JP5723070B2 - Textile glue and its application - Google Patents

Description

  The present invention relates to a fiber paste and its application. Specifically, the present invention relates to a warp sizing agent that is particularly preferably used during weaving, a sizing yarn obtained by sizing the sizing agent, and a method for producing a fabric performed using the sizing yarn. .

Various performances such as adhesive strength, water resistance, abrasion resistance, tack resistance, and scouring properties are required for the glue used for weaving fibers. Further, when weaving using filament yarn, weaving is performed using a loom to improve the production efficiency (for example, Patent Document 1).
Recently, the number of warp deniers has become smaller (fine denier). A yarn having a small number of deniers is thinner and weaker than normal denier, so warp breakage during weaving is likely to occur. Usually, in order to prevent warp breakage at the time of weaving, the amount of glue is increased to increase the convergence of monofilaments. However, when the amount of glue is increased, there is a problem that adhesion that causes poor opening of the warp during weaving occurs or falling glue occurs. From such a point of view, it is desired to develop a glue that can give the yarn an adhesive property that suppresses warp breakage during weaving and an adhesive property that can suppress poor opening, and can suppress the occurrence of falling paste. ing.

Japanese Unexamined Patent Publication No. 2000-45145

  An object of the present invention is to provide a fiber sizing agent capable of imparting excellent adhesiveness and tack resistance to a yarn and suppressing the occurrence of falling glue, and a sizing yarn obtained by sizing the fiber sizing agent. And a method for producing a woven fabric performed using the glued yarn.

  As a result of intensive studies, the present inventors have included a specific copolymer and / or a neutralized product thereof, wax and water as essential components, and adjusted the weight concentration of solids contained in the paste to 12%. It has been found that if the surface tension of the aqueous solution is within a specific range, the fiber paste can impart excellent adhesion and tack resistance to the yarn and suppress the occurrence of falling paste.

  That is, the fiber paste of the present invention is a copolymer obtained by copolymerizing a polymerizable component containing (meth) acrylic acid, a (meth) acrylic acid alkyl ester monomer and a styrene monomer. And the surface tension of the aqueous solution which contained the neutralized material, the wax, and water as an essential component, and adjusted the weight concentration of the solid content contained in this paste to 12% is 30-60 mN / m.

  The weight ratio of the (meth) acrylic acid in the polymerizable component is preferably 1 to 30% by weight. Similarly, the weight ratio of the (meth) acrylic acid alkyl ester monomer is preferably 40 to 95% by weight. Similarly, the weight ratio of the styrenic monomer is preferably 1 to 30% by weight.

The copolymer preferably has a weight average molecular weight of 80,000 to 200,000.
The acid value of the copolymer is preferably 90 to 200.
The total weight ratio of the (meth) acrylic acid, the (meth) acrylic acid ester monomer and the styrene monomer in the polymerizable component is preferably 95% by weight or more.

The weight ratio of the neutralized product of the copolymer to the solid content of the fiber paste is preferably 70 to 98% by weight. Similarly, the weight ratio of the wax is preferably 1 to 30% by weight.
The pH of the aqueous solution in which the weight concentration of the solid content contained in the fiber paste is adjusted to 1% is preferably in the range of 7-10.

  The glued yarn of the present invention is formed by sizing the above-mentioned fiber sizing agent into a yarn. The yarn is preferably a multifilament yarn composed of polyamide or polyester. The yarn is preferably a multifilament yarn of 56 dtex or less.

In addition, the sizing yarn of the present invention obtained by sizing the fiber sizing agent into the multifilament yarn has a space ratio defined by the following formula (1) when the number of filaments of the multifilament yarn is 3 to 7 When the number of filaments of the multifilament yarn is 8 to 36, it can be expressed as 8% or less.
Space ratio (%) = ((N1 / (N2 × N3)) × 100 (1)
N1: Spatial area inside the glued yarn in the glued yarn section N2: Cross-sectional area of the monofilament in the glued thread section N3: Number of filaments

  The method for producing a woven fabric according to the present invention includes a step of weaving a warp made of the above-mentioned glued yarn and a weft using a weaving machine. The method for producing a woven fabric of the present invention is suitable when the loom is a water jet loom.

The fiber paste of the present invention can impart excellent adhesiveness and tack resistance to yarns. In addition, when the fiber paste of the present invention is used, generation of falling paste during weaving can be suppressed.
Since the glued yarn of the present invention uses the fiber paste of the present invention, it has excellent adhesiveness and can suppress warp breakage during weaving. In addition, it has excellent adhesion resistance and can suppress the occurrence of poor opening of warp and falling glue during weaving.
In the method for producing a woven fabric of the present invention, since the glued yarn of the present invention is used as a warp, warp breakage at the time of weaving, poor opening of warp and generation of falling glue can be suppressed.

Schematic diagram of glued yarn cross section

[Fiber paste]
The fiber paste of the present invention contains a specific copolymer and / or a neutralized product thereof (hereinafter sometimes referred to as paste component A), wax and water as essential components, and is contained in the paste. The surface tension of the aqueous solution in which the weight concentration of the solid content is adjusted to 12% is 30 to 60 mN / m. According to the fiber sizing agent of the present invention, the sizing agent component can be infiltrated into the yarn, and the abnormal adhesion portion of the sizing agent on the surface of the yarn can be suppressed. Moreover, plasticization of the paste can also be suppressed. Therefore, it is considered that excellent anti-adhesion property can be imparted to the yarn and the occurrence of falling glue can be suppressed. Further, since the paste penetrates into the inside of the yarn, it is considered that the convergence is improved and the adhesiveness is improved.

Hereinafter, the liquid containing the paste component A and water is referred to as a paste component liquid. The paste component liquid generally has a high viscosity. When measuring the pH of the paste component liquid as it is using a pH meter, the pH concentration after the measurement may be hindered, so the weight concentration of solids contained in the paste component liquid was adjusted to 1%. A value obtained by measuring the pH of the aqueous solution at 20 ° C. is defined as the pH of the paste component liquid. Similarly, the pH of the fiber paste means a value obtained by measuring the pH of an aqueous solution in which the weight concentration of solids contained in the fiber paste is adjusted to 1% at 20 ° C. The method for adjusting the weight concentration to 1% is not particularly limited, but a method of adding distilled water or ion-exchanged water or heating and / or drying to the paste component liquid or the fiber paste. And a method of removing volatile components such as water and hydrophilic solvents.
Here, solid content means the non-volatile component remove | excluding volatile components, such as water and a hydrophilic solvent, from the paste component liquid or the fiber paste. As shown in the Examples, the weight of the solid content is the weight of the component remaining after heating and / or drying the paste component liquid and the fiber paste. In the following description, the weight of the paste component means the weight of the solid content of the reaction mixture obtained after the manufacture of the paste component.

As for the viscosity of the paste component liquid and the fiber paste, the viscosity of the aqueous solution in which the weight concentration of the solids contained in the paste component liquid and the fiber paste is adjusted to 20% is the same as the pH explained in detail above. It shall mean the value measured at ° C. The method for adjusting the weight concentration to 20% is the same as described above.
Similarly to the above, the surface tension of the fiber sizing agent means a value obtained by measuring the surface tension of an aqueous solution in which the weight concentration of solids contained in the fiber sizing agent is adjusted to 12% at 20 ° C. . The method for adjusting the weight concentration to 12% is the same as described above.

