JP5689002B2 - Manufacturing method of fiber paste and its application - Google Patents

Description

  The present invention relates to a method for producing a fiber paste and its application. More specifically, the present invention relates to a method for producing a warp sizing agent that is particularly preferably used during weaving and its application.

  Various performances such as adhesiveness, 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, weaving is performed using a loom in order to improve the production efficiency (for example, Patent Document 1).

In 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, when a loom is used, the glue that has fallen off is creased, that is, a trouble that warps occur in the fabric tends to occur. Further, the scourability in the scouring and dyeing process after weaving is not satisfactory, and further improvement in scourability is required.
In addition, due to the high functionality of the yarn, the resulting change in the cross-sectional shape of the yarn, and the diversification of the yarn oil agent, the acrylic glue generally used is poor in adhesiveness and is troublesome, resulting in an improvement. Is desired.

JP 2000-45145 A

  The object of the present invention is to provide a method for producing a fiber sizing agent that is excellent in scouring properties in a post-processing step after weaving, can impart adhesiveness enough to suppress warp breakage, and can suppress the occurrence of fallen paste, An object of the present invention is to provide a glued yarn obtained by sizing the fiber paste obtained by this production method and a method for producing a woven fabric performed using the fiber paste.

  As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a fiber paste obtained by a specific production method, and have reached the present invention. Specifically, in the method for producing a fiber paste containing a copolymer neutralized product, when a specific polymerizable component containing a styrene monomer is copolymerized by emulsion polymerization, warp Adhesiveness sufficient to suppress cutting can be imparted, and generation of falling paste can be suppressed. Furthermore, compared with the case where the polymerizable component is copolymerized by solution polymerization, the scouring property is markedly improved in the post-processing step after weaving. I found that it is excellent.

  That is, this invention is a manufacturing method of the paste for fibers containing the neutralized product of a copolymer, Comprising: (meth) acrylic acid, (meth) acrylic acid ester monomer, and styrene monomer And a neutralization step for neutralizing the copolymer obtained in the copolymerization step, and a neutralizing step for neutralizing the copolymer obtained in the copolymerization step.

  The weight ratio of the styrene monomer in the polymerizable component is preferably 5 to 40% by weight, and the weight ratio of the (meth) acrylic acid is preferably 16 to 30% by weight.

  The weight average molecular weight of the copolymer neutralized product is preferably 10,000 to 200,000.

  The copolymerization step is preferably a step of emulsifying and dispersing the polymerizable component in the presence of a water-based medium and an emulsifier, and copolymerizing the polymerizable component.

  The method for producing a fiber paste of the present invention preferably further includes a step of adding a wax.

  The fiber sizing agent of the present invention is a fiber sizing agent obtained by the above production method, and the pH of the aqueous solution in which the weight concentration of the solid content contained in the fiber sizing agent is adjusted to 1% is 7 to It is in the range of 10.

  Further, the glued yarn of the present invention is formed by sizing a fiber paste obtained by the above production method into a thread.

  The method for producing a woven fabric of the present invention includes a step of weaving the warp yarn and the weft yarn made of the above-mentioned glued yarn 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.

When the fiber paste obtained by the production method of the present invention is used, the scourability is excellent in the post-processing step after weaving. Moreover, the adhesiveness which suppresses the warp breakage at the time of weaving can be provided, and generation | occurrence | production of fallen glue 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. Moreover, warp breakage during weaving is suppressed, and 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, warp breakage during weaving is suppressed, and generation of fallen glue during weaving is suppressed.

[Production method of fiber paste]
The present invention is a method for producing a fiber paste containing a copolymer neutralized product (hereinafter sometimes referred to as paste component A). 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.
Such a liquid containing the paste component A and water is hereinafter 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 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, 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 25%. Is the value measured at 20 ° C. The method for adjusting the weight concentration to 25% is the same as described above.

Hereinafter, the manufacturing method of the fiber paste containing the neutralized product (glue component A) of the copolymer of the present invention will be described in detail.
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. It 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 emulsion 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. Thus, the obtained paste component A coexists with water. The mixture containing s becomes a paste for fibers.

