JP3409388B2 - Sizing agent for glass fiber and glass fiber to which it is attached - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sizing agent for glass fibers and a glass fiber to which the sizing agent is attached.

[0002]

2. Description of the Related Art As a sizing agent, it is roughly classified into yarn and roving. As a sizing agent for yarns, starch, lubricants, cationic softening agents, surfactants, preservatives, etc. are used in combination. Starch is used for the purpose of forming a film to bond hundreds of glass filaments together into a single strand and to protect the yarn from any bending and friction on the machine. Corn, potato, etc. are often used as a raw material of starch, and chemically modified products of those starches, for example, etherification products such as hydroxyalkylation, esterification products such as acetylation, and cross-linking agents such as epichlorohydrin. A cross-linked product and the like reacted by the method disclosed in JP-B-53-35639, and a low-viscosity product or the like for reducing the starch molecular weight and the viscosity by any method are generally used. There are several kinds of the same corn starch and potato starch, for example, about 30% of amylose component and about 70% of amylopectin component, and about 7% of amylose component.
There is a high amylose type starch containing 0% and an amylopectin component of about 30%. The former is excellent in adhesiveness, and the latter is excellent in film forming property. Therefore, it is common to use them in combination in order to make the best use of the features of both. Lubricants are used to lubricate the strands, reduce friction on the machine and protect the yarn. As the type of lubricant, hydrogenated hardened oils of animal and vegetable oils, paraffin wax, synthetic oils such as condensation products of higher saturated fatty acids and higher saturated alcohols, etc. are disclosed in JP-B-56-41584 and are often used. ing. Cationic softening agents are used to soften hard glass threads and to selectively adsorb on the glass surface to reduce friction between filaments in the strand and to show some degree of lubricity. There is. For example, amide or imidazoline obtained by reacting tetraethylenepentamine and stearic acid,
Fatty acids with 8 to 18 carbon atoms and molecular weight of 600 to 1
A reaction product of about 800 with polyethyleneimine is disclosed in JP-A-3-183644. Surfactants are mainly used as emulsifiers for lubricants, and for example, polyoxyethylene polyalkyl ether, polyoxyethylene alkyl ether, etc. are often used. Formalin is mainly used as a preservative.

[0003]

Yarn sizing agents composed of such combinations of compounds have quite good properties and have been used up to now. However, with the increase in the speed of the loom, it is desired to solve the following problems due to the demands for improving the process performance of the yarn and the demand for further improving the quality of the woven glass cloth. 1) When weaving with an air jet loom, the warp yarn is struck by the reed and the air guide to cut a part of the filaments in the strand which is the warp yarn, and when the weft yarn is driven, it is strong. The problem of fluff in the woven glass cloth caused by the fact that some filaments in the weft yarn are cut by being blown by air, 2) When weaving with an air jet loom, the weft yarn is blown by air. It is driven, but when it is driven, the weft does not get into the air enough and the yarn does not reach the specified position. Problem of the flying property of the strand used for the weft, 3) Remaining in the woven glass cloth. The existing sizing agent is removed by incineration or the like. This removal is called deoiling, but during deoiling, the sizing agent is not sufficiently thermally decomposed, and a part of the sizing agent remains on the cloth, causing a problem such as poor deoiling due to coloring.

The present invention solves the above problems.
A sizing agent that has excellent degreasing properties and extremely little fluff, a sizing agent that can obtain strands used for weft yarn that have sufficient and stable flying properties, and glass fibers to which this sizing agent is attached The purpose is to provide.

[0005]

In order to achieve the above object, the first aspect of the present invention is a sizing agent for glass fibers, which comprises starch and at least one ammonium sulfate compound. And Further, the present invention provides
0.001-10.00% by weight of the glass fiber sizing agent
The second gist is a glass fiber yarn characterized by being adhered.

