JP5465984B2 - Textile glue - Google Patents

Description

  The present invention relates to a fiber paste and its application. More specifically, the present invention relates to a warp sizing agent that is particularly preferably used in the water jet loom weaving and its application.

Various performances such as adhesive strength, water resistance, abrasion resistance, and scourability are required for the glue used for weaving fibers. In particular, it is important to improve scourability in the scouring and dyeing process after weaving.
Further, when weaving using filament yarn, water jet loom weaving is performed as shown in Patent Document 1 in order to improve the production efficiency.

In the water jet loom weaving, a water-resistant acrylic glue is generally attached to the warp, and the weft is used as it is without the glue treatment. However, in water jet loom weaving, the fallen glue is likely to become wrinkles, that is, a trouble that warps occur in the fabric is likely to occur. Further, the scourability in the scouring and dyeing process after weaving is not satisfactory, and further improvement in scourability is required.
Recently, water jet loom weaving has been accelerated significantly. For this reason, the warp is damaged more by warp, wrinkles, and wrinkles, etc., so that the falling paste (separation of the adhesive film) is further increased, the warp is damaged, and the quality of the fabric is likely to deteriorate. Improvement is desired.

JP 2000-45145 A

  An object of the present invention is to provide a fiber sizing agent that is excellent in scouring properties in a post-processing step after weaving, and can suppress the occurrence of falling paste in the case of water jet loom weaving, and sizing this fiber sizing agent. It is providing the glued thread | yarn obtained by this, and the manufacturing method of the textile fabric performed using this adhesive agent for fibers.

As a result of intensive studies, the present inventors include a neutralized product of a copolymer obtained from a specific polymerizable component such as (meth) acrylic acid, a (meth) acrylamide monomer and a reactive surfactant. The present inventors have found that the above problem can be solved by using a fiber sizing agent, and have reached the present invention.
That is, the fiber paste of the present invention is a neutralization of a copolymer obtained by copolymerizing a polymerizable component containing (meth) acrylic acid, a (meth) acrylamide monomer and a reactive surfactant. And water as essential components.

The polymerizable component preferably further includes a (meth) acrylic acid alkyl ester monomer and / or a styrene monomer. Moreover, it is preferable in the weight ratio of the said reactive surfactant to the said polymeric component that it is 0.1 to 10 weight%.
The fiber sizing agent contains (meth) acrylic acid, an acrylic acid alkyl ester monomer and a methacrylic acid alkyl ester monomer as essential components, and a polymerizable component which may contain a styrene monomer. It is preferable to further contain a neutralized copolymer obtained by polymerization and a wax.

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 a glued yarn obtained by sizing the above-mentioned fiber glue on a thread. The yarn is preferably a filament yarn made of polyamide or polyester.

  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 loom. The loom is preferably a water jet loom.

When the fiber paste of the present invention is used, the scourability is excellent in the post-processing step after weaving. Further, when water jet loom weaving is performed, generation of falling paste can be suppressed.
When the glued yarn of the present invention is used, the scouring property is excellent in the post-processing step after weaving. In addition, when the glued yarn of the present invention is obtained by water jet loom weaving, generation of fallen glue during weaving is suppressed.

  In the method for producing a woven fabric of the present invention, a woven fabric having excellent scourability in the post-processing step is obtained. Moreover, when the manufacturing method of a textile fabric is obtained by water jet loom weaving, generation | occurrence | production of fallen glue at the time of weaving is suppressed.

[Fiber paste]
The paste for fibers of the present invention contains a neutralized copolymer (hereinafter sometimes referred to as paste component A) and water as essential components. The paste component A acts as a component that imparts adhesiveness and conjugation when the fiber paste is applied to the fiber, so-called a paste component.
Hereinafter, the liquid containing the paste component 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 to the paste component liquid or the fiber paste, heating and / or drying is performed. And a method of removing volatile components such as water and a hydrophilic solvent.

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, similarly to the pH described in detail above, the viscosity of the aqueous solution in which the weight concentration of the solids contained in each of the paste component liquid and the fiber paste is adjusted to 20%. Is the value measured at 20 ° C. The method for adjusting the weight concentration to 20% is the same as described above.

Hereinafter, the paste for fibers of the present invention will be described in detail while explaining the method for producing the paste component A contained therein.
The copolymer contains, for example, a (meth) acrylic acid, a (meth) acrylamide monomer and a reactive surfactant, and a polymerizable component that may contain other monomers as necessary ( Hereinafter, this polymerizable component may be referred to as polymerizable component A.) and is produced by a copolymerization step in which emulsion copolymerization is performed in the presence of water. Furthermore, the paste component A contained in the fiber paste of the present invention can be produced through a neutralization step in which an alkaline substance is added to the aqueous dispersion containing the copolymer and neutralized after the copolymerization. Since the obtained paste component A usually coexists with water, the mixture containing the paste component A and water is the fiber paste of the present invention.

The polymerizable component A used in the copolymerization step contains (meth) acrylic acid, a (meth) acrylamide monomer and a reactive surfactant, 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) acrylamide monomer means acrylamide monomer and / or methacrylamide monomer.
(Meth) acrylic acid is a component that imparts water solubility, adhesiveness, and conjugation properties, which are basic physical properties required as a fiber paste.

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 70 to 90% by weight. When the weight ratio of methacrylic acid is too small, the compatibility with other hydrophobic monomers that may be contained in the polymerizable component A is lowered, and emulsion polymerization may be affected. Moreover, when there are too many weight ratios of methacrylic acid, compatibility with hydrophilic monomers, such as the (meth) acrylamide type monomer in polymeric component A, will fall, and the water solubility of the paste for fibers will become low. Sometimes.
The (meth) acrylamide monomer is a component that imparts hydrophilicity, adhesiveness, and conjugation to the fiber paste and enhances scourability in a post-processing step after weaving.