  The polymerizable component a used in the copolymerization step contains a polymerizable component containing (meth) acrylic acid, a (meth) acrylic acid ester monomer and a styrene monomer, and contains other monomers. You may do it. 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 monomer. Means the body.

(Meth) acrylic acid is a component that imparts water solubility, adhesiveness, and conjugation, which are basic physical properties required as a fiber paste, and improves scourability in a post-processing step after weaving.
The weight ratio of methacrylic acid in (meth) acrylic acid is preferably 20 to 100% by weight, more preferably 50 to 100% by weight, and particularly preferably 70 to 100% 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, making it difficult to obtain a uniform polymer.

  A (meth) acrylic acid ester monomer is a component that imparts adhesiveness and conjugation properties required as a fiber paste. 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, mellicinyl acrylate, palmitole acrylate Nyl, oleyl acrylate, linoleyl acrylate, linolenyl acrylate, phenyl acrylate, isobornyl acrylate, cyclohexyl acrylate, and other acrylic ester monomers; 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, melitynyl methacrylate, palmitoleyl methacrylate, oleyl methacrylate, linoleyl methacrylate, linolenyl methacrylate, phenyl methacrylate, isobornyl methacrylate And methacrylic acid ester monomers such as cyclohexyl methacrylate.

  The styrene monomer is a component that imparts adhesiveness and conjugation properties as a fiber paste, and suppresses the occurrence of falling paste. In particular, it is more effective in the case of filament yarns composed of polyester having an aromatic skeleton. Examples of the styrene 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.

Other monomers are not essential in the polymerizable component a, but they give one layer of adhesiveness and conjugation to the fiber paste and adjust the hardness of the film formed by drying the fiber paste. It may be used for the purpose.
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-dihydroxyproacrylate Hydroxyalkyl acrylate monomers such as pills, 2,3-dihydroxybutyl acrylate, 2,4-dihydroxybutyl acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, polybutylene glycol acrylate; 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 monomers such as 2,4-dihydroxybutyl phosphate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, polybutylene glycol methacrylate; vinyl halides such as vinyl chloride, vinyl bromide, and vinyl fluoride Monomeric monomers; vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl butyrate.
These other monomers may be used alone or in combination of two or more.

  In polymerizable component a, the essential component (meth) acrylic acid, (meth) acrylic acid ester monomer, polymerizable component containing a styrene monomer, and other single quantities 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.

  From the point of giving more adhesiveness to suppress warp breakage and further suppressing the occurrence of falling paste, the weight ratio of the styrene monomer in the polymerizable component a is preferably 5 to 40% by weight, Preferably it is 10 to 35 weight%, Most preferably, it is 15 to 30 weight%. When the styrene monomer is less than 5% by weight, the adhesiveness of the paste 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 40% by weight, the film forming property of the paste component A is poor, and the falling paste may be amplified.

  Furthermore, when the weight ratio of the styrene monomer is the above, the weight ratio of (meth) acrylic acid in the polymerizable component a is preferably 16 to 30% by weight, more preferably 18 to 28% by weight, Most preferably, it is 20-25 weight%. When the (meth) acrylic acid is less than 16% by weight, the water-solubility of the paste component A is low, and even if it is neutralized in a later neutralization step, it may not become an aqueous solution. On the other hand, when (meth) acrylic acid is more than 30% by weight, the viscosity of the neutralized product tends to increase and handling tends to be difficult.

  The weight ratio of the (meth) acrylic acid ester monomer in the polymerizable component a is preferably 10 to 94% by weight, more preferably 22 to 85% by weight, and particularly preferably 40 to 80% by weight. When the (meth) acrylic acid ester monomer is less than 20% by weight, the adhesiveness tends to be inferior. On the other hand, if the (meth) acrylic acid ester monomer exceeds 94% by weight, the adhesiveness becomes excessively strong, which may cause sticking problems such as poor opening on the weaving machine.

  The weight proportion of the (meth) acrylic acid ester monomer in the polymerizable component a is the remainder obtained by subtracting the sum of the weight proportions of (meth) acrylic acid and styrene monomer from 100% by weight. In the case where the monomer is contained, it is the remainder obtained by further subtracting this weight ratio.