The present invention will be described in detail below. The ammonium sulfate-based compound of the present invention is

Embedded image R ₁ —SO ₄ —R ₂ (1) (In the above formula (1), R ₁ is a group containing ammonium or ammonium, and R ₂ is a group containing ammonium or ammonium, or a group containing these. Groups represented by formula (1), wherein the groups having ammonium in R ₁ and R ₂ include triethylammonium ((C ₂ H ₅ ) ₃ NH) and octyltrimethylammonium (C ₈ H ₁₇ (CH ₃ ) ₃ N), oleylamidopropyldimethylethylammonium (CH ₃ (CH ₂ ) _{7
CH = CH (CH 2) 7} CONH chromatography (CH _{2) 3} C ₂ H
₅ (CH ₃ ) ₂ N), stearyldihydrooxyethylmethylammonium (C ₁₈ H ₃₇ CH ₃ (C ₂ H ₅ O) ₂
N), stearyl diacetylmethyl ammonium (C _{18
H 37 CH 3 (CH 3 COO} ) 2 N) and the like can be exemplified. Those having other functional groups are also effective. Examples of the organic group other than these in R ₂ include an alkyl group, an alkylarene group, an aryl group, an alkenyl group and an alkynyl group, and any group can be used as long as it does not prevent the solubility of the ammonium sulfate compound in water. Applicable.

Examples of the ammonium sulfate compound of the present invention include ammonium sulfate, trimethylammonium sulfate ([(CH ₃ ) ₃ NH] ₂ SO ₄ ) and triethylammonium sulfate ([(C ₂ H ₅ ) ₃ NH] ₂ SO ₄ ). ,
Tributylammonium sulfate ([(C ₄ H ₉ ) ₃ NH]
₂ SO ₄ ), octyltrimethylammonium ethosulfate (C ₈ H ₁₇ (CH ₃ ) ₃ NC ₂ H ₅ SO ₄ ),
Lauryl trimethyl ammonium ethosulfate (C
_{12 H 25 (CH 3) 3} NC 2 H 5 SO 4), oleyl amidopropyl dimethyl ethyl ammonium ethosulfate _{(CH 3 - (CH 2)} 7 CH = CH (CH 2) 7 CO
_{NH (CH 2) 3 C 2} H 5 - (CH 3) 2 NC 2 H 5 S
O _4), lauryl amidopropyl trimethyl ammonium methosulfate _{(C 11 H 23 CONH (CH} 2)
_{3 (CH 3) 3 NCH 3} -SO 4), stearyl amidopropyl dimethyl ethyl ammonium ethosulfate _{(C 17 H 35 CONH (CH} 2) 3 C 2 H 5 (CH 3) 2
NC ₂ H ₅ SO _4), stearyl dihydroxy-ethyl methyl ammonium methosulfate (C ₁₇ -H ₃₅ CH
_{3 (C 2 H 5 O)} 2 NCH 3 SO 4), stearyl diacetyl ammonium methosulfate (C ₁₇ H _{35
CH 3 (CH 3 COO) 2} NCH 3 -SO 4) and the like can be exemplified.

The ammonium sulphate compound of the present invention is used as a mixture with other sizing agent compounds. One of the ammonium sulfate-based compounds of the present invention may be used as a mixture with another sizing agent compound, or two or more of the ammonium sulfate-based compounds of the present invention may be used as a mixture with another sizing agent compound. Good. As the other sizing agent compound used by mixing with the ammonium sulfate-based compound of the present invention, any compound can be used as long as there is no problem in compatibility with the ammonium sulfate-based compound of the present invention.

The content of the ammonium sulfate compound of the present invention in the sizing agent is preferably 0.002 to 11.00% by weight, particularly preferably 0.01 to 1.10% by weight,
More preferably, it is 0.05-0.50% by weight.

The sizing agent containing the ammonium sulfate-based compound of the present invention is attached to the yarn, and the yarn has a glass composition, a filament diameter, a filament cross-sectional shape,
It is not limited by the number of filaments forming the strand, and can be effectively applied to any yarn. The amount of the sizing agent containing the ammonium sulfate compound of the present invention attached to the yarn is from 0.001 to 10.0% by weight, preferably from 0.1 to 3.00% by weight, particularly preferably from 0.3 to It is 1.00% by weight.

