JPH0930842A - Low-migrating glass fiber sizing agent and glass fiber to which it is attached - Google Patents

Abstract

(57) Abstract: The solid content of the sizing agent moves to the outer peripheral surface of the cake during the drying process of the cake wound with the glass fiber strands with the sizing agent, and the uneven adhesion amount is partially present. Can be done. This transition is suppressed to prevent the quality of the manufactured glass cloth from being adversely affected. SOLUTION: A sucrose fatty acid ester is added to a sizing agent containing a starch-based film-forming agent in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of starch so that the sizing agent component is transferred to the surface of a cake by drying. I reduced it.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass fiber sizing agent for use in a glass fiber yarn (hereinafter referred to as a yarn) which is a material for a glass cloth, and a yarn treated with the sizing agent.

[0002]

2. Description of the Related Art Since glass fibers are vulnerable to friction and bending, molten glass is drawn out from hundreds or thousands of platinum nozzles at high speed to form glass fibers, and at the same time, a sizing agent is used to protect the glass fibers from a roller applicator or a belt. Attach with a mold applicator. Strands, which are bundles of glass fibers to which a sizing agent is attached, have a central portion with a cross-sectional shape when cut along a winding shaft, for example, on a plastic tube attached to a winding collet of a winder. It is wound into a shape that becomes thinner as it goes higher and lower, and is formed into a form called a cake. This cake is left in the room as it is,
Alternatively, it is pre-dried to a suitable state at a temperature of about 50 ° C. The strand is pulled out from the outside of the cake that has been dried appropriately, and twisted by a twisting machine to form a yarn and wound on a bobbin. As a general component of the sizing agent attached to this strand, for example, starch, a lubricant, a cationic softening agent, a surfactant, and a preservative are used.

Hundreds of glass filaments are glued together into a single strand, twisted and yarned, and then in a sizing agent to protect the yarn from any bending and rubbing in the process of forming a glass cloth. Starch is used as an adhesive and film-forming agent. There are several kinds of corn starch and potato starch with different properties, for example, normal starch containing about 30% amylose component and about 70% amylopectin component, about 70% amylose component and about 70% amylopectin component. There is a high amylose-type starch containing about 30% of ingredients. 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 yarn, reduce friction on the machine and protect the yarn. As the type of lubricant, hydrogenated hardened oils of animal and vegetable oils, paraffin wax, and synthetic oils such as condensation products of higher saturated fatty acids and higher saturated alcohols are often used. The cationic softening agent is a material which softens the yarn adhered with the sizing agent and which is selectively adsorbed on the glass surface in order to reduce friction between filaments in the strand and further shows a certain degree of lubricity. Is used. For example, amide or imidazoline obtained by reacting tetraethylenepentamine and stearic acid, or about C ₈
The reaction product of a fatty acid of about C ₁₈ to C ₁₈ and a polyethyleneimine of about 600 to 1800 in molecular weight is used. The surfactant is mainly used as a lubricant emulsifier, and for example, polyoxyethylene polyalkyl ether or polyoxyethylene alkyl ether is often used. Formalin is generally used as the preservative.

The glass cloth is manufactured by using the yarn to which the sizing agent is attached, but there are various problems. The main ones are the flying property of whether the weft threads when weaving a cloth with an air jet loom are successfully blown out by the jet of air, the generation of fluff of the woven glass cloth, and the focusing on the glass cloth. Problems such as degreasing property of whether or not degreasing for removing the agent by thermal decomposition can be sufficiently performed in a short time are raised. What is thought to have a great influence on the flying property and the generation of fluff is uneven adhesion of the sizing agent due to the phenomenon of partial migration of the sizing agent attached to the cake wound with glass fiber strands. The phenomenon of partial migration is such that when moisture evaporates from the surface of a cake obtained by winding a strand of glass fiber with a sizing agent on a tube, starch in the sizing agent attached to the fiber inside the cake The solid content moves to the surface of the cake as the water moves. Since the sizing agent moves from the inside to the surface and accumulates, many sizing agents adhere to the glass fibers on the surface of the cake,
There is less glass fiber inside, and the properties of the finished yarn change. Also, in the part where the sizing agent is abundant, if the glass fiber strands adhere to each other and are forcibly peeled off, the glass fibers may be partially cut and cause fluffing, and especially the part where the sizing agent is abundant may be discarded. .

