight to 5.0% by weight.