[0011]

【Example】

Example 1 2 k of high amylose type etherified corn starch
2g of normal esterified low-viscosity corn starch
g is weighed and dispersed in 80 kg of water. This is heated and heated, gelatinized at 95 ° C for 30 minutes, and then cooled to 65 ° C (Liquid A). Separately, 700 g of hydrogenated vegetable oil, 700 g of paraffin wax, and an emulsifier (polyoxyethylene polypropylene ether) that have been dissolved by heating in advance.
Weigh 200 g, add hot water while stirring with a homomixer, continue stirring for 5 minutes, and dilute with hot water to 4 kg (liquid B). In a separate container, weigh 200 g of the acetic acid activated product of the condensate of tetraethylenepentamine and stearic acid,
Add boiling water to make 3 kg (Liquid C). Furthermore, 150 g of octyl trimethyl ammonium ethosulfate
(Product name: Cationogen ESO, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Is diluted with water three times (solution D). Formalin is 3
Weigh 3 g (100% conversion of pure content) and dilute 10 times (Solution E). Solution B, Solution C, Solution D and Solution E were sequentially added to Solution A at 65 ° C., and then hot water was added to make the total weight 100 kg.
Keep warm at 0 ° C. Using the yarn to which 0.89% by weight of the sizing agent of the present invention was adhered, the quality of the glass cloth woven by a high-speed air jet loom (ZA manufactured by Tsudakoma Industries Co., Ltd.) and the flying property of the yarn were evaluated. As shown in Table 1, it showed extremely little fluff, sufficient and stable flight performance, and excellent degreasing property.

Example 2 High amylose type etherified corn starch 2.0% by weight, normal type esterified low viscosity corn starch 2.0
2% by weight, 0.7% by weight of hydrogenated vegetable oil, 0.8% by weight of paraffin wax, 0.25% by weight of acetic acid activated product of a condensation product of tetraethylenepentamine and stearic acid, 0.2% by weight of emulsifier, 0 of ammonium sulfate. 0.1% by weight, formalin 0.03% by weight (100% pure content) and water 94
The quality of the glass cloth woven by a high speed air jet loom (ZA manufactured by Tsudakoma Kogyo Co., Ltd.) and the flying of the yarn using the yarn to which 0.92% by weight of the sizing agent of the present invention consisting of 1% by weight was attached. The runnability is shown in Table 1, and it showed extremely few fluffs, and sufficient and stable flightability and excellent deoiling property.

Example 3 High amylose type etherified corn starch 1.9% by weight, normal type esterified low viscosity corn starch 1.
9% by weight, 0.7% by weight hydrogenated vegetable oil, 0.7% by weight paraffin wax, 0.2% by weight acetic acid activated product of a condensation product of tetraethylenepentamine and stearic acid, 0.2% by weight emulsifier, triethyl sulfate. 0.8% by weight of the sizing agent of the present invention comprising 0.3% by weight of ammonium, 0.03% by weight of formalin (100% of pure content) and 94% by weight of water.
The quality of the glass cloth woven by the high-speed air jet loom (ZA manufactured by Tsudakoma Kogyo Co., Ltd.) using the attached yarn is shown in Table 1, and the flying properties of the yarn are shown in Table 1. It also showed stable flight performance and excellent deoiling property.

Example 4 2.0% by weight of high amylose type etherified corn starch, normal type esterified low viscosity corn starch 2.0
0% by weight, hydrogenated vegetable oil 0.65% by weight, paraffin wax 0.7% by weight, acetic acid activated product of a condensate of tetraethylenepentamine and stearic acid 0.2% by weight, emulsifier 0.2% by weight, laurylamide Using a yarn to which 0.82% by weight of the sizing agent of the present invention consisting of 0.15% by weight of propyltrimethylammonium methosulfate, 0.03% by weight of formalin (converted to 100% of pure content) and 94% by weight of water was applied, high speed was used. Table 1 shows the quality of the glass cloth woven by an air jet loom (ZA manufactured by Tsudakoma Kogyo Co., Ltd.) and the flying performance of the yarn. It has extremely few fluffs and sufficient and stable flying performance. It exhibited degreasing properties.