[0006] In order to solve this problem, many studies have been made, and various patents have been applied for starch because it is the main component of the sizing agent. Many of these applications use a film-forming adhesive containing a sizing agent in which the starch particles are not completely ruptured even after the starch is gelatinized and partially swollen particles remain. . Japanese Patent Publication 47-44
479 discloses that the above object is achieved by using starch ethers of cyclic hydrocarbons and their derivatives. In JP-A-51-49987, a starch ester of isoalkanoic acid is used, and JP-B-53-35639 is used.
Crosslinked etherified starch is used for
No. 25, using high-amylose corn as a raw material, and using a fatty acid ester compound having a substitution degree of 0.02-0.05, Japanese Patent Publication No. 4-76338 discloses an example of using a succinic acid ester starch derivative. There is. Other than the method of leaving the swollen particles, JP-B-56-322261 discloses an example of using pullulan, and JP-A-59-182253 discloses an example of attaching an appropriate amount of starch having an average molecular weight of 20000 or more to glass fibers.

[0007]

The yarn sizing agent composed of such raw materials has considerably excellent properties, and in many cases it has been used up to now. However, regarding partial migration of the sizing agent, although starch, which is the main component of the sizing agent, is directly improved, it has not been solved yet. The use of characteristic starches with various improvements has been made, but it is very difficult to balance the stability of the sizing agent, the processability and the required properties of the yarn. There is such a problem. 1) During storage or preliminary drying of the cake, the sizing agent migrates to the cake surface portion, and the amount of adhesion on that portion increases. As a result, when pulling out the strand for twisting, it causes the breakage of the glass fiber at the adhesive part of the strand and the dispersion of the quality of the yarn, and the problem that the surface part needs to be discarded. 2) When weaving with an air jet loom, the warp yarn is struck by the "sasa" and the air guide, some filaments in the strand that is the warp yarn are cut, and when the weft yarn is driven in, The problem of fluff in the woven glass cloth caused by the fact that some filaments in the strands, which are weft yarns, are cut by being blown by strong air.

3) When weaving with an air jet loom, the weft yarn is driven in by air, but when driven, the weft yarn cannot be sufficiently caught in the air and the yarn cannot reach the predetermined position. Problem 4) When deoiling in the deoiling process that removes the sizing agent remaining in the woven glass cloth by thermal decomposition, etc., the thermal decomposition of the sizing agent does not take place smoothly However, there are problems such as poor oil removal due to coloring, and not all of them were satisfied. An object of the present invention is to solve the above-mentioned problems in a well-balanced manner by providing a sizing agent having a low migration property upon drying and stabilizing the yarn quality.

[0009]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in order to achieve the above object, and a composition in which a sucrose fatty acid ester is mixed in a sizing agent containing starch causes migration of the sizing agent due to drying. It was found to be difficult, and these problems were solved.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The essential and essential component of the sizing agent used in the present invention is starch paste. The starch for starch paste used in the present invention includes various processed products as described above, and includes those of the following embodiments. Natural raw starch, such as corn and potato (potato), and their chemical modifications, such as etherification products such as hydroxyalkylation, esterification products such as acetylation, and cross-linking agents such as epichlorohydrin. There are known cross-linked products obtained by reacting with, and low-viscosity products known in the art, such as acid treatment, in which the molecular weight of starch is reduced to lower the viscosity. A concrete example of the compounding of the conventional sizing agent using these starches is a starch-based material,
2% to 10% by weight, lubricant, 0.2% to 5% by weight, cationic lubricant 0.03% to 1.0% by weight,
Surfactant 0.05% -1.0% by weight, preservative
Such as 0.1% -0.5% by weight. However, the sucrose fatty acid ester of the present invention suppresses the movement of starch by forming a complex in which the starch in the sizing agent is mainly wrapped in the helical form of the amylose component. The sizing agent containing is not limited to the above sizing agent formulation as long as there is no problem in mixing with the sucrose fatty acid ester. The sucrose fatty acid ester used in the present invention is a dehydration-condensation product of fatty acid and sucrose, but there are innumerable types depending on the type and number of fatty acids.