Examples of (meth) acrylamide monomers include acrylamide; methacrylamide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, and the like. N-monosubstituted (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, etc. N, N-disubstituted (meth) acrylamide and the like. These (meth) acrylamide monomers may be used alone or in combination of two or more. Of these, acrylamide and methacrylamide are preferred because of their high hydrophilicity.
The reactive surfactant has a double bond in the molecule and is a polymerizable surfactant. The reactive surfactant is considered to be a component that promotes the removal of paste as an emulsifier in the post-processing step after weaving, and enhances the scourability. In addition, the reactive surfactant also acts as an emulsifier when copolymerizing the polymerizable component A, and the (meth) acrylamide monomer and (meth) acrylic acid and other monomers having high copolymerization reactivity. There is also an advantage that a copolymer having a uniform molecular structure can be obtained.

The reactive surfactant may be any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. However, if the reactive surfactant is an anionic surfactant, Adsorbs to the copolymer obtained by polymerization to give a negative charge, generates repulsive force between the particles made of the copolymer, prevents coalescence of the particles, the dispersion of the reaction mixture during copolymerization This is preferable not only for stabilization but also for stabilizing the dispersion of the fiber paste.
In addition, if an anionic surfactant is present in the ionic fiber paste, the compatibility is enhanced, and in the post-processing step after weaving, the emulsifiability of the fiber paste is enhanced in a scouring bath, which is preferable.

Examples of the reactive surfactant include polyoxyethylene-propenyl alkylphenyl ether sulfate, polyoxyethylene alkylpropylene phenyl ether (AQUALON RN-10, RN-20, RN-30, RN-50 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). ), Polyoxyethylene alkylpropylene phenyl ether sulfate ammonium salt (Daiichi Kogyo Seiyaku Aqualon HS-10, HS-20, BC-05, BC-10, BC-20), sulfosuccinic acid diester ammonium salt (Kao Latemu) S-180A), alkylallylsulfosuccinic acid sodium salt (Eleminol JS-2 manufactured by Sanyo Chemical Industries), α- [1-[(allyloxy) methyl] -ω-polyoxyethylene sulfate ester salt (Adeka Soap SE manufactured by Asahi Denka Kogyo Co., Ltd.) -10N), screw (poly And oxyethylene polycyclic phenyl ether) methacrylate sulfate (Antox MS-60 manufactured by Nippon Emulsifier). These reactive surfactants may be used alone or in combination of two or more. Among these, polyoxyethylene alkylpropylene phenyl ether sulfate ammonium salt and sulfosuccinic acid diester ammonium salt have good compatibility with other hydrophobic monomers that may be contained in polymerizable component A, and are used for fibers. This is preferable in order to stabilize the dispersion of the paste.
Other monomers are not essential in the polymerizable component A, but the fiber paste is given further adhesion and conjugation, and the hardness of the film formed by drying the fiber paste is adjusted. It may be used for the purpose.

Other monomers are roughly classified into hydrophobic monomers and hydrophilic monomers.
Examples of the hydrophobic monomer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, Acrylic acid alkyl ester monomers such as stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, isobornyl acrylate, cyclohexyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid Pentyl, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, 2-chloro methacrylate Methacrylic acid alkyl ester monomers such as chill, phenyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate; styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 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 monomers such as styrene, α-methylstyrene, dimethylstyrene, n-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile , Α-ethoxyacrylonitrile, fuma Nitrile monomers such as nitriles; vinyl halide monomers such as vinyl chloride, vinyl bromide and vinyl fluoride; vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl butyrate .

Examples of the hydrophilic monomer include hydroxyalkyl ester monomers such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and the like. And methacrylic acid hydroxyalkyl ester monomers.
These other monomers may be used alone or in combination of two or more. Among other monomers, hydrophobic monomers such as (meth) acrylic acid alkyl ester monomers and styrene monomers are preferable. Among hydrophobic monomers, alkyl acrylate monomers and styrene monomers are preferred. Acrylic acid alkyl ester monomers are preferred because the homopolymer has a low glass transition point (Tg) and high adhesion and conjugation properties. Preferred examples of the alkyl acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, and the like. Styrenic monomers are preferred because they have good compatibility with the polyester skeleton and high adhesion and conjugation when the fiber paste is used for polyester fibers. Preferred examples of the styrene monomer include styrene.

In the polymerizable component A, the weight ratio of the essential components (meth) acrylic acid, (meth) acrylamide monomer and reactive surfactant, and other monomers included as necessary, There is no particular limitation.
The weight ratio of (meth) acrylic acid in the polymerizable component A is preferably 1 to 20% by weight, more preferably 3 to 15% by weight, and particularly preferably 5 to 12% by weight. When the (meth) acrylic acid is less than 1% by weight, the water solubility of the paste component A is low, and even if it is neutralized in the subsequent neutralization step, it may not be an aqueous solution. On the other hand, when (meth) acrylic acid is more than 20% by weight, the glass transition point (Tg) of the copolymer is high, and there is a tendency that the adhesion and conjugation properties are inferior.

The weight ratio of the (meth) acrylamide monomer in the polymerizable component A is preferably 5 to 50% by weight, more preferably 8 to 30% by weight, and particularly preferably 10 to 20% by weight. When the (meth) acrylamide monomer is less than 5% by weight, the water solubility of the paste component A is low, and the scouring property may be inferior in the post-processing step after weaving. On the other hand, when the (meth) acrylamide monomer is more than 50% by weight, the water-solubility of the paste component A is too high, and when the water jet loom is woven, the fiber paste is formed by drying. The coating film absorbs moisture and tends to soften, and may cause adhesion problems such as poor opening on the weaving machine.
The weight ratio of the reactive surfactant in the polymerizable component A is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, and particularly preferably 1 to 2% by weight. If the reactive surfactant is less than 0.1% by weight, the emulsifiability at the time of copolymerization is inferior, so a uniform copolymer cannot be obtained, and there is a tendency to be inferior in scouring in the post-processing step. This is not preferable. On the other hand, when the reactive surfactant is more than 10% by weight, when weaving, the film formed by drying the fiber paste is plasticized, and adhesion problems such as poor opening on the weaving machine May cause.

When the polymerizable component A contains other monomers, the weight ratio is from 100% by weight to the sum of the weight ratios of (meth) acrylic acid, (meth) acrylamide monomers and reactive surfactants. The remainder after deduction.
Polymerizable component A is essential (meth) acrylic acid, (meth) acrylamide monomer and reactive surfactant, methacrylic acid alkyl ester monomer, acrylic acid alkyl ester monomer and styrene The case where it contains with the at least 1 sort (s) of other monomer chosen from a system-type monomer is preferable.