(Glue component A)
The paste component A is an essential component of the fiber paste of the present invention. By using such a specific paste component A together with other essential components and further setting the fiber paste to a specific surface tension, it is possible to impart excellent adhesiveness and tack resistance to the yarn during weaving. The generation of falling glue can be suppressed.
The copolymer contains a polymerizable component containing (meth) acrylic acid, a (meth) acrylic acid ester monomer, and a styrene monomer, and may contain other monomers as necessary. Is produced by a copolymerization step in which a polymerizable component (hereinafter, this polymerizable component is sometimes referred to as a polymerizable component a) is copolymerized by solution polymerization. Furthermore, paste component A can be manufactured through the neutralization process which neutralizes the copolymer obtained at the copolymerization process. Usually, in the neutralization step, an alkaline substance is added in the presence of water to convert the copolymer into a neutralized product thereof, so that the obtained paste component A coexists with water.

  The polymerizable component a contains a polymerizable component containing (meth) acrylic acid, a (meth) acrylic ester monomer and a styrene monomer, and may contain other monomers. . In the present application, (meth) acryl means acryl and / or methacryl. Therefore, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and (meth) acrylic acid ester monomer means an acrylic acid ester monomer and / or methacrylic acid ester single monomer. Means the body.

  The weight ratio of methacrylic acid in (meth) acrylic acid is preferably 20 to 100% by weight, more preferably 50 to 95% by weight, and particularly preferably 60 to 90% by weight. When the weight ratio of methacrylic acid is too small, compatibility with other hydrophobic monomers that may be contained in the polymerizable component a is lowered, and it becomes difficult to obtain a uniform polymer.

The (meth) acrylic acid ester monomer in the present invention has a structure in which a hydrogen atom of a carboxyl group in (meth) acrylic acid is substituted with a hydrocarbon group.
The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an alicyclic hydrocarbon group, but an aliphatic hydrocarbon group is preferred from the viewpoint of ease of copolymerization. The aliphatic hydrocarbon group may be saturated or unsaturated, but an alkyl group which is a saturated aliphatic hydrocarbon group is preferable from the viewpoint of ease of copolymerization. That is, a (meth) acrylic acid alkyl ester monomer is preferred. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 26, and particularly preferably 1 to 22 from the viewpoint of ease of copolymerization.

  Examples of (meth) acrylate monomers include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, and nonyl acrylate. Decyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, tert-butyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate , Octadecyl acrylate, nonadecyl acrylate, arachidyl acrylate, behenyl acrylate, lignoselenyl acrylate, cerothinyl acrylate, merlicinyl acrylate, palmitoly acrylate Acrylate, oleyl acrylate, linoleyl acrylate, linolenyl acrylate, phenyl acrylate, isobornyl acrylate, cyclohexyl acrylate, etc .; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate , Pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, 2-ethylhexyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, undecyl methacrylate, dodecyl methacrylate , Tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate Nonadecyl methacrylate, arachidyl methacrylate, behenyl methacrylate, lignoselenyl methacrylate, serotinyl methacrylate, melicinyl methacrylate, palmitoleyl methacrylate, oleyl methacrylate, linoleyl methacrylate, linolenyl methacrylate, phenyl methacrylate, isobornyl methacrylate, And methacrylic acid ester monomers such as cyclohexyl methacrylate.

  Examples of the styrenic monomer include styrene, vinyl toluene, α-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn- Hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, α-methyl styrene, dimethyl styrene, n-methoxy styrene, p-phenyl styrene, p -Chlorstyrene, 3, 4- dichlorostyrene, etc. are mentioned. These styrenic monomers may be used alone or in combination of two or more. Among these, styrene, vinyl toluene, α-methyl styrene, p-ethyl styrene, and 2,4-dimethyl styrene are preferable because of high adhesiveness.

The polymerizable component a may contain other monomers as long as the effects of the present invention are not impaired. Examples of other monomers include nitrile monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile; acrylic amide, methacrylamide, diacetone acrylamide, acrylamide-t. -Acrylic amide monomers such as butyl sulfonic acid; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, acrylic acid 4-hydroxybutyl, 2-hydroxypentyl acrylate, 3-hydroxypentyl acrylate, 4-hydroxypentyl acrylate, 5-hydroxypentyl acrylate, 2,3-dihydroxypropylene acrylate Acrylate, 2,3-dihydroxybutyl acrylate, 2,4-dihydroxybutyl acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, polybutylene glycol acrylate, etc .; Hydroxyethyl, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypentyl methacrylate, 3-hydroxy methacrylate Pentyl, 4-hydroxypentyl methacrylate, 5-hydroxypentyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxybutyl methacrylate, methacrylate Hydroxyalkyl methacrylate monomers such as 2,4-dihydroxybutyl acid, polyethylene glycol methacrylate, polypropylene glycol methacrylate and polybutylene glycol methacrylate; vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride Monomers; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, etc.
These other monomers may be used alone or in combination of two or more.

  In the polymerizable component a, an essential component (meth) acrylic acid, a (meth) acrylic acid ester monomer, a polymerizable component containing a styrene monomer, and other single amounts included as necessary Although there is no limitation in particular about the weight ratio of a body, the following ratios are preferable from the point which exhibits the effect of this invention more.

  The weight ratio of (meth) acrylic acid in the polymerizable component a is preferably 1 to 30% by weight, more preferably 5 to 25% by weight, and particularly preferably 10 to 20% by weight. If (meth) acrylic acid is less than 1% by weight, abnormal adhesion may occur during pasting. On the other hand, when (meth) acrylic acid is more than 30% by weight, the glue does not penetrate into the inside of the yarn and tends to adhere to the surface of the yarn at the time of gluing. May cause sticking problems.

  The weight ratio of the (meth) acrylic acid ester monomer in the polymerizable component a is preferably 40 to 95% by weight, more preferably 45 to 90% by weight, and particularly preferably 50 to 85% by weight. When the (meth) acrylic acid ester monomer is less than 40% by weight, the adhesiveness tends to be inferior. On the other hand, if the (meth) acrylic acid ester monomer is more than 95% by weight, there is a possibility of causing adhesion problems such as defective opening on the loom.

  The weight ratio of the styrene monomer in the polymerizable component a is preferably 1 to 30% by weight, more preferably 1.5 to 20% by weight, and particularly preferably 2 to 10% by weight. When the styrene monomer is less than 1% by weight, the adhesiveness of the glue component A to the polyester having an aromatic skeleton is poor, which may cause warp breakage. On the other hand, when the styrene monomer is more than 30% by weight, the adhesiveness and conjugation tend to be inferior.

When the polymerizable component a contains other monomer, the weight ratio is from 100% by weight to the weight ratio of (meth) acrylic acid, (meth) acrylic acid ester monomer and styrene monomer. The remainder after subtracting the sum.
From the standpoint of further exerting the effects of the present invention, the total weight ratio of (meth) acrylic acid, (meth) acrylic acid ester monomer and styrene monomer in the polymerizable component a is 95% by weight or more. Is preferable, 96% by weight or more is more preferable, 98% by weight or more is further preferable, and 100% by weight is particularly preferable.