However, the linear portion of the monocarboxylic acid of the sucrose fatty acid ester used here is used for the purpose of forming a complex encapsulated in the structure of starch-like amylose, Therefore, it is desirable to use a straight chain of C4 or more,
More preferably, a straight chain product having C10 or more is used. Specifically, C ₁₂ lauric acid, C ₁₄ myristic acid, C ₁₆ palmitic acid, C ₁₈ stearic acid, C ₂₁ behenic acid,
There are straight-chain saturated and straight-chain unsaturated fatty acids such as C ₁₈ oleic acid.

Regarding the number to be attached, it can be attached as long as the prepared sizing agent does not cause stability problems. That is,
Positions containing hydroxyl groups 2, 3, 4, 6 of the D-glucose moiety of saccharose and 1, 3, of the D-fructose moiety,
It can be attached to a position containing 4 or 6 hydroxyl groups. Specific examples thereof include saccharo-slaurate monoester, or a mixture thereof with di, tri, poly, or ester, saccharo-smyristate monoester, or a mixture thereof, di, tri, poly, or ester, saccharo- Known straight-chain fatty acid and saccharose monoester such as spalmitate monoester or a mixture thereof with di-, tri-, polyester, etc. Examples thereof include dehydrated condensates of saturated and linear unsaturated fatty acids and sucrose. Sucrose saccharose ester has a monoester content of 50 even if it contains a poorly water-soluble diester or triester.
% Or more, it can be melted transparently and often causes no problem in use. Thus, even if the sucrose saccharose ester itself is poorly soluble, it can be used as long as it is soluble in water by some means. Since sucrose is the same sugar as starch, it has good compatibility with starch and does not adversely affect the adhesiveness and film forming property of the sizing agent. Further, since it does not contain metals and has a smaller molecular weight than starch, it is easier to deoil than starch. The sucrose fatty acid ester used in the present invention may be used alone as a mixture with a sizing agent compound containing other starch-based components.
You may use it in mixture of 2 or more types.

The content of sucrose fatty acid ester in the sizing agent is preferably 0.005-10.0% by weight, more preferably 0.01-2.00% by weight, particularly preferably 0.02-. It is 0.50% by weight. If it is 0.005% by weight or less, the migration property does not decrease, and if it is 10% by weight or more, the migration property does not change. The weight ratio of the sucrose fatty acid ester and the starch component in the sizing agent is 1 part: 100 parts-50 parts: 1.
It is desirable that the range is 00 parts. If 1 part: 100 parts or less, the transferability does not decrease, and if 50 parts: 100 parts or more, the transferability does not change.

The sucrose fatty acid ester-containing sizing agent of the present invention is attached to a glass fiber strand during spinning, and the strand has a glass composition, a filament diameter, a filament cross-sectional shape, and the number of filaments constituting the strand. It is not limited by The sucrose fatty acid ester-containing sizing agent attached to the yarn has a solid content of 0.05 to 10.00% by weight, preferably 0.10 to 3.00% by weight, particularly preferably 0.3.
It is 0 to 1.00% by weight. The amount of sizing agent attached is 0.05
If it is less than 10% by weight, the effect as a sizing agent is not obtained, and if it is more than 10.0% by weight, the yarn becomes too hard and a problem occurs in the production of glass cloth. Although the action of the sucrose fatty acid ester of the present invention is not well understood, since the amylose in the starch wraps the sucrose fatty acid ester, the size of the sizing agent in the cake is cooled after the sizing agent is applied to the glass fiber. It is speculated that the action of increasing viscosity may reduce the migration of starch during drying. In addition, the starch film becomes soft and strong, and the occurrence of fluff is suppressed with less mechanical damage in a high-speed air jet loom.