  The total weight proportion of (meth) acrylic acid, (meth) acrylic acid ester monomer and styrene monomer in the polymerizable component a is preferably 90% by weight or more, more preferably 92% by weight or more, Especially preferably, it is 94 weight% or more. When the polymerization ratio of the essential monomer is less than 90% by weight, the scourability may be poor and the adhesiveness may be insufficient.

  The copolymerization step is a step of copolymerizing the polymerizable component a by emulsion polymerization. In this way, in the post-processing step after weaving, if it is a fiber paste containing a copolymer neutralized product obtained by copolymerizing the polymerizable component a by emulsion polymerization and undergoing a neutralization step described later, Compared with the case of copolymerization by solution polymerization, the scourability is remarkably excellent. In particular, when the weight ratio of the styrene monomer and (meth) acrylic acid in the polymerizable component a is as described above, the effect is more exhibited. The reason is not clear, but it can be considered as follows. When the polymerizable component a is copolymerized by the solution polymerization method, the polymerization rate of the styrene monomer is greatly different from that of the (meth) acrylic acid and (meth) acrylic acid ester monomers. This will form a heterogeneous copolymer with many monomers. As a result, there is a possibility that the appearance of the paste component becomes cloudy or causes a problem of poor scouring. On the other hand, in the copolymerization by the emulsion polymerization method, since the amount of monomer in the micelle can be controlled, homopolymerization of the styrene monomer can be suppressed. In particular, this effect is more exhibited when the weight ratio of the styrene monomer and (meth) acrylic acid in the polymerizable component a is as described above.

  In the copolymerization step, in addition to the polymerizable component a, a medium such as water or a solvent, an emulsifier, a polymerization initiator, a chain transfer agent, a reactive surfactant, and the like are used, but if the polymerization method is carried out by emulsion polymerization, There is no particular limitation. Here, emulsion polymerization is one of radical polymerization, and a medium such as water or a solvent is mixed with a polymerizable component (monomer) that is hardly soluble in the medium, and the polymerizable component is emulsified and dispersed in the medium. This is a polymerization method performed using a polymerization initiator. By such emulsion polymerization, a so-called emulsion in which the copolymer is dispersed in a medium such as water can be obtained. Usually, a method of polymerizing a monomer that is hardly soluble in water using water as a medium is common, and the obtained emulsion is sometimes called an O / W type emulsion or a W / W type emulsion. In addition, there is a method in which a solvent is used as a medium and a monomer that is hardly soluble in the solvent is polymerized (W / O emulsion, O / O emulsion). That is, in the present invention, any polymerization method capable of obtaining any emulsion may be used. Further, as a polymerization method similar to emulsion polymerization, methods such as miniemulsion polymerization, microemulsion polymerization, soap-free emulsion polymerization, and suspension polymerization are known, and these methods are also included in the emulsion polymerization referred to in the present invention. .

  The medium used in the present invention may be any medium as long as the polymerizable component a is insoluble or hardly soluble. Examples of the medium include water and a solvent described later, but a medium mainly composed of water is preferable from the viewpoint of workability such as removal of the solvent. The weight ratio of water in the medium is preferably 60% by weight or more, more preferably 75% by weight or more, and further preferably 90% by weight or more. If it is less than 60% by weight, the weight average molecular weight of the copolymer may be lowered.

  The solvent as a medium may be used for the purpose of controlling the polymerization temperature 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. There is no particular limitation on the weight ratio of the solvent.

  The emulsifier is not particularly limited as long as the polymerization component a can be emulsified and dispersed in the medium, and examples thereof include an anionic surfactant or a nonionic surfactant, and these may be used alone or in combination. Can do. Moreover, an amphoteric surfactant and a cationic surfactant can also be used as needed.