In addition, the polymerizable component A is essential (meth) acrylic acid, (meth) acrylamide monomers and reactive surfactants, and acrylic acid alkyl ester monomers and styrene as other monomers. The case where at least five components in total with the system monomer are included is more preferable because both the copolymerizability at the time of manufacturing the fiber paste and the scouring property in the post-processing step after weaving are excellent. Moreover, when the fiber paste obtained from the polymerizable component A containing at least the above five components is used for water jet loom weaving, generation of falling paste can be effectively suppressed.
In this case, the weight proportion of the acrylic acid alkyl ester monomer in the polymerizable component A is preferably 20 to 80% by weight, more preferably 40 to 75% by weight, and particularly preferably 50 to 70% by weight. When the acrylic acid alkyl ester monomer is less than 20% by weight, the glass transition point (Tg) of the paste component A is increased and the adhesiveness tends to be inferior. On the other hand, if the alkyl ester monomer content exceeds 80% by weight, the glass transition point (Tg) of the glue component A becomes low, the film becomes soft, and causes adhesion problems such as defective opening on the weaving machine. there is a possibility.

Further, the weight ratio of the styrene monomer in the polymerizable component A is preferably 1 to 25% by weight, more preferably 2 to 15% by weight, and particularly preferably 3 to 10% by weight. When the styrenic monomer is less than 1% by weight, the adhesiveness and conjugation property with the polyester tend to be inferior when the fiber paste is used for the polyester fiber. On the other hand, when the styrene monomer is more than 25% by weight, the glass transition point (Tg) of the paste component A is high, and there is a tendency that the adhesion and conjugation tend to be inferior.
In the copolymerization step, it is preferable to carry out emulsion copolymerization using a hydrophilic solvent, a polymerization initiator, a chain transfer agent and the like in addition to the polymerizable component A and water.

The hydrophilic solvent 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 hydrophilic 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 hydrophilic solvent, Preferably it is 4-18 weight% with respect to the polymeric component A, More preferably, it is 6-15 weight%, Most preferably, it is 8-12 weight%. When the weight ratio of the hydrophilic solvent is less than 4% by weight, the emulsification stability at the time of copolymerization tends to be deteriorated, and the molecular weight of the copolymer is increased, whereby a highly viscous product is produced. In the scouring in the post-processing step, an inferior tendency is seen, which is not preferable. On the other hand, when the weight ratio of the hydrophilic solvent is more than 18% by weight, the molecular weight of the copolymer is lowered, and the adhesiveness and conjugation property of the fiber sizing agent tend to be inferior.
The polymerization initiator is preferably a water-soluble polymerization initiator, for example, persulfates such as ammonium persulfate, potassium persulfate, sodium persulfate; t-butyl hydroperoxide, t-butyl peroxymaleic acid, succinic acid And peroxides such as peroxides; azo compounds such as 2,2′-azobis- (2-amidinopropane dihydrochloride) and the like. The weight ratio of the polymerization initiator is not particularly limited, but is preferably 0.1 to 2% by weight, more preferably 0.3 to 1.5% by weight, and particularly preferably 0.5% with respect to the polymerizable component A. ˜1% 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 2% by weight, the molecular weight of the copolymer is lowered, and the adhesiveness and conjugation property of the fiber paste are inferior.

The chain transfer agent is used for suppressing 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 and lauryl mercaptan; thioglycolic acids such as octyl thioglycolate and 2-ethylhexyl thioglycolate Examples include esters. The weight ratio of the chain transfer agent is preferably 0.1 to 0.8% by weight, more preferably 0.15 to 0.6% by weight, and particularly preferably 0.2 to 0.4% by weight with respect to the polymerizable component A. % By weight. When the weight ratio of the chain transfer agent is less than 0.1% by weight, the molecular weight of the copolymer is increased, a highly viscous product is produced, and this tends to be inferior in scouring in the post-processing step. On the other hand, 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 sizing agent tend to be inferior.
In the copolymerization step, a hydrophilic solvent, a polymerization initiator, a chain transfer agent and the like are used as necessary, and if the polymerizable component A is subjected to emulsion copolymerization in water, the preparation of charged components in advance, There is no limitation in particular about the addition order. As an operation method of the copolymerization step, for example, a mixture 1 containing a polymerizable component A, a hydrophilic solvent, a chain transfer agent and water and a mixture 2 containing a polymerization initiator and water are prepared, and the mixture 1 is mixed. Operation method (1) in which the copolymerization step is carried out by dropping into 2; Operation method (2) in which the polymerization component A, hydrophilic solvent, chain transfer agent, polymerization initiator and water are charged and the copolymerization step is performed in a lump. Mixture (1) containing (meth) acrylic acid, other monomer and chain transfer agent contained as required, (meth) acrylamide monomer, reactive surfactant, hydrophilic solvent, polymerization initiator And a mixture 2 containing water, respectively, and an operation method (3) in which the mixture 1 is dropped into the mixture 2 to perform a copolymerization step. Among these operation methods, in the case of operation method (1), the balance of polymerization reactivity with other polymerizable components A is considered in consideration of the high polymerization reactivity of (meth) acrylamide monomers. This is preferable because the desired uniform copolymer can be easily obtained.

The weight ratio of the polymerizable component A in the mixture 1 is preferably 20 to 80% by weight of the mixture 1, more preferably 30 to 70% by weight, and particularly preferably 40 to 60% by weight. When the polymerizable component A in the mixture 1 is less than 20% by weight, the concentration of the polymerizable component A in the reaction mixture at the time of dropping may be low, the polymerization initiator may be deactivated, and the reaction time may be prolonged. Therefore, it is not preferable. On the other hand, if the polymerizable component A in the mixture 1 is more than 80% by weight, the concentration of the polymerizable component A in the reaction mixture becomes high at the time of dropping, so that the reactivity becomes high and the temperature is rapidly increased. Since it becomes difficult to control a copolymerization reaction, it is not preferable.
The polymerization temperature during emulsion copolymerization is preferably 75 to 90 ° C. The dropping time of the mixture 1 is preferably 60 to 120 minutes, and the aging time after dropping is preferably 60 to 90 minutes.