The present invention will be described in detail below with reference to examples.

Example 1 2 kg of high amylose type etherified corn starch and 2 kg of normal type esterified low viscosity corn starch are weighed and dispersed in 80 kg of water. Furthermore,
Product name: S-1670 (MITSUBISI-KASEI FOODS CORP.
Saccharose stearate (75% monoester, 25% di, tri, poly, ester) known as
Is weighed and added to the above starch suspension. This is heated and heated, and gelatinized at 95 ° C. for 30 minutes, and then cooled to 65 ° C. Separately, weigh 700 g of hydrogenated vegetable oil, 700 g of paraffin wax, and 200 g of emulsifier (polyoxyethylene polypropylene ether) that had been heated and dissolved in advance, add hot water while stirring with a homomixer, and continue stirring for 5 minutes after inversion. Then dilute with hot water to 4 kg. In a separate container, 200 g of an acetic acid activated product of a condensate of tetraethylenepentamine and stearic acid is weighed, and hot water is added to make it 3 kg. 10 formalin
Weigh 0 g and dilute 10 times. An emulsion of oil, an aqueous solution of a cationic softening agent, and an aqueous solution of formalin are sequentially added to a starch paste solution at 65 ° C, and then hot water is added to make a total weight of 100.
Incubate at 60 ° C according to kg. Table 1 shows the quality of the glass cloth and the flying properties of the yarn, which were woven by a high-speed air jet loom (ZA type manufactured by Tsudakoma Kogyo Co., Ltd.) using the yarn to which 0.90% by weight of the sizing agent of the present invention was attached. Show. The size migration index in Table 1 is the case of the glass fiber strand.
G The value obtained by dividing the adhesion rate of the part showing the maximum adhesion amount on the surface of the surface by the adhesion rate of the part showing the minimum adhesion amount in the center near the plastic tube.The smaller the value, the smaller the degree of partial transfer of size. Represents The evaluation of the fluff was compared with a standard in which the fluff on the cloth surface after being woven by a loom was counted and divided into 8 ranks. 1 is the least, 8 is the most, 2-3
If it is below, it is sufficiently durable for normal use. The flying performance is divided into 8 ranks by comprehensively judging the result of driving the yarn into the loom as a weft and measuring the arrival timing with a measuring machine, and the weavability such as the number of times the loom is stopped.
In all cases, the smaller the value, the better the result obtained. Regarding the degreasing property, the smaller the value is, the more the value is compared with the criteria of 8 ranks after comprehensively judging the whiteness and coloration (poor deoiling) after heat deoiling the cloth (350 ° C, 20 hours). It means that the result was obtained.

[0016]

Example 2 2.0% by weight of high amylose-type etherified corn starch, 2.2% by weight of normal ester low-viscosity corn starch, sucrose stearate (S-
1670) 0.05% by weight, hydrogenated vegetable oil 0.7% by weight, paraffin wax 0.8%, acetic acid activated product 0.2 of a condensate of tetraethylenepentamine and stearic acid.
The sizing agent of the present invention comprising 0.9% by weight of emulsifier, 0.2% by weight of emulsifier, 0.03% by weight of formalin (100% of pure content) and 94% by weight of water is adhered to glass fiber in a solid content of 0.92% by weight. The yarn was woven with a high-speed air jet loom (Type ZA manufactured by Tsudakoma Kogyo Co., Ltd.), and the quality of the glass cloth and the flying property of the yarn are shown in Table 1.