Example 5 High amylose type etherified corn starch 1.8% by weight, normal type esterified low viscosity corn starch 2.
0% by weight, 0.7% by weight of hydrogenated vegetable oil, 0.7% by weight of paraffin wax, 0.2% by weight of acetic acid activated product of a condensation product of tetraethylenepentamine and stearic acid, 0.2% by weight of emulsifier, stearylamide. Using a yarn to which 0.83% by weight of the sizing agent of the present invention consisting of 0.2% by weight of propyldimethylethylammonium ethosulfate, 0.03% by weight of formalin (converted to 100% of pure content) and 94% by weight of water is attached, Table 1 shows the quality of the glass cloth woven by the high-speed air jet loom (ZA manufactured by Tsudakoma Kogyo Co., Ltd.) and the flying properties of the yarn.
And it showed sufficient and stable flight performance and excellent deoiling property.

Example 6 High amylose type etherified corn starch 2.0% by weight, normal type esterified low viscosity corn starch 2.0
0% by weight, hydrogenated vegetable oil 0.65% by weight, paraffin wax 0.7% by weight, acetic acid activated product of a condensate of tetraethylenepentamine and stearic acid 0.2% by weight, emulsifier 0.2% by weight, stearyldihydroxy. Using a yarn to which 0.83% by weight of the sizing agent of the present invention consisting of 0.15% by weight of ethylmethylammonium methosulfate, 0.03% by weight of formalin (100% of pure content) and 94% by weight of water was adhered, was used. Table 1 shows the quality of the glass cloth woven by an air jet loom (ZA manufactured by Tsudakoma Kogyo Co., Ltd.) and the flying properties of the yarn.
And it showed sufficient and stable flight performance and excellent deoiling property.

Example 7 5.0% by weight of conventional etherified low-viscosity corn starch, 0.35% by weight of hydrogenated vegetable oil, 1.2% by weight of paraffin wax, acetic acid activity of a condensate of tetraethylenepentamine and stearic acid. Compound 0.25% by weight, emulsifier 0.2% by weight, aqueous urethane emulsion 0.05% by weight, octyltrimethylammonium ethosulfate 0.15% by weight, formalin 0.03% by weight (purity 10
Glass woven by a high speed air jet loom (ZA manufactured by Tsudakoma Kogyo Co., Ltd.) using a yarn to which 0.93% by weight of the sizing agent of the present invention consisting of 93% by weight of water and 93% by weight of water is attached. The quality of the cloth and the flying properties of the yarn are shown in Table 1, and it showed extremely few fluffs, sufficient and stable flying properties, and excellent oil removal property.

Example 8 1.5% by weight of high amylose-type crosslinked etherified corn starch, 3.0% by weight of normal type etherified low-viscosity corn starch, 0.40% by weight of hydrogenated vegetable oil, and 1.6% of paraffin wax. % By weight, 0.3% by weight of an activated product of a condensate of polyethyleneimine and pelargonic acid, 0.3% by weight of an emulsifier, 0.15% by weight of octyltrimethylammonium ethosulfate, 0.03% by weight of formalin (100% of pure content). And a high-speed air jet loom (Z, manufactured by Tsudakoma Kogyo Co., Ltd.) using a yarn to which 0.90% by weight of the sizing agent of the present invention consisting of 93% by weight of water and water is attached.
The quality of the glass cloth woven in A) and the flying properties of the yarn are shown in Table 1. However, it showed extremely few fluffs, sufficient and stable flying properties, and excellent degreasing properties.

Example 9 1.5% by weight of high amylose type crosslinked etherified corn starch, 2.0% by weight of normal type etherified and low viscosity corn starch, 0.30% by weight of hydrogenated vegetable oil, and 1.15 of paraffin wax. % By weight, 0.2% by weight of acetic acid activated product of a condensate of polyethyleneimine and pelargonic acid,
Emulsifier 0.2% by weight, octyltrimethylammonium ethosulfate 0.10% by weight, formalin 0.02
A high-speed air-jet loom (Zd produced by Tsudakoma Industries Co., Ltd.) was used with a yarn having 0.55% by weight of the sizing agent of the present invention consisting of 100% by weight (converted to 100% of pure content) and 95% by weight of water.
The quality of the glass cloth woven in A) and the flying properties of the yarn are shown in Table 1. However, it showed extremely few fluffs, sufficient and stable flying properties, and excellent degreasing properties.