Next, in the neutralization step, an alkaline substance is added to the aqueous dispersion containing the copolymer to convert the copolymer into a neutralized product. The composition (glue component liquid A) containing the paste component A and water obtained here is the fiber paste of the present invention.
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 20% by weight is prepared, and an aqueous dispersion containing a copolymer is taken over 10 to 30 minutes. It should be dripped. The end point of dropping the alkaline substance can be determined, for example, by changing the aqueous dispersion containing the copolymer to a transparent state.

The pH of the paste component liquid A is preferably 7 to 10, more preferably 7.2 to 9, still more preferably 7.5 to 8.8, and particularly preferably 7.8 to 8.6. When the pH of the paste component liquid A is lower than 7, the water solubility of the paste component A is low, and even if neutralized, it may not become an aqueous solution. On the other hand, when the pH of the paste component liquid A is higher than 10, it is predicted that the viscosity of the paste component A becomes high and the handling becomes difficult.
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 adhesion amount of the paste component A at the time of sizing decreases, and there is a tendency that the adhesion and conjugation tend to be inferior. On the other hand, when the viscosity of the paste component liquid A is larger than 1000 mPa · s, compatibility with the paste component B and other components described later is deteriorated, which is not preferable.

The fiber paste of the present invention is a neutralized product of a copolymer obtained by copolymerizing a polymerizable component A containing (meth) acrylic acid, a (meth) acrylamide monomer and a reactive surfactant. It is a paste for fibers containing (glue component A) and water as essential components. Accordingly, in the fiber sizing agent of the present invention, the sizing component meaning the component that imparts adhesiveness and conjugation when the fiber sizing agent is applied to the fiber is only the fiber sizing agent containing only the sizing component A. Does not mean. The fiber paste of the present invention further contains a paste component other than the paste component A (hereinafter, the other paste component may be referred to as “glue component B”) together with the paste component A and water. Also included.
The paste component B 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, (meth) acrylic acid ester heavy And a (meth) acrylic acid- (meth) acrylic acid ester polymer, a maleic acid polymer and a salt thereof, and the like.

When the paste component contained in the fiber paste of the present invention further includes the paste component B together with the paste component A, the weight ratio of the paste component A and the paste component B (glue component A / glue component B) is particularly limited. However, it is preferably 10/90 to 90/10, more preferably 30/70 to 80/20, and particularly preferably 50/50 to 70/30. If the weight ratio is less than 10/90, the scourability tends to be poor in the post-processing step. On the other hand, if the weight ratio is larger than 90/10, the film formed by drying the fiber paste is likely to absorb moisture and soften, which may cause adhesion problems such as defective opening on the weaving machine. Moreover, in water jet loom weaving, adhesion and conjugation may not be sufficient. The paste component A generally has a high hygroscopic property. The weight ratio is obtained by drying the paste components under the conditions for measuring the solid content shown below, measuring the weight, and calculating the weight ratio thereto.
The fiber paste of the present invention may contain other components such as a wax, a surfactant, an antistatic agent, a penetrating agent, an antifoaming agent, and an antibacterial agent in addition to the paste component. Among other components, it is preferable to contain a wax that imparts flexibility and smoothness to the warp.

Examples of the wax include petroleum waxes such as paraffin wax; synthetic waxes such as polyhydric alcohol fatty acid esters and polyethylene oxide; animal and plant waxes such as carnauba wax, candelilla wax, beeswax and rice wax; mineral waxes and the like. It is done. These waxes may be used alone or in combination of two or more. 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.
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 10% 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.

In view of physical properties such as conjugation during weaving, it is generally preferable that the fiber sizing agent does not contain a surfactant. However, it is preferable to include a surfactant (preferably a nonionic surfactant) in terms of the stability of the wax contained in the fiber paste and the scourability in the post-processing step. In the fiber sizing agent, the surfactant may be blended with the wax as an aqueous dispersion of the wax, or may be blended separately from the wax, but the former is preferred over the latter. For these reasons, when the fiber paste contains a surfactant, the amount is determined in consideration of the balance of physical properties in weaving and post-processing. The weight ratio of the surfactant is preferably 5 to 30% by weight of the wax, more preferably 8 to 25% by weight, and particularly preferably 10 to 20% by weight.
When the paste component contained in the fiber paste of the present invention is a mixture of paste component A and paste component B, and the fiber paste further contains other components, any of the following 1) to 4) A fiber paste may be prepared by mixing.
1) Method of mixing paste component A, paste component B and other components simultaneously or sequentially 2) Method of mixing paste component A and other components prepared in advance with paste component B 3) Prepared in advance Method of mixing the mixture of the paste component B and other components and the paste component A 4) The mixture of the paste component A prepared in advance and some other components, the paste component B prepared in advance and the remaining other components To mix each with a mixture of

Among these methods, the method 3) is preferable. That is, the paste component A is more water-soluble than the conventional fiber paste, and affects the stability with the highly hydrophobic paste component. Therefore, the mixture and the paste component A are mixed immediately before sizing. The method is preferred.
In addition, when the paste component of the fiber paste of the present invention includes paste component A and paste component B, it is better not to leave for a long time before using the fiber paste, considering its dispersion stability, It is desirable to use them by sizing them into a thread form, preferably within 48 hours, more preferably within 24 hours, and particularly preferably within 12 hours after mixing them.

The fiber paste of the present invention requires water. The weight concentration of the solid content contained in the fiber paste is preferably 6 to 14%, more preferably 7 to 13%, and particularly preferably 8 to 12% of the entire fiber paste. If the weight concentration of the solid content is less than 6%, 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, when the weight concentration of the solid content exceeds 14%, the amount of the adhesive for the fiber during sizing increases, which may cause sticking problems such as poor opening on the weaving machine.
The pH of the fiber paste is preferably 7 to 10, more preferably 7.2 to 9, still more preferably 7.5 to 8.8, and particularly preferably 7.8 to 8.6. If the pH of the fiber sizing agent is lower than 7, the water solubility of the sizing component such as the sizing component A is low, and the fiber sizing agent may not become an aqueous solution. On the other hand, if the pH of the fiber sizing agent is higher than 10, the viscosity of the sizing component such as the sizing component A is generally high, and it may be difficult to handle.