  In addition, the polymerizable component a does not contain an acrylamide monomer such as acrylamide, methacrylamide, diacetone acrylamide, acrylamide-t-butylsulfonic acid, or the weight ratio thereof as other monomers. It is preferable to make it as small as possible. Specifically, the weight ratio of the acrylamide monomer in the polymerizable component a is preferably less than 3% by weight, more preferably less than 2% by weight, further preferably less than 1% by weight, particularly preferably 0% by weight. preferable. When the weight ratio of the acrylic amide monomer is 3% by weight or more, the glue does not penetrate into the inside of the yarn and tends to adhere to the surface of the yarn, which may cause adhesion problems such as defective opening on the weaving machine. There is sex.

The copolymerization step is a step of copolymerizing the polymerizable component a by solution polymerization. Thus, if the fiber paste contains a copolymer neutralized product obtained by copolymerizing the polymerizable component a by solution polymerization and undergoing a neutralization step described later, warp breakage during weaving is suppressed. Excellent adhesion and tack resistance.
In the copolymerization step, a solvent, a polymerization initiator, a chain transfer agent and the like are used in addition to the polymerizable component a and water, but the polymerization method is not particularly limited as long as it is known. That is, one or two or more methods can be used by methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization. The solution polymerization is preferably performed.

  The solvent used for the polymerization is used for the purpose of improving the compatibility of the polymerizable component a and suppressing the molecular weight of the resulting copolymer. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, i-propanol, butanol, pentanol, ethylene glycol, and glycerin. Although there is no limitation in particular about the weight ratio of a solvent, Preferably it is 2 to 50 weight% with respect to the polymeric component a, More preferably, it is 6 to 40 weight%, Most preferably, it is 8 to 35 weight%. If the weight ratio of the solvent is less than 2% by weight, the solution stability during copolymerization tends to deteriorate, and further, the molecular weight of the copolymer increases, resulting in the production of a highly viscous product and post-processing. In the scouring in the process, an inferior tendency is seen, which is not preferable. On the other hand, when the weight ratio of the solvent is more than 50% by weight, the molecular weight of the copolymer is lowered, and the adhesiveness and conjugation property of the fiber paste are inferior.

  Although it does not specifically limit as a polymerization initiator, A water-soluble polymerization initiator, an oil-soluble initiator, etc. are preferable. For example, water-soluble polymerization initiators include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; peroxides such as t-butyl hydroperoxide, t-butyl peroxymaleic acid, and succinic peroxide. Azo compounds such as 2,2′-azobis- (2-amidinopropane dihydrochloride); Examples of the oil-soluble initiator include peroxides such as benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, cumyl peroxyneodecanoate, cumyl peroxyoctoate; azobiscyclohexanecarbonyl, azobis Examples thereof include azo compounds such as isobutylamidine hydrochloride and azobisisobutyronitrile. The weight ratio of the polymerization initiator is not particularly limited, but is preferably 0.1 to 3% by weight, more preferably 0.3 to 2.5% by weight, particularly preferably 0. 0% with respect to the polymerizable component a. 5 to 2% by weight. When the weight ratio of the polymerization initiator is less than 0.1% by weight, it is preferable because the molecular weight of the copolymer is increased, so that a highly viscous product is generated, and in the scouring in the post-processing step, an inferior tendency is seen. Absent. On the other hand, when the weight ratio of the polymerization initiator is more than 3% by weight, the molecular weight of the copolymer is lowered, and the adhesiveness and conjugation property of the fiber paste are inferior.

  Chain transfer agents are sometimes used to suppress the molecular weight of the copolymer. Examples of the chain transfer agent include alkyl mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, cyclohexyl mercaptan, lauryl mercaptan; thioglycolic acid such as octyl thioglycolate and 2-ethylhexyl thioglycolate Examples include esters. The weight ratio of the chain transfer agent is preferably 0.8% by weight or less, more preferably 0.6% by weight or less, and particularly preferably 0.5% by weight or less with respect to the polymerizable component a. When the weight ratio of the polymerization initiator is more than 0.8% by weight, the molecular weight of the copolymer is lowered, and the adhesiveness and conjugation property of the fiber paste are inferior.

  Although it does not specifically limit in a copolymerization process, It can carry out with the superposition | polymerization temperature and superposition | polymerization time which were adapted by methods, such as emulsion polymerization, solution polymerization, suspension polymerization, and block polymerization.

  The acid value of the copolymer obtained in the copolymerization step is preferably 90 to 200, more preferably 95 to 180, and still more preferably 100 to 160. A copolymer copolymerized with an acid value within this range can easily penetrate into the interior due to increased wettability between fibers, and can impart excellent adhesion and anti-tacking properties to the yarn. The generation of falling glue can be suppressed. In addition, the acid value as used in the field of this invention means the milligram number of potassium hydroxide required in order to neutralize the carboxyl group derived from (meth) acrylic acid contained in 1 gram of copolymers.

  Next, the neutralization process which neutralizes the copolymer obtained at the copolymerization process is demonstrated. In the neutralization step, an alkaline substance is added to the dispersion containing the copolymer in the presence of water to convert the copolymer into a neutralized product.

  Examples of the alkaline substance include metal hydroxides such as sodium hydroxide, potassium hydroxide, and barium hydroxide; ammonia; trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, methyldiethanolamine, dimethylethanolamine, and the like. Organic amines etc. are mentioned. These alkaline substances are preferably added dropwise as an aqueous solution dissolved in water. For example, an aqueous solution of an alkaline substance having a concentration of 10 to 30% by weight is prepared and added dropwise to a dispersion containing a copolymer over 10 to 30 minutes. Good. The end point of dropping the alkaline substance can be determined, for example, by changing the dispersion containing the copolymer into a transparent state. In this case, the paste component A is in a state dissolved in water, and the paste component liquid A can be said to be an aqueous solution in which the paste component A is dissolved.

  The neutralization degree of the paste component A is preferably 40 to 100 mol%, more preferably 50 to 90 mol%, and particularly preferably 60 to 80 mol%. If the degree of neutralization of the paste component A is lower than 40 mol%, abnormal adhesion may occur during pasting. Here, the degree of neutralization refers to mol% of the alkali component that has undergone a neutralization reaction with respect to the total acid amount of the carboxyl group-containing monomer.

  The pH of the paste component liquid A is preferably 7 to 10, more preferably 7.2 to 9.5, still more preferably 7.5 to 9.2, and particularly preferably 7.8 to 9.0. If the pH of the paste component liquid A is lower than 7, there is a possibility that abnormal adhesion may occur during pasting. On the other hand, when the pH of the glue component liquid A is higher than 10, the glue does not penetrate into the inside of the yarn during gluing, and tends to adhere to the surface of the yarn. May cause problems.

  The viscosity of the paste component liquid A is preferably 60 to 1000 mPa · s, more preferably 80 to 800 mPa · s, and particularly preferably 100 to 600 mPa · s. When the viscosity of the paste component liquid A is lower than 60 mPa · s, the adhesiveness and conjugation tend to be inferior. On the other hand, when the viscosity of the glue component liquid A is larger than 1000 mPa · s, the glue does not penetrate into the inside of the yarn during gluing and tends to adhere to the yarn surface. May cause sticking problems.