Example 3 1.9% by weight of high amylose type etherified corn starch, 1.9% by weight of normal type esterified corn starch, sucrose laurate (monoester 75 di-, tri-, poly-, ester 25% MITSUBISI-KASEI) FOODS COR
P.) 0.2% by weight, hydrogenated vegetable oil 0.7% by weight, parafung wax 0.7% by weight, tetraethylene pentamine and stearic acid condensate 0.2% by weight, emulsifier 0.2% by weight, formalin 0.03% by weight
0.8% by weight of the sizing agent of the present invention consisting of 94% by weight of water (converted to 100% of pure content) and 0.8% by weight of the sizing agent are applied to the yarn, and the yarn is woven with a high speed air jet loom (ZA type manufactured by Tsudakoma Industries Co., Ltd.) Table 1 shows the quality of the glass cloth and the flying property of the yarn.

Example 4 High amylose type etherified corn starch 2.0% by weight, normal type ester low viscosity corn starch 2.0
% By weight, sucrose butyrate (75% mono-ester,
Di, tri, poly, ester 25%) 0.5% by weight, hydrogenated vegetable oil 0.65% paraffin wax 0.7% by weight, acetic acid activator of a mixture of tetraethylenepentamine and stearic acid 0.2% by weight , Emulsifier 0.2% by weight, formalin 0.03% by weight (converted to 100% pure content) and water 9
0.8% by weight of the sizing agent of the invention consisting of 4.4% by weight
The adhered yarn was woven with a high speed air jet loom (ZA type manufactured by Tsudakoma Kogyo Co., Ltd.), and the quality of the glass cloth and the flying property of the yarn are shown in Table 1.

Example 5 High amylose type etherified corn starch 2.0% by weight, normal type ester low viscosity corn starch 2.0
% By weight, saccharose stearate (S-1670)
0.03% by weight, sucrose butyrate (75% monoester, 25% di, tri, poly, ester) 0.05
% By weight, 0.7% by weight of hydrogenated vegetable oil, 0.8% by weight of paraffin washes, 0.25% by weight of acetic acid activity of a condensate of tetraethylenepentamine and stearic acid, 0.2% by weight of emulsifier, 0 of formalin. .03% by weight (100 net)
%) And 92.9% by weight of water and 0.92% by weight of the sizing agent of the present invention attached to the yarn, and weaving with a high-speed air jet loom (Type ZA manufactured by Tsudakoma Industries Co., Ltd.). Table 1 shows the quality of the glass cloth and the flying properties of the yarn.
Shown in

Comparative Example 1 A glass cloth was woven in the same manner as in Example 1 except that water was added instead of 0.05% by weight of sucrose fatty acid ester, and the quality and yarn of the obtained glass cloth were obtained. Table 1 shows the flight performance of the.

[0021]

As described above, according to the present invention, the presence of starch and sucrose fatty acid ester in the sizing agent causes the sizing agent of the cake obtained by winding the glass fiber strand to which the sizing agent is attached to dry. The amount of partial transfer to the surface due to can be reduced. As a result, there is less variation in the amount of sizing agent attached to the glass fiber strands,
The quality of the yarn produced by twisting the glass fiber strands is stable and the change is small, and the fluff of the glass cloth is reduced, the stable flying property of the yarn is exhibited, and the excellent degreasing property is exhibited. In addition to the effect on quality, it also has an economical effect that the migration of components to the surface is reduced and the amount of waste of the portion having a large amount of sizing agent in the outermost cake layer portion of the strand is reduced.

[0022]

[Table 1]

Claims (3)

[Claims] 1. A sizing agent for glass fibers, comprising a starch-containing sizing agent for glass fibers containing sucrose fatty acid ester. 2. The sizing agent according to claim 1, wherein the compounding ratio of sucrose fatty acid ester to 100 parts by weight of starch is 1 to 50 parts by weight. 3. The solid content of the sizing agent of claim 1 is 0.05-1.
Glass fiber yarn with 0.0% by weight attached.