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 sizing agent is lower than 10 mPa · s, the adhesion amount of the fiber sizing agent at the time of sizing decreases, and there is a tendency that adhesion and conjugation tend to be inferior. On the other hand, if the viscosity of the fiber sizing agent is greater than 800 mPa · s, the amount of the fiber sizing agent adhering during sizing increases, which may cause adhesion problems such as poor opening on the weaving machine.
When the fiber paste of the present invention is used for water jet loom weaving, the paste component of the fiber paste preferably contains paste component A and paste component B. In that case, if the paste component B is a (meth) acrylic acid polymer or a (meth) acrylic acid- (meth) acrylic acid ester polymer, the adhesive component and the conjugation property are excellent, and fluffing and yarn during weaving This is preferable to prevent cutting. In addition, as other components contained in the fiber glue, the warp yarns are given flexibility and smoothness, and wax, glue yarn peeling and triboelectric charging to cope with adhesion problems such as poor opening during weaving. Anti-static agent for preventing fiber, penetrant for the purpose of assisting the penetration of fiber paste into yarn, antifoaming agent for suppressing foaming of fiber paste, microorganisms of raw machinery manufactured by weaving Antibacterial agents are used to prevent contamination.

When used for water jet loom weaving, the paste component B used here is a (meth) acrylic acid polymer or a neutralized product of a (meth) acrylic acid- (meth) acrylic acid ester polymer. And preferred. The paste component B can be manufactured through, for example, the same copolymerization step and neutralization step as those described above except that a polymerizable component that is not the polymerizable component A is used.
The polymerizable component used in the production of the paste component B is not particularly limited as long as (meth) acrylic acid is essential and does not contain a reactive surfactant, but (meth) acrylic acid is essential, and the reaction. It is preferable that it is a polymerizable component containing no other surfactant and containing the above-mentioned other monomers (hereinafter, this polymerizable component may be referred to as the polymerizable component B). Here, the other monomer is preferably at least one selected from an alkyl acrylate monomer, an alkyl methacrylate monomer, and a styrene monomer. It is more preferable to use a monomer and a methacrylic acid alkyl ester monomer and to use a styrene monomer in combination, and it is particularly preferable to use these three monomers in combination.

The weight ratio of (meth) acrylic acid in the polymerizable component B is preferably 1 to 40% by weight, more preferably 2 to 30% by weight, and particularly preferably 3 to 20% by weight. When the (meth) acrylic acid is less than 1% by weight, the water-solubility of the neutralized product of the (meth) acrylic acid polymer is low, and even if it is neutralized in the subsequent neutralization step, an aqueous solution may not be obtained. On the other hand, when (meth) acrylic acid is more than 40% by weight, the glass transition point (Tg) of the (meth) acrylic acid polymer is high, and there is a tendency that adhesion and conjugation tend to be inferior.
The weight ratio of the acrylic acid alkyl ester monomer in the polymerizable component B is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and particularly preferably 15 to 60% by weight. When the acrylic acid alkyl ester monomer is less than 5% by weight, the glass transition point (Tg) of the neutralized product of the (meth) acrylic acid polymer is increased, and the adhesiveness tends to be inferior. On the other hand, when the acrylic acid alkyl ester monomer content exceeds 80% by weight, the glass transition point (Tg) of the neutralized product of the (meth) acrylic acid polymer becomes low, the film becomes soft, and on the loom There is a possibility of causing adhesion problems such as defective openings.

The weight ratio of the methacrylic acid alkyl ester monomer in the polymerizable component B is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and particularly preferably 15 to 60% by weight. When the amount of the methacrylic acid alkyl ester monomer is less than 5% by weight, the glass transition point (Tg) of the neutralized product of the (meth) acrylic acid polymer is lowered, the film becomes soft, and the opening on the loom It may cause adhesion problems such as defects. On the other hand, when the acrylic acid alkyl ester monomer is more than 80% by weight, the glass transition point (Tg) of the neutralized product of the (meth) acrylic acid polymer tends to be high and the adhesiveness tends to be inferior.
Moreover, the weight ratio of the styrenic monomer in the polymerizable component B is preferably 0 to 20% by weight, more preferably 0.5 to 15% by weight, and particularly preferably 1 to 10% by weight. The styrene monomer may be 0% by weight, but if the amount is small, the adhesiveness and conjugation with the polyester may be inferior when the fiber paste is used for the polyester fiber. On the other hand, when the styrene monomer is more than 20% by weight, the glass transition point (Tg) of the neutralized product of the (meth) acrylic acid polymer is high, and there is a tendency that the adhesion and conjugation tend to be inferior.

In the copolymerization step, it is preferable to carry out the copolymerization using the above-described hydrophilic solvent, polymerization initiator, chain transfer agent and the like in addition to the polymerizable component B and water in the same manner as the method for producing the paste component A. The polymerizable component B is more preferably subjected to solution copolymerization.
When performing solution copolymerization, the type of hydrophilic solvent used is the same as described above. The weight ratio of the hydrophilic solvent is not particularly limited, but is preferably 5 to 35% by weight, more preferably 10 to 30% by weight, and particularly preferably 15 to 25% by weight with respect to the polymerizable component B. When the weight ratio of the hydrophilic solvent is less than 5% by weight, the dispersibility of the hydrophobic monomer tends to be inferior during copolymerization, and the molecular weight of the (meth) acrylic acid polymer increases. This is not preferable because a highly viscous product is formed and a tendency to be inferior is observed in the scouring in the post-processing step. On the other hand, when the weight ratio of the hydrophilic solvent is more than 35% by weight, the molecular weight of the (meth) acrylic acid polymer is lowered, and the adhesiveness and conjugation property of the fiber sizing agent tend to be inferior.