  A copolymer or a neutralized product thereof is an aggregate of homologues having different molecular weights, and the molecular weight is obtained as an average amount. There are several types of definitions of the average molecular weight. For example, number average molecular weight, weight average molecular weight, viscosity average molecular weight and the like are generally used. In the present invention, the weight average molecular weight is used. The weight average molecular weight can be adjusted by a known method such as the ratio of the initiator, the presence or absence of a chain transfer agent, and a solvent. The weight average molecular weight of the copolymer obtained by copolymerizing the polymerizable component a or a neutralized product thereof is preferably 80,000 to 200,000, more preferably 90,000 to 190,000, and particularly preferably 100,000 to 180,000. When the weight average molecular weight is more than 200,000, the glue does not penetrate into the inside of the yarn and tends to adhere to the surface of the yarn when gluing, which may cause adhesion problems such as defective opening on the weaving machine. There is. On the other hand, when the weight average molecular weight is less than 80000, the adhesion and conjugation properties may be inferior.

30-90 degreeC is preferable, as for a glass transition point when a copolymer is measured with a differential scanning calorimeter (DSC), 40-80 degreeC is more preferable, and 50-70 degreeC is further more preferable. If the glass transition point is less than 30 ° C., adhesion problems such as defective opening may occur on the loom. If it exceeds 90 ° C., the adhesiveness tends to be inferior.
In addition, the glass transition point as used in the field of this invention is based on JIS-K7121, and in the part which shows the step-like change of the DSC curve obtained by the DSC measurement mentioned later, from the extended straight line of each base line to the vertical axis direction etc. It is defined as the point (unit: ° C) where the straight line at the distance and the curve of the step-like change part intersect.

  The weight ratio of the paste component A to the solid content contained in the fiber paste is preferably 65 to 98% by weight, more preferably 70 to 98% by weight, still more preferably 75 to 95% by weight, and particularly preferably 80%. ~ 90% by weight. If the weight ratio of the paste component A is less than 65% by weight of the solid content contained in the fiber paste, the adhesiveness is poor, which may cause warp breakage.

(wax)
Along with the paste component A, the wax is an essential component of the fiber paste of the present invention. By containing a wax, smoothness is improved, and warp breakage during weaving, poor opening of warp and generation of falling paste can be suppressed.
Examples of the wax include petroleum wax such as paraffin wax and microcrystalline wax; synthetic wax such as polyhydric alcohol fatty acid ester, polyethylene wax and polyethylene oxide; wood wax, carnauba wax, candelilla wax, beeswax, lanolin, rice wax, Animal and plant waxes such as banana wax and sugarcane wax; mineral waxes such as montan wax, ozokerite and ceresin, stearic acid, hardened beef tallow, hardened pork fat and the like. These waxes may be used alone or in combination of two or more.
Among these, from the viewpoint of smoothness, petroleum waxes, synthetic waxes, animal and vegetable waxes, and mineral waxes are preferable, animal and vegetable waxes, petroleum waxes, and synthetic waxes are more preferable, and animal and vegetable waxes and petroleum waxes are particularly preferable. preferable.

Since the wax is oil-soluble, it is usually used as an aqueous dispersion emulsified with a surfactant such as a nonionic surfactant or an anionic surfactant in consideration of dispersibility.
Nonionic surfactants include ethylene oxide adducts of higher alcohols such as lauryl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, and ethylene oxide adducts of phenol alkylated with octyl, nonyl, dodecyl, etc. Is mentioned. Among these, a higher alcohol ethylene oxide adduct of a lauryl alcohol / cetyl alcohol / stearyl alcohol combination system is preferable, and a higher alcohol ethylene oxide adduct of a lauryl alcohol / stearyl alcohol combination system is more preferable.

  Examples of the anionic surfactant include sulfate ester salts and phosphate ester salts of ethylene oxide adducts of higher alcohols such as lauryl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, and benzene sulfonate alkylated with a dodecyl group. Can be mentioned. Among these, a sulfate ester salt of a higher alcohol ethylene oxide adduct of a lauryl alcohol / cetyl alcohol / stearyl alcohol combination system is preferable, and a sulfate ester salt of a higher alcohol ethylene oxide adduct of a lauryl alcohol / stearyl alcohol combination system is further included. preferable.

As a method for preparing the wax, for example, a melted wax and an emulsifier are added to a system in which warm water at 90 ° C. is stirred, and the wax emulsion is diluted with a solid content concentration of 20% while maintaining the emulsification temperature at 90 ° C. Can be obtained.
The weight ratio of the surfactant to the total of the wax and the surfactant is 5 to 45% by weight, more preferably 8 to 40% by weight, and particularly preferably 10 to 35% by weight. When the weight ratio of the surfactant is less than 5% by weight, the emulsification of the wax decreases and it is difficult to obtain a uniform emulsion. On the other hand, when the weight ratio of the surfactant is more than 45% by weight, the film becomes soft and may cause adhesion problems such as poor opening on the weaving machine.

As the step of adding the wax, for example, an aqueous dispersion of wax is prepared separately, and the aqueous dispersion of wax is added to the paste component A obtained in the above neutralization step, and these are mixed and stirred. A process etc. are mentioned.
The weight ratio of the wax in the solid content contained in the fiber paste is not particularly limited, but is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, and particularly preferably 3 to 17% by weight. It mix | blends so that it may become. When the weight ratio of the wax is less than 1% by weight of the solid content contained in the fiber paste, the smoothness tends to be inferior. On the other hand, when the weight ratio is more than 30% by weight of the solid content contained in the fiber paste, the adhesiveness and conjugation tend to be hindered by the wax peeling effect.

(Other ingredients)
The fiber paste of the present invention is a fiber paste containing the paste component A, wax and water as essential components. Therefore, in the fiber sizing agent of the present invention, when the fiber sizing agent is applied to the fiber, it does not mean only the fiber sizing agent containing only the glue component A and the wax. The fiber paste of the present invention may further contain a paste component other than the paste component A as long as the effects of the present invention are not impaired.

  The paste component other than the paste component A is not particularly limited as long as it is not the paste component A. For example, starch, polyvinyl alcohol, carboxymethyl cellulose, synthetic paste ((meth) acrylic acid polymer, (meta ) Acrylic acid ester polymer, (meth) acrylic acid- (meth) acrylic acid ester polymer, maleic acid polymer and salts thereof, water-soluble polyester, water-soluble urethane, etc.).

  The fiber sizing agent of the present invention is not limited to the effect of the present invention, and in addition to the sizing component, an antistatic agent for preventing peeling of the glued yarn and frictional charging, and foaming of the fiber sizing agent. It may contain other components such as an antifoaming agent for suppressing and an antibacterial agent for preventing microbial contamination of raw machinery produced by weaving.

  In the method for producing a fiber paste of the present invention, other components may be added in a copolymerization step or a neutralization step, or may be added in a step separate from the copolymerization step or the neutralization step.