Example 10 2.0% by weight of high amylose type etherified corn starch, 0.70% by weight of hydrogenated vegetable oil, 0.7% by weight of a condensate of higher saturated fatty acid and higher saturated alcohol, tetraethylenepentamine and stearin. 0.2% by weight of an activated product of a condensate of an acid, 0.2% by weight of an emulsifier, 0.15% by weight of octyltrimethylammonium ethosulfate, 0.03% by weight of formalin (100% of pure content) and water 9
Using the yarn to which 0.84% by weight of the sizing agent of the present invention consisting of 4% by weight was applied, the quality of the glass cloth woven by a high speed air jet loom (ZA manufactured by Tsudakoma Industries Co., Ltd.) and the yarn The flight performance is shown in Table 1, and it showed extremely few fluffs, sufficient and stable flight performance, and excellent deoiling property.

Comparative Example 1 The quality of the glass cloth and the flying properties of the yarn obtained in the same manner as in Example 2 except that water was added in place of 0.1% by weight of ammonium sulfate are shown in Table 1. Shown in.

[0022]

The evaluation of the fluff in Table 1 is that the fluff on the cloth surface after weaving by the loom is counted and divided into 8 ranks. 1 is the least, 5 is the most, 2-3
If it is below, it is sufficiently durable for normal use. The flying performance is the result of driving the yarn into the weaving machine as weft and measuring the arrival timing with a measuring machine, and comprehensively judging the weaving property such as the number of the loom stopped, and dividing it into 8 ranks. The smaller the value, the better the result obtained. The degreasing property is obtained by comprehensively judging the whiteness and the color (defective deoiling) after heating and deoiling the cloth, and dividing into 8 ranks.
Similarly, a smaller value means that excellent results were obtained. As shown in Table 1, the glass cloth and the yarn using the sizing agent to which the ammonium sulfate-based compound was added were much less fluff and sufficiently and stable as compared with the glass cloth and the yarn using the sizing agent to which the ammonium sulfate-based compound was not added. It had excellent flying performance and excellent deoiling property. The fluff of the glass cloth depends on the quality of the yarn, and the extremely small fluff cloth shown in Table 1 is obtained because the glass fiber of the present invention is extremely excellent in the process performance of the high speed loom. The cloth of Table 1 has excellent deoiling property because the sizing agent of the present invention easily undergoes thermal decomposition during deoiling. The downgrading rate of the glass cloth due to the fluff of Example 2 was about ½ of the downgrading rate of the glass cloth due to the fluff of Comparative Example 1, and the number of times the loom was stopped due to the flight performance of Example 2 was a comparative example. It was about 1/10 of the number of times the loom was stopped due to the flying property of 1.

[0023]   Table 1 Quality of glass cloth and flying performance of yarn                     Adhesion rate Fluff Flyability Degreasing                     (%) (Grade) (Grade) (Grade)         Example 1 0.85 1 1 1         Example 2 0.87 2 2 1-2         Example 3 0.88 2-32 1         Example 4 0.86 2-3 1-2 1-2 1-2         Example 5 0.85 2 1 1-2         Example 6 0.87 2 1 1-2         Example 7 0.93 1 2-3 2-3         Example 8 0.90 1 1-2 2-3         Example 9 0.55 2-3 2-3 1-2         Example 10 0.84 2 2-3 1         Comparative Example 1 0.84 3 3 3

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-59-57931 (JP, A) JP-A-1-252554 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C03C 25/00-25/70 D06C 7/00 D06M 13/463

Claims (3)

(57) [Claims] 1. A sizing agent for glass fiber yarn to be used for glass cloth, comprising a starch and at least one ammonium sulfate compound, wherein the sizing agent is for glass fiber. 2. A glass fiber yarn, wherein the glass fiber sizing agent according to claim 1 is adhered in an amount of 0.001-10.00% by weight. 3. The glass fiber yarn according to claim 2,
A method for producing a glass cloth, which comprises weaving with an air jet loom and then deoiling by incineration or the like to remove the sizing agent.