When solution copolymerization is performed, the polymerization initiator to be used is not particularly limited, but an oil-soluble initiator is preferable. Examples of oil-soluble initiators include peroxides such as benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, cumyl peroxyneodecanoate, cumyl peroxy octoate; azobiscyclohexanecarbonyl, azobis Examples thereof include azo compounds such as isobutylamidine hydrochloride and azobisisobutyronitrile. The weight ratio of the polymerization initiator is the same as described above.
When performing solution copolymerization, the type of chain transfer agent used is the same as described above. The weight ratio of the chain transfer agent is not particularly limited, but is preferably 0.03 to 0.4% by weight, more preferably 0.06 to 0.3% by weight, particularly preferably 0, based on the polymerizable component B. 0.08 to 0.2% by weight. When the weight ratio of the chain transfer agent is less than 0.03% by weight, the molecular weight of the (meth) acrylic acid polymer is increased, a highly viscous product is generated, and a tendency to be inferior in scouring in the post-processing step is observed. Therefore, it is not preferable. On the other hand, when the weight ratio of the polymerization initiator is more than 0.4% by weight, the molecular weight of the (meth) acrylic acid polymer is lowered, and the adhesiveness and conjugation property of the fiber sizing agent tend to be inferior.

A neutralization process is also performed similarly to the manufacturing method of the paste component A. It is preferable that the pH of the paste component liquid B including the paste component B thus manufactured is the same as the pH of the paste component liquid A.
Needless to say, when the fiber paste contains paste component A and paste component B, the fiber paste can be used for weaving air jet loom.

[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 filament yarn or a spun yarn (spun yarn). 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 -Polyesters such as naphthalene dicarboxylate; Aliphatic polyamides (nylon) such as poly-ε-capramide and polyhexamethylenediamine adipamide; Polymetaphenylene isophthalamide and copolyparaphenylene-3,4-oxydiphenylene tele Aromatic polyamide (aramid) such as phthalamide can be used. 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.

It is preferable that the yarn is a filament yarn composed of polyester or polyamide because of good adhesion and conjugation with the fiber paste.
Although there is no restriction | limiting in the thickness of a thread | yarn, Preferably, it is 10-75 denier in a filament yarn, and 40-60 counts in a spun yarn (spun yarn).

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 from the warping 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, it is preferably 2 to 15% by weight, more preferably 3 to 3% by weight. 13% by weight, particularly preferably 4 to 11% 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 12% by weight, more preferably 4 to 11% by weight, and particularly preferably 5 to 9% 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 adhesion amount is more than 12% by weight, the adhesion amount is too large, which may cause an adhesion problem such as a defective opening on the weaving machine.
When the yarn is a polyamide filament yarn, the adhesion amount of the fiber sizing agent in the glued yarn is preferably 2 to 12% by weight, more preferably 4 to 11% by weight, particularly preferably 6 to 6%. 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 adhesion amount is more than 12% by weight, the adhesion amount is too large, which may cause an adhesion problem such as a 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. It is preferable that the weaving machine is a water jet loom because generation of falling paste can be suppressed.
For weaving, for example, the warp yarns described above are drawn one by one through the reeds and reeds to prepare the warp yarns and apply them to the 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.

  In the above weaving, for example, when 4,000 to 20,000 warps are prepared and polyester filament yarn or polyamide filament yarn (both 10 to 75 denier, 5 to 70 filament) is used as the weft, polyester taffeta or polyamide The taffeta can be woven from 100 to 200 cm at a weaving speed of 500 to 800 rpm and 50 m as a glance (weaving width: 70 to 200 cm).

The present invention is 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) 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-times 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

(5-1) 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 / d per yarn
(For polyester filament yarn 30 denier 24 filament, 180 g / 20 (= 9 g / piece), for 50 denier 24 filament, 200 g / 20 (= 10 g / piece), for polyamide filament yarn 70 denier 52 filament, 300 g / 20 (= 15g / piece))

(5-2) 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 yarn cracking 4th grade: There is little yarn cracking 3rd grade: There is yarn cracking 2nd grade: There are many yarn cracks 1st grade: There is overall yarn cracking

(6-1) Dry paste properties (evaluation of paste properties in a 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.
Yarn tension: 0.2 to 0.6 g / d per yarn
(Measured with polyester filament yarn 30 denier 24 filament 6g, 50 denier 24 filament 10g, polyamide filament yarn 70 denier 52 filament 15g)

(6-2) 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 of dry and wet paste-fastening properties>
Grade 5: Dropping of glue, no sticking of glue on the comb Grade 4: Dropping of glue, a little sticking of glue on the comb, Grade 3: Dropping of glue, sticking of glue on the comb, Grade 2: Dropping of glue, dropping on the comb Grade 1 with a little amount of glue adhesion: Adhesion of glue and a lot of adhesive paste on comb Dry ligation force and dry defogging properties are evaluated assuming rapier rooms and air jet looms. This is an evaluation that assumes

(7) Wrinkle-adhering paste properties (Evaluation of paste properties in practical weaving tests)
The wrinkle adhesion fallen property (the degree of fallen glue adhering to the wrinkles) at the time of weaving using an actual machine 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.
<Evaluation criteria for wrinkle adhesion and paste>
5th grade: No glue sticking on the heels 4th grade: Little glue sticking on the heels 3rd grade: Some glue sticking on the heels 2nd grade: A little glue sticking on the heels 1st grade: Many glue drops on the heels

(8) Scouring properties Polyester taffeta and polyamide taffeta (10 cm × 10 cm square) are each immersed in a solution in which ion exchange water is added to the fiber paste and the weight concentration of the solid content is adjusted to 10%. Squeeze and dry. The taffeta obtained by drying is scoured for 30 seconds under the following two scouring conditions, and washed with water. Thereafter, the polyester taffeta is immersed in a rhodamine dyeing solution and the polyamide taffeta in a Bokenstein dyeing solution for 15 minutes, washed again with water and dried. The dyed taffeta obtained by drying is visually observed, and the color tone is evaluated according to the following evaluation criteria (1-5 grades). In this evaluation standard, grade 5 is the best and grade 1 is the worst.
(Scouring condition 1)
Scouring liquid: Sodium carbonate 0.5 g / L, POE 10 mol addition nonylphenol ether 0.5 g / L
Scouring temperature: 85 ℃
Bath ratio: 100 times (scouring condition 2)
Scouring liquid: Caustic soda 2 g / L, POE 10 mol addition nonylphenol ether 1 g / L
Scouring temperature: 90 ° C
Bath ratio: 100 times <Evaluation criteria for scourability>
5th grade: No color 4th grade: Slightly red
Level 3: slightly red Level 2: slightly red Level 1: red