(General glue for fibers)
The surface tension (20 ° C.) of the aqueous solution in which the weight concentration of solids contained in the fiber paste is adjusted to 12% is preferably 30 to 60 mN / m, more preferably 40 to 58 mN / m, and particularly preferably 50 to 56 mN / m. When the surface tension is lower than 30 mN / m, the amount of the fiber sizing agent adhering during sizing decreases, and the adhesion and conjugation properties are poor. On the other hand, when the surface tension is greater than 60 mN / m, the amount of the fiber paste used during sizing increases, causing adhesion problems such as poor opening on the weaving machine.

If a surfactant is used, the surface tension of the fiber sizing agent can be lowered. However, if the surfactant is used more than necessary, the sizing agent may be plasticized to cause adhesion problems during weaving. In the fiber sizing agent of the present invention, by using a specific copolymer and / or a neutralized product thereof and a wax, an optimum surface tension can be obtained without using a surfactant more than necessary. it can. Therefore, excellent adhesiveness and tack resistance can be imparted to the yarn, and the occurrence of falling glue can be suppressed.
The weight ratio of the surfactant contained in the fiber paste is preferably 0.5 to 4%, more preferably 1.0 to 3.5%, particularly preferably 1.5 to 3% of the entire fiber paste. 0.0%. When the weight concentration of the surfactant is less than 0.5%, the adhesiveness tends to be inferior. On the other hand, when the weight concentration of the surfactant is more than 4%, the film becomes soft and may cause adhesion problems such as poor opening on the weaving machine.

  The fiber paste of the present invention requires water. The weight concentration of the solid content contained in the fiber paste is preferably 5 to 18%, more preferably 6 to 15%, and particularly preferably 7 to 13% of the entire fiber paste. When the weight concentration of the solid content is less than 5%, the amount of the adhesive for fiber during sizing decreases, and there is a tendency that the adhesion and conjugation tend to be inferior. On the other hand, if the weight concentration of the solid content exceeds 18%, the glue does not penetrate into the inside of the yarn during gluing and tends to adhere to the surface of the yarn, which causes adhesion problems such as defective opening on the weaving machine. There is a possibility of waking up.

  The pH of the fiber paste is preferably 7 to 10, more preferably 7.2 to 9.5, still more preferably 7.5 to 9.2, and particularly preferably 7.8 to 9.0. If the pH of the fiber sizing agent is lower than 7, abnormal adhesion may occur during sizing. On the other hand, when the pH of the glue component liquid A is higher than 10, the glue does not penetrate into the inside of the yarn during gluing, and tends to adhere to the surface of the yarn. May cause problems.

  The viscosity of the fiber paste is preferably 10 to 800 mPa · s, more preferably 20 to 600 mPa · s, and particularly preferably 30 to 400 mPa · s. When the viscosity of the fiber paste is lower than 10 mPa · s, there is a tendency that the adhesion and conjugation tend to be inferior. On the other hand, when the viscosity of the fiber sizing agent is greater than 800 mPa · s, the sizing agent does not penetrate into the inside of the yarn during gluing and tends to adhere to the yarn surface. May cause sticking problems.

  The fiber sizing agent of the present invention can be particularly suitably used for thin threads because the effects of the present invention can be further exhibited. A suitable thread thickness is as described later.

[Glued yarn]
The glued yarn of the present invention is obtained by sizing the above-described fiber paste on a yarn.
The yarn may be either a multifilament yarn or a spun yarn (spun yarn), but a multifilament yarn is preferred from the viewpoint of further exerting the effects of the present invention. There are no particular limitations on the type of yarn constituting the yarn, cotton; rayon; acetate; hemp; wool; acrylic; polyethylene; terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexanedimethylene terephthalate, and polyethylene-2,6 -Polyester fibers such as naphthalene dicarboxylate; Aliphatic polyamide fibers (nylon fibers) such as poly-ε-capramide and polyhexamethylenediamine adipamide; Polymetaphenylene isophthalamide and copolyparaphenylene-3,4-oxy Aromatic polyamide fibers (aramid fibers) such as diphenylene terephthalamide. In particular, it is preferable that the yarn type constituting the yarn is a multifilament yarn composed of polyester having an aromatic skeleton because of good adhesiveness and conjugation property with the fiber paste. Multifilament yarns composed of polyester having an aromatic skeleton are preferably substantially made of polyethylene terephthalate, but are also good for polyesters having other aromatic skeletons and polyamides having aromatic skeletons. Good adhesion and conjugation. The yarn may be composed of a single yarn type, or may be a blended yarn, a blended yarn or a multifilament yarn composed of a plurality of yarn types.

  The glued yarn of the present invention is particularly preferably a thin yarn from the viewpoint that the fiber paste of the present invention can penetrate into the yarn and the effects of the present invention can be further exhibited. In detail, in multifilament yarn, it is preferably 56 dtex or less, more preferably 6 to 44 dtex, and particularly preferably 8 to 33 dtex. The number of filaments of the multifilament yarn suitable for the fiber paste of the present invention is 3 to 36. The spun yarn (spun yarn) is preferably 20 to 100, more preferably 30 to 90, and particularly preferably 40 to 80.

  The glued yarn obtained by sizing the fiber paste of the present invention into a multifilament yarn penetrates into the multifilament yarn, so that the space ratio defined by the above formula (1) is Smaller than glued yarn. The effect of the present invention can be further exhibited by setting the space ratio to be equal to or less than a predetermined value below.

  When the number of filaments of the multifilament yarn is 3 to 7, the space ratio is preferably 3% or less, more preferably 1% or less, and further preferably 0.5% or less. When the number of filaments of the multifilament yarn is 8 to 36, the space ratio is 8% or less, preferably 5% or less, more preferably 3% or less. In the case of glued yarn with a space ratio of more than 3% (3 to 7 filaments) or more than 8% (8 to 36 filaments), the paste does not penetrate into the multifilament yarn, and the multifilament yarn There is a tendency to adhere to the surface, which may cause adhesion problems such as poor opening on the weaving machine.

The space ratio defined by the above formula (1) is calculated from the space area N1 inside the glued yarn, the cross-sectional area N2 of the monofilament, and the number of filaments N3 in the glued yarn cross section taken by the electron micrograph. The glued yarn cross section indicates a cross section when cut perpendicular to the extending direction of the multifilament yarn. The inside of the glued yarn refers to the entire inside of the glued yarn having the cross section. The space area is a gap formed between the monofilaments inside the glued yarn, and indicates the total area of the space where the glue component does not exist.
FIG. 1 is a conceptual diagram of the glued yarn showing the space area N1 inside the glued yarn in the section of the glued yarn, the cross-sectional area N2 of the monofilament, and the number N3 of filaments (seven in this case). The left side of FIG. 1 is a conceptual diagram of a glued yarn cross section with a space ratio of 10%, and the right side of FIG. 1 is a conceptual diagram of a glued thread cross section with a space ratio of 0%.

  The sizing method is not particularly limited, and examples thereof include a beam-to-beam method. In the beam-to-beam method, first, a warp beam obtained by drawing a yarn from a creel and a gluing box containing a fiber paste are prepared. Next, the yarn is pulled out of the warp beam, passed through the glue box, and the fiber glue is adhered (glued) to the yarn, followed by non-touch hot air drying and touch cylinder drying. The glued yarn is wound around a glued beam (gluing speed: 50 to 300 m / min, non-touch hot air drying temperature: 80 to 150 ° C., touch cylinder drying temperature: 50 to 130 ° C.).

The adhesion amount of the fiber sizing agent in the glued yarn is not particularly limited because it differs depending on the type and thickness of the yarn, but in general, preferably 2 to 18% by weight, more preferably 3 to 3%. 15% by weight, particularly preferably 4 to 13% by weight. The measurement conditions and the like of the adhesion amount of the fiber paste are described in detail below.
When the yarn is a polyester filament yarn, the adhesion amount of the fiber sizing agent in the glued yarn is preferably 2 to 13% by weight, more preferably 4 to 11% by weight, and particularly preferably 5 to 10% by weight. If the adhesion amount is less than 2% by weight, the adhesion and conjugation tend to be inferior. On the other hand, if the amount of adhesion exceeds 13% by weight, the amount of adhesion is too large, which may cause adhesion problems such as defective opening on the weaving machine.

  When the glued yarn of the present invention is used for weaving, it can be used for either warp or weft, but it is usually preferable to use it for warp. As shown above, the warp is obtained by attaching a fiber glue to the yarn and winding the dried glued yarn around a glued beam.

[Textile manufacturing method]
The method for producing a woven fabric of the present invention is a method including a step of weaving a warp made of the above-mentioned glued yarn and a weft using a weaving machine.
The warp is obtained by winding the glued yarn around a glued beam. For the weft, the yarn may be processed, but usually the raw yarn is generally used without any special treatment.

Examples of the weaving machine include a rapier room and an air jet room dry weaving machine; a water jet room and the like. Among these, it is more preferable that the loom is a water jet loom.
In the weaving, for example, the warp yarns described above are drawn one by one through the scissors and the scissors (drawing) to prepare warp yarns, which are applied to a weaving machine. Next, weaving is performed by sandwiching the warp yarn between the warp yarns while moving the warp yarn up and down alternately, for example, and a woven fabric is produced. When the weaving machine is a water jet weaving machine, the fallen glue generated on the weave of the weaving machine is washed away by the jet water used when flying the weft, so that the fallen glue can be effectively suppressed.

  As the weaving step, for example, 4,000 to 20,000 glued yarns described above as warp yarns and polyester filament yarns (6 to 167 decitex, 4 to 144 filaments) as weft yarns are prepared. Using a water jet loom (such as a water jet loom manufactured by Tsuda Koma Kogyo Co., Ltd.) or an air jet room (such as an air jet loom manufactured by Tsuda Koma Kogyo Co., Ltd.), with a loom rotating speed of 500 to 800 rpm and 50 m as a glance, polyester Taffeta can be woven 100 to 200 cm (weaving width: 70 to 200 cm).

  The present invention will be described in detail in the following examples and comparative examples, but the present invention is not limited thereto. First, measurement methods such as physical properties shown in Examples and Comparative Examples are shown below.

(1) Weight concentration of solid content For a certain amount (usually 1.0 to 2.0 g) of a sample (weight: M1), an infrared moisture meter device (Kett Science Laboratory, loss on drying method, FD230) was used. To measure the weight concentration of solids.
The weight concentration of the solid content is automatically calculated by using an infrared moisture meter device. The principle of the measurement is based on the above M1 and the weight (M2) obtained by drying the sample with the infrared moisture meter device and reaching a constant weight. The weight concentration of the solid content is calculated by the following formula. M2 is the weight of the solid content.
Solid content weight concentration (%) = (M2 / M1) × 100

(2) pH
It measures at 20 degreeC using a glass electrode pH measuring apparatus (Horiba Ltd. make, navihF-51).

(3) Viscosity Using a B-type rotational viscometer (manufactured by BROOK FIELD), the rotor No. Measure at 20 ° C. with 30 revolutions at 62.

(4) Surface tension measurement Using a dynamic wettability tester WET-6000 (manufactured by Reska Co., Ltd.), measurement is performed at 20 ° C. using a PET film.

(5) Weight average molecular weight Measured by a gel permeation chromatography method (GPC) using a calibration curve with a standard material polystyrene (Tosoh Corp.).
(Measurement condition)
Equipment used: High Performance Liquid Chromatography HLC-8020 (Tosoh Corporation)
Column: TSKgelGMHXL × 2 (Tosoh Corporation)
Solvent: THF (tetrahydrofuran) (Wako Pure Chemical Industries, Ltd., for liquid high performance chromatography)
Measurement temperature: 40 ° C
Flow rate: 1.0 ml / min.
Detector: differential refractometer Injection volume: 20 μl

(6) Adhesive amount of sizing agent for fiber A sized sizing yarn (about 2 g) was used as a sample, dried at 110 ° C. for 30 minutes, weighed (W1), and 100-fold scouring bath (sodium carbonate: 2 g / L) , POE 10 mol addition nonylphenol ether: 2 g / L) and immerse at 90 ° C. for 30 minutes and rinse with hot water. After the sample was further washed with water and dried for 1 hour, the sample was weighed (W2), and the adhesion amount was determined from the following formula.
Adhesion amount (%) = [(W1-W2) / W2] × 100

(7-1) Dry conjugation force (Evaluation of adhesion and conjugation in a dry state)
The conjugation force is measured with a TM conjugation force tester. Twenty glued yarns are aligned and stretched while applying the following thread tension. Between the combs arranged in three rows at an angle of 150 ° on the left and right and 120 ° on the center (comb: 20 needles × 3 rows; Interval: 30 mm; Comb reciprocating distance: 27 mm) is reciprocated (comb moving speed: 150 times / min), and the glued yarn is rubbed. After rubbing 20 times, the degree of cracking of the glued yarn is visually observed and evaluated according to the following evaluation criteria (1 to 5 grades). In this evaluation standard, grade 5 is the best and grade 1 is the worst.
Yarn tension: 0.2 to 0.6 g / dtex per yarn (120 g / 20 for polyester filament yarn 22 dtex 20 filament (= 6 g / y), 90 g / 20 for polyamide filament yarn 17 dtex 7 filament (= 4 .5g / book)

(7-2) Wet conjugation force (Evaluation of adhesion and conjugation in a wet state)
In the measurement of the dry conjugation force, the wet conjugation force is evaluated in the same manner as the dry conjugation force measurement, except that ion-exchanged water is added at a rate of 0.1 g / s to the portion of the glued yarn that is rubbed by the reciprocating motion. To do.
<Evaluation criteria for dry and wet conjugation power>
5th grade: No thread cracking 4th grade: Some thread cracking 3rd grade: There are thread cracks 2nd grade: Many thread cracks 1st grade: Overall thread cracks

(8-1) Dry paste properties (Evaluation of paste properties in dry state)
Between the combs bent at an angle of 150 ° on the left and right and 120 ° on the center while applying the yarn tension shown below for one 1000m glued yarn (comb: 20 needles x 3 rows; comb spacing: 100mm) Is run at a glued yarn feed speed of 50 m / min to rub the glued yarn. The amount of fallen paste and the fallen paste adhering to the comb are observed and evaluated according to the following evaluation criteria (1 to 5 grades). In this evaluation standard, grade 5 is the best and grade 1 is the worst.
(6g for polyester filament yarn 22 decitex 20 filament, 4.5g for polyamide filament yarn 17 dtex 7 filament)