[Example 1-1] (Production of glue component A in the specification)
(Copolymerization process)
A polymerizable component (the type and amount are shown in Table 1), 0.3 g of 2-ethylhexyl thioglycolate as a chain transfer agent, 65 g of ion-exchanged water and 8 g of i-propanol as a solvent are mixed with stirring to obtain a mixture 1 It was. A four-necked flask (capacity 1000 mL) equipped with a thermometer, a stirrer, a condenser and a nitrogen gas blowing port was charged with 150 g of ion-exchanged water and heated to 78 ° C. while blowing nitrogen gas. Next, while stirring the charge in the four-necked flask, the mixture 1 was added dropwise, and 0.5 g of ammonium persulfate was further added to the four-necked flask. Dropped into the flask. After completion of the dropwise addition, copolymerization was carried out for 20 minutes, and further 0.2 g of ammonium persulfate was added and post-polymerization aging was carried out for 1 hour to obtain a reaction mixture containing the copolymer.

(Neutralization process)
After the copolymerization, 15 g of ammonia water having a concentration of 13.6% was gradually added to the reaction mixture to neutralize the copolymer (pH 7 to 10), and cooled to room temperature. Thereafter, by adding ion-exchanged water and adjusting so that the weight concentration of the solids contained in the paste component liquid is 20%, a paste component liquid A1 containing the paste component A1 made of a neutralized product of the copolymer is obtained. Obtained.
The viscosity of the aqueous solution adjusted to a weight concentration of 20% of the solid content contained in the paste component liquid A1 (viscosity of the paste component liquid A1) was 112 mPa · s. The pH of the aqueous solution in which the weight concentration of the solid content contained in the paste component liquid A1 was adjusted to 1% (pH of the paste component liquid A1) was 8.0. For dilution for pH measurement, ion-exchanged water was used as in the viscosity measurement.

[Examples 1-2 to 1-3] (Production of glue component A in the specification)
Except for changing the polymerizable component to the type and amount shown in Table 1, the copolymerization step and the neutralization step are performed in the same manner as in Example 1-1, and ion exchange water is added to the paste component including the paste component A2. Liquid A2 and paste component liquid A3 containing paste component A3 were obtained, respectively. The weight concentration of solids contained in each paste component liquid was 20%.
Table 1 shows the viscosity and pH of the paste component liquids A2 to A3 measured in the same manner as in Example 1-1.

[Comparative Example 1-1] (Production of glue component B in the specification)
The kind and amount of polymerizable components shown in Table 1 and 30 g of soft water were added to the four-necked flask used in Example 1 above. Next, 0.1 g of 2-ethylhexyl thioglycolate as a chain transfer agent, 20 g of i-propanol as a solvent and 1 g of benzoyl peroxide are further added to a four-necked flask, mixed with stirring, and copolymerized at 82 ° C. for 5 hours. To obtain a reaction mixture containing a copolymer.
After the copolymerization, 15 g of aqueous ammonia having a concentration of 13.6% was gradually added to the reaction mixture to neutralize, cooled to room temperature, and ion exchange water was added to obtain paste component liquid B1 containing paste component B1. The weight concentration of the solid content contained in the paste component liquid B1 was 20%.

  In the same manner as in Example 1-1, the viscosity and pH of the paste component liquid B1 were measured. The viscosity of the paste component liquid B1 was 152 mPa · s, and the pH of the paste component liquid B1 was 8.2.

[Comparative Example 1-2] (Production of glue component B in the specification produced without using a reactive surfactant)
The polymerizable components were changed to the types and amounts shown in Table 1, and the copolymerization step and the neutralization step were performed in the same manner as in Example 1-1 except that no reactive surfactant was used, and ion-exchanged water was added. Thus, paste component liquid B2 containing paste component B2 was obtained. The weight concentration of the solid content contained in the paste component liquid B2 was 20%. Table 1 shows the viscosity and pH of the paste component liquid B2 measured in the same manner as in Example 1-1.
Since the paste component liquids A1 to A3 include the paste component A and water, all are examples of the fiber paste. Moreover, since the paste component liquid B1 and the paste component liquid B2 do not contain the paste component A, both are comparative examples of the fiber paste.

  In order to comprehensively judge the physical properties when used by being attached to fibers, in the following Examples and Comparative Examples, various physical properties of a fiber paste containing a wax as an aqueous dispersion were examined.

[Example 2-1]
Paste component liquid A1 containing paste component A1 obtained in Example 1-1, and an aqueous dispersion of wax obtained by emulsifying paraffin wax and ester wax with a nonionic surfactant (sizing wax K-2, Matsumoto Yushi Seiyaku Co., Ltd.) )) Was mixed to prepare a fiber paste 1 having a weight ratio of paste component A1 / wax / surfactant = 96 / 3.5 / 0.5.
The pH of the aqueous solution in which the weight concentration of the solid content contained in the fiber paste 1 was adjusted to 1% (pH of the fiber paste 1) was measured, and the results are shown in Table 2.

Within 12 hours from the preparation of the fiber paste 1, the polyester filament yarn (30 denier 24 filament), the polyester filament yarn (50 denier 24 filament) and the polyamide filament yarn 70 denier 52 filament, A sizing machine was used under the sizing conditions shown below to attach the fiber sizing agent 1 to obtain a glued yarn 1. The adhesion amount of the fiber paste 1 was 5% for the polyester filament yarn and 8% for the polyamide filament yarn.
<Sizing conditions>
Beam-to-beam method Gluing speed: 80m / min
Non-touch hot air drying temperature: 130 ° C (polyester yarn), 110 ° C (polyamide yarn)
Touch cylinder drying temperature: 100 ° C
Number of touch cylinders: 7 The obtained glued yarn 1 was evaluated for dry and wet conjugation force and adhesive properties. The scourability of the fiber paste 1 was evaluated using a polyester taffeta and a polyamide taffeta. The results are shown in Table 2.