(8-2) Wet sag properties (evaluation of sizing properties in a wet state)
In the above measurement of dry paste, the wet paste properties are evaluated in the same manner as the measurement of dry paste properties, except that ion-exchanged water is added to the portion of the glued yarn that is rubbed at a rate of 0.1 g / s. To do.
<Evaluation criteria for dry and wet paste properties>
Grade 5: Dropping of glue, no sticking of glue on comb Grade 4: Dropping of glue, little sticking of glue on comb 3rd grade: Dropping of glue, sticking of glue on comb Combining grade 2: Dropping of glue, dropping on comb Adhesive adhesion a little 1st grade: Adhesive loss, Adhesive adhesion to combs

(9) Adhesive test One gluing yarn of 1000 m was wound around a cone while applying the yarn tension shown below, left in an environmental tester at 30 ° C. and 80%, and then with a gluing yarn feed rate of 100 m / min. It was run and the resistance at that time was measured. The smaller the value, the better the adhesion, and the larger the value, the worse.
(Polyester filament yarn 22 decitex 20 filament with 12 g polyamide filament yarn 17 decitex 7 filament with 9.0 g)

(10) Adhesive fallen paste (Evaluation of fallen paste in practical weaving test)
The wrinkle adhesion fallen property (degree of fallen glue adhering to the wrinkles) at the time of weaving using a water jet loom (water jet loom manufactured by Tsudakoma Kogyo Co., Ltd.) was visually observed, and the following evaluation criteria (1 to Evaluate according to grade 5. In this evaluation standard, grade 5 is the best and grade 1 is the worst.
<Evaluation criteria for wrinkle adhesion and paste>
5th grade: No glue sticking on the heel 4th grade: Little glue sticking on the heel 3rd grade: Some glue sticking on the heel 2nd grade: Little glue sticking on the heel 1st grade: Many glue sticking on the heel

(11) Openability (Evaluation of openability in practical weaving test)
Openness (degree of opening between adjacent warps) during weaving using a water jet loom (water jet loom manufactured by Tsudakoma Kogyo Co., Ltd.) was visually observed, and the following evaluation criteria (1-5 grades) Evaluate according to In this evaluation standard, grade 5 is the best and grade 1 is the worst.
<Evaluation criteria for wrinkle adhesion and paste>
5th grade: No adhesion between adjacent warps 4th grade: There is little adhesion between adjacent warps 3rd grade: There is adhesion between adjacent warps 2nd grade: A little adhesion between adjacent warps 1st grade: Between adjacent warps Sticky

[Production Example 1-1] (Production of glue component A in the specification)
In a four-necked flask (capacity 1000 mL) equipped with a thermometer, a stirrer, a condenser and a nitrogen gas inlet, polymerizable components (type and amount are shown in Table 1), ion-exchanged water 150 g and ethanol 95 g as a solvent, 30 g of i-propanol and 4.5 g of polymerization initiator benzoyl peroxide were stirred and mixed to obtain a mixture. While blowing nitrogen gas, copolymerization was performed at 82 ° C. for 5 hours to obtain a reaction mixture containing the copolymer.
After the copolymerization, 72 g of ammonia water having a concentration of 16% is gradually added to the reaction mixture to neutralize the copolymer (pH 7 to 10), and cooled to room temperature. A paste component liquid 1-1 containing 1 was obtained.
The viscosity (the viscosity of the paste component liquid 1-1) of the aqueous solution adjusted to a weight concentration of 20% of the solid content contained in the paste component liquid 1-1 was 115 mPa · s. Moreover, pH (pH of paste component liquid 1-1) of the aqueous solution which adjusted the weight concentration of the solid content contained in paste component liquid 1-1 to 1% was 8.0. For dilution for pH measurement, ion-exchanged water was used as in the viscosity measurement. Further, after naturally drying the paste component liquid 1-1, the paste component solution 1-1 was dissolved in THF (tetrahydrofuran) (Wako Pure Chemical Industries, Ltd., for liquid high-speed chromatography) so as to have a concentration of 0.5 mg / ml. A weight average molecular weight of 1 was measured. Moreover, the acid value of the paste component 1-1 was 108.0, and the neutralization degree was 70 mol%.

[Production Examples 1-2 to 1-15]
The kinds and amounts of polymerizable components, ion-exchanged water and solvent shown in Tables 1 and 2 were added to the same four-necked flask used in Production Example 1-1. Subsequently, the polymerization initiator benzoyl peroxide shown in Table 1 was further added to the four-necked flask, mixed with stirring, and copolymerized at 82 ° C. for 5 hours to obtain a reaction mixture containing the copolymer.
After the copolymerization, ammonia water having a concentration of 16% shown in Tables 1 and 2 was gradually added to the reaction mixture to neutralize, cooled to room temperature, ion-exchanged water was added, and paste components 1-2 to 1- 15 paste component liquid 1-2 to 1-15 was obtained. The weight concentration of the solid content contained in the paste component liquid 1-2 to 1-15 was 20%. Others were evaluated in the same manner as in Production Example 1-1. The results are shown in Tables 1 and 2. In addition, when the glass transition point measurement of the obtained paste components 1-1 to 1-15 was performed, all were in the range of 50 to 80 ° C.

[Example 2-1]
Paste component liquid 1-1 containing paste component 1-1 obtained in the above production example, and an aqueous dispersion of a wax obtained by emulsifying paraffin wax and ester wax with a nonionic surfactant (sizing wax K-2, Matsumoto Yushi Seiyaku) And a fiber paste 2-1 having a weight ratio of paste component 1-1 / wax / surfactant = 88 / 9.6 / 2.4.
The pH of the aqueous solution in which the weight concentration of the solid content contained in the fiber paste 2-1 was adjusted to 1% (pH of the fiber paste 1), and the surface tension of the aqueous solution in which the weight concentration was adjusted to 12% were measured. The results are shown in Table 3.
Within 12 hours after the preparation of the fiber sizing agent 2-1, the polyester filament yarn (22 dtex 20 filament (22T / 20f)) and polyamide filament yarn (17 dtex 7 filament (17T / 7f)) Then, the sizing machine was used under the sizing conditions shown below to attach the fiber sizing agent 2-1 to obtain a sizing yarn 2-1. The adhesion amount of the fiber sizing agent 2-1 was 10% for the polyester filament yarn and 12% for the polyamide filament yarn.

<Sizing conditions>
Beam-to-beam method Gluing speed: 100m / min
Non-touch hot air drying temperature: 130 ° C
Touch cylinder drying temperature: 100 ° C
The number of touch cylinders: 3 About the obtained glued yarn 2-1, the conjugation force in the dry type and the wet type, the falling paste property, and the adhesiveness were evaluated. The results are shown in Table 3.

[Examples 2-2 to 2-12 and Comparative Examples 2-13 to 2-19]
In Example 2-1, the paste components used, the types of waxes (Sizing Wax V-2, Matsumoto Yushi Seiyaku Co., Ltd.), the weight ratios of the paste components, waxes and surfactants are shown in Tables 3 and 4, respectively. Except for changing to those shown, fiber pastes 2-2 to 2-19 were respectively prepared in the same manner as in Example 2-1, and the pH and surface tension were measured in the same manner as in Example 2-1. did. Next, in the same manner as in Example 2-1, sizing was performed within 12 hours after preparing the fiber paste, and glued yarns 2-2 to 2-19 were obtained, respectively. In addition, the adhesion amount of the fiber sizing agents 2-2 to 2-19 in the respective glued yarns 2-2 to 2-19 was 10% for the polyester filament yarn and 12% for the polyamide filament yarn. The obtained glued yarns 2-2 to 2-19 were each evaluated in the same manner as in Example 2-1, for the conjugation force in the dry type and the wet type, the paste-removing property, and the tackiness. The results are shown in Tables 3 and 4. In addition, the weight ratio in Tables 3 and 4 indicates the weight ratio of each component in the solid content of the fiber paste.

  Moreover, the cross section cut | judged perpendicularly | vertically with respect to the extending | stretching direction of a filament yarn was image | photographed with the electron microscope photograph about both the polyester filament yarn and polyamide filament yarn of the obtained paste yarns 2-1 to 2-19. Calculate the space area N1 inside the glued yarn and the area of the cross-sectional area N2 of the monofilament from the photographed glued yarn cross-sectional image, and measure the percentage (%) of the glued yarn using the above formula (1). did. The results are shown in Tables 3 and 4.

From Tables 3 and 4, the dry-type conjugation force and the wet-type conjugation force are satisfactory in the fiber sizing agents 2-1 to 2-12 of the examples. On the other hand, it is inferior in the fiber paste 2-13 to 2-19 of the comparative example.
Moreover, about the dry paste property and wet paste property, it can be satisfied in the fiber pastes 2-1 to 2-12 of the examples. On the other hand, it is inferior in the fiber paste 2-13 to 2-19 of the comparative example. In particular, with respect to wet conjugation force and wet paste-removing property, it can be satisfied with the fiber pastes 2-1 to 2-12 as examples. It is done.
About adhesion, it can be satisfied in the fiber pastes 2-1 to 2-12 in the examples. On the other hand, it is inferior in the fiber paste 2-13 to 2-19 of the comparative example.
About the space rate, the space rate of the glued yarns 2-1 to 2-12 of the examples was smaller than that of the glued yarns 2-13 to 2-19 of the comparative example.

[Example 3-1] (Practical weaving test)
Using a sizing device (Sizer KS-200 manufactured by Tsudakoma Kogyo Co., Ltd.) under the sizing conditions shown below, the fiber sizing agent 2-1 of Example 2-1 was sized to 22 dtex 20 filament polyester yarn. The obtained glued yarn was prepared as a warp. A 22 dtex 20 filament polyester yarn was prepared as a weft. In Example 3-1, a water jet loom (water jet loom manufactured by Tsudakoma Kogyo Co., Ltd .; loom rotation speed: 650 rpm; warp yarn: 8000; weaving width: 173 cm) was used to weave these warp yarns and weft yarns. A polyester taffeta of 200 mm was manufactured.

<Sizing conditions>
Beam-to-beam method Gluing speed: 100m / min
Non-touch hot air drying temperature: 130 ° C
Touch cylinder drying temperature: 100 ° C
Number of touch cylinders: 3 In addition, the weaving machine operation rate (the total time required for weaving is subtracted from the total time required for weaving by subtracting the time the weaving machine stagnated due to a problem during weaving. % Display of the divided value) was calculated. These results are shown in Table 5.

[Examples 3-2 to 3-12 and Comparative Examples 3-13 to 3-19] (Practical weaving property test)
A polyester taffeta was produced and evaluated by weaving in the same manner as in Example 3-1, except that the fiber paste shown in Tables 5 and 6 was used. The results are shown in Tables 5 and 6.

  From Tables 5 and 6, also in the water jet loom weaving, Examples 3-1 to 3-12 are superior in openability and wrinkle adhesion paste properties to Comparative Examples 3-13 to 3-19. Furthermore, it turns out that 3-1 to 3-12 of an Example is superior to 3-13 to 3-19 of a comparative example also at the point of the operation rate of a weaving machine. In particular, it is a remarkable effect that the operating rate of the weaving machine is improved by 10% or more.

  The fiber sizing agent of the present invention can be suitably used as a warp sizing agent used during weaving.

N1 Spatial area inside glued yarn in the section of glued yarn N2 Cross-sectional area of monofilament in the section of glued yarn S Sizing agent component α Space factor

Claims (11)

A fiber paste,
A neutralized product of a copolymer obtained by copolymerizing a polymerizable component containing (meth) acrylic acid, a (meth) acrylic acid alkyl ester monomer and a styrene monomer, a wax, and water As an essential component,
The total weight ratio of the (meth) acrylic acid, the (meth) acrylic acid ester monomer, and the styrene monomer in the polymerizable component is 95% by weight or more,
The copolymer has a weight average molecular weight of 100,000 to 180,000,
The weight ratio of the neutralized product of the copolymer in the solid content of the fiber paste is 70 to 98% by weight,
The paste for fibers whose surface tension of the aqueous solution which adjusted solid weight concentration contained in this paste to 12% is 30-60 mN / m.   The weight proportion of the (meth) acrylic acid in the polymerizable component is 1 to 30% by weight, the weight proportion of the (meth) acrylic acid alkyl ester monomer is 40 to 95% by weight, and the styrenic The paste for fibers according to claim 1, wherein the monomer has a weight ratio of 1 to 30% by weight. The paste for fibers according to claim 1 or 2 , wherein the acid value of the copolymer is 90 to 200. Further comprising a surfactant, the weight ratio of the wax to total solid content of the textile sizing agent is Ri 1 to 30 wt% der, the weight ratio of the surfactant is 0.5 to 4% by weight, The fiber paste according to any one of claims 1 to 3 . The fiber paste according to any one of claims 1 to 4 , wherein the pH of the aqueous solution in which the weight concentration of solids contained in the fiber paste is adjusted to 1% is in the range of 7 to 10. A glued yarn obtained by sizing the fiber paste according to any one of claims 1 to 5 into a yarn. The glued yarn according to claim 6 , wherein the yarn is a multifilament yarn made of polyamide or polyester. The glued yarn according to claim 6 or 7 , wherein the yarn is a multifilament yarn of 56 dtex or less. The space ratio defined by the following formula (1) is 3% or less when the number of filaments of the multifilament yarn is 3 to 7, and 8% or less when the number of filaments of the multifilament yarn is 8 to 36. The glued yarn according to claim 7 or 8, wherein
Space ratio (%) = ((N1 / (N2 × N3)) × 100 (1)
N1: Spatial area inside the glued yarn in the glued yarn section N2: Cross-sectional area of the monofilament in the glued thread section N3: Number of filaments A method for producing a woven fabric, comprising a step of weaving a warp comprising a glued yarn according to any one of claims 6 to 9 and a weft using a weaving machine. The method for producing a woven fabric according to claim 10 , wherein the loom is a water jet loom.

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