[Examples 2-2 to 2-6 and Comparative Examples 2-1 to 2-3]
In Example 2-1, the same as in Example 2-1, except that the type of paste component used, the weight ratio of the paste component, the wax, and the surfactant are changed to those shown in Table 2, respectively. Fiber pastes 2 to 9 were prepared, and the pH was measured in the same manner as in Example 2-1. Next, in the same manner as in Example 2-1, sizing was performed within 12 hours after the preparation of the fiber paste, to obtain glued yarns 2 to 9, and the conjugation force, sizing properties and scouring properties were obtained. evaluated. The results are shown in Table 2.
Here, in Example 2-2 (fiber paste 2), Example 2-4 (fiber paste 4) and Example 2-6 (fiber paste 6), paste component A and paste component B It is a fiber sizing agent having both of these as a paste component. In these examples, since the paste component A is included as the paste component, both are examples. In each of these examples, a mixture in which the paste component liquid B and the aqueous dispersion of wax were mixed in advance was prepared, and then the mixture and the paste component liquid A were mixed to prepare a fiber paste. .

In Example 2-3 (fiber paste 3) and Example 2-5 (fiber paste 5), it is a fiber paste containing only the paste component A as a paste component.
Comparative Example 2-1 (fiber paste 7) is a fiber paste containing only the paste component B as a paste component. Comparative Example 2-2 (fiber paste 8) is a fiber paste containing only the paste component B as the paste component. Comparative Example 2-3 (fiber paste 9) is a fiber paste containing only paste component B (consisting of two types of paste component B1 and paste component B2) as a paste component.

  “0/36 + 60 / 3.5 / 0.5” is listed in the column of the weight ratio of Comparative Example 2-3 in Table 2. Here, “36 + 60” indicates that the total weight ratio of the paste component B is 96. Of these, the paste component B1 is 36 and the paste component B2 is 60.

From Table 2, the scourability is excellent in the fiber pastes 1 to 6 as examples, but is inferior in the fiber pastes 7 to 9 as comparative examples.
About the dry-type conjugation force and dry-type paste-falling property, it can be satisfied in the fiber pastes 1 to 6 as examples. However, the fiber paste 7 as a comparative example is a little inferior.

Moreover, about the wet conjugation force, it can be satisfied in the fiber pastes 1 to 6 as examples. With regard to the wet sizing property, the fiber sizing agents 1 to 6 as examples are excellent because the detachment of the paste and the sizing agent do not adhere to the comb. However, the fiber paste 7 as a comparative example is inferior.
Therefore, when water jet loom weaving is performed using the fiber sizing agents 1 to 6, excellent results with no falling paste can be obtained.

[Examples 3-1 to 3-2] (Practical weaving test)
It is obtained by sizing the fiber paste 2 of Example 2-2 to 50 denier 24 filament polyester yarn using a sizing device (Sizer KS-200 manufactured by Tsudakoma Kogyo Co., Ltd.) under the sizing conditions shown below. A glued yarn was prepared as a warp. A 50 denier 36 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: 8000; weaving width: 173 cm) was used, and in Example 3-2 an air jet loom (Tsuda These warp yarns and weft yarns were woven using an air jet loom manufactured by Koma Kogyo Co., Ltd .; loom rotation speed: 600 rpm; warp yarn: 8000 pieces; weaving width: 173 cm) to produce a 200-liter polyester taffeta.
<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

Next, a polyester taffeta 10 cm × 10 cm square after weaving was prepared, and scouring was performed under the scouring condition 1 of the scourability measuring method, and the scourability was evaluated.
In addition, weaving machine operation rate (% of the total time required for weaving, subtracting the time the weaving machine stagnated due to trouble during weaving, and dividing that time by the total time required for weaving. ) Was calculated. These results are shown in Table 3.

[Comparative Examples 3-1 to 3-2] (Practical weaving test)
Example 3-1 and Example 3-2 except that the fiber glue 2 of Example 2-2 is changed to the fiber glue 7 of Comparative Example 2-2 in Example 3-1 and Example 3-2. The polyester taffeta was produced and evaluated by weaving in the same manner as in 3-2. The results are shown in Table 3.

表３から、ウォータージェットルーム製織およびエアージェットルーム製織のいずれにおいても、繊維用糊剤２は、繊維用糊剤７よりも精練性に優れていることが分かる。また、ウォータージェットルーム製織においては、繊維用糊剤２は、繊維用糊剤７よりも筬付着落糊性および稼働率の点でも優れていることが分かる。特に、製織機の稼働率が７％も向上することは顕著な効果である。

From Table 3, it can be seen that the fiber sizing agent 2 is superior to the fiber sizing agent 7 in both the water jet loom weaving and the air jet loom weaving. Moreover, in the water jet loom weaving, it can be seen that the fiber paste 2 is superior to the fiber paste 7 in terms of wrinkle adhesion and adhesiveness and operation rate. In particular, it is a remarkable effect that the operating rate of the weaving machine is improved by 7%.

Claims (10)

A paste for fibers attached to yarns used for weaving,
A neutralized product of a copolymer obtained by copolymerizing a polymerizable component containing (meth) acrylic acid, a (meth) acrylamide monomer and a reactive surfactant, and water as essential components. Textile glue.   The paste for fibers according to claim 1, wherein the polymerizable component further contains a (meth) acrylic acid alkyl ester monomer and / or a styrene monomer.   The paste for fibers according to claim 1 or 2, wherein a weight ratio of the reactive surfactant in the polymerizable component is 0.1 to 10% by weight. It further includes a neutralized product of a copolymer obtained by copolymerizing a polymerizable component essentially containing (meth) acrylic acid, an acrylic acid alkyl ester monomer and a methacrylic acid alkyl ester monomer, Item 4. A paste for fibers according to any one of Items 1 to 3. Further seen containing a wax, pH of the aqueous solution was adjusted concentration by weight of solids contained in the textile sizing agent to 1% is in the range of 7-10, for fiber according to claim 1 Glue. The paste for fibers according to any one of claims 1 to 5, wherein the reactive surfactant is a reactive anionic surfactant .   Glued yarn formed by sizing the fiber paste according to any one of claims 1 to 6 into a yarn.   The glued yarn according to claim 7, wherein the yarn is a filament yarn composed of polyamide or polyester.   A method for producing a woven fabric, comprising a step of weaving a warp comprising the glued yarn according to claim 7 or 8 and a weft using a weaving machine.   The method for manufacturing a woven fabric according to claim 9, wherein the loom is a water jet loom.