  Examples of the anionic surfactant include alkyl sulfates, alkylaryl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkylaryl ether sulfates (polyoxyalkylene tristyryl phenyl ether sulfates, polyoxyalkyls). Range styryl phenyl ether sulfate, polyoxyalkylene styryl phenyl ether sulfate, polyoxyalkylene nonyl phenyl ether sulfate, etc.), polyoxyalkylene alkyl polyhydric alcohol ether sulfate, alkyl sulfonate, alkyl aryl sulfonate (dodecyl) Benzene sulfonate, xylene sulfonate, toluene sulfonate, cumene sulfonate, etc.), alkylaryl disulfonate (alkyl diphenyl disulfonate, etc.) Alkyl sulfosuccinate, alkyl phosphate, alkyl aryl phosphate, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkyl aryl ether phosphate, polyoxyalkylene alkyl polyhydric alcohol ether phosphate, aromatic sulfone Examples include acid formalin condensate salts (naphthalene sulfonate formalin condensate salts, etc.), polyoxyalkylene alkyl ether carboxylates, polycarboxylates, funnel oil, lignin sulfonates and the like. When the anionic surfactant is a salt, examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts. These anionic surfactants may be used alone or in combination of two or more. Among these, alkylbenzene sulfonate, alkyl sulfate, polyoxyethylene alkyl (or alkylphenyl) ether sulfate, and the like are preferable.

  Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl aryl ether (polyoxyalkylene tristyryl phenyl ether, polyoxyalkylene distyryl phenyl ether, polyoxyalkylene styryl phenyl ether, polyoxyalkylene. Nonylphenyl ether, etc.), polyoxyalkylene alkylamine, polyoxyalkylene alkylamide, polyoxyalkylene fatty acid ester, polyoxyalkylene castor oil ether, polyoxyalkylene hydrogenated castor oil ether, polyoxyalkylene polyhydric alcohol ether, etc. . These nonionic surfactants may be used alone or in combination of two or more. Among these, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, and the like are preferable.

  Examples of amphoteric surfactants include alkylamino fatty acid salts, alkylbetaines, and alkylamine oxides. Among these, lauryl betaine is preferable.

  Examples of the cationic emulsifier include alkyl trimethyl ammonium salt and dialkyl dimethyl ammonium salt.

  The weight ratio of the emulsifier is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight, and particularly preferably 0.5 to 3% by weight with respect to the polymerizable component a. It is. If the weight ratio of the emulsifier is less than 0.1% by weight, it may be difficult to dissolve in water after neutralization due to poor emulsification during polymerization. On the other hand, when the weight ratio of the emulsifier is 10% by weight or more, the water resistance of the film is inferior, and it is not practical as a paste for water jet loom.

  Although it does not specifically limit as a polymerization initiator, What can melt | dissolve in a medium is preferable, and a water-soluble polymerization initiator, an oil-soluble polymerization initiator, etc. can be mentioned. 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 polymerization initiator include peroxides such as benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, cumyl peroxyneodecanoate, cumyl peroxyoctoate; azobiscyclohexanecarbonyl, azo Examples thereof include azo compounds such as bisisobutylamidine 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, and particularly preferably 0.5% with respect to the polymerizable component a. ~ 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.

  As a polymerization initiation method, a method in which an oxidizing agent and a reducing agent are used and decomposed in a redox manner can also be used. A known redox catalyst can be used as the oxidizing agent and the reducing agent. For example, examples of the oxidizing agent include potassium persulfate, sodium persulfate, ammonium persulfate, and sodium chlorite, and ammonium persulfate is particularly preferable. On the other hand, examples of the reducing agent include sodium hydrogen sulfite, ammonium hydrogen sulfite, and alkyl mercaptans, and sodium hydrogen sulfite and ammonium hydrogen sulfite are particularly preferable.

The weight ratio of the oxidizing agent is not particularly limited, but is preferably 0.05 to 3% by weight, more preferably 0.1 to 2.5% by weight, and particularly preferably 0.5 to 3% by weight with respect to the polymerizable component a. 2% by weight. When the weight ratio of the oxidizer is less than 0.05% by weight, the molecular weight of the copolymer is increased, so that a highly viscous product is generated, and this tends to be inferior in scouring in the post-processing step. . On the other hand, when the weight ratio of the oxidizing agent 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 apt to be inferior.
Although there is no limitation in particular about the weight ratio of a reducing agent, Preferably it is 0.05 to 4 weight% with respect to the polymeric component a, More preferably, it is 0.1 to 3 weight%. If the weight ratio of the reducing agent is less than 0.05% by weight, the reaction time is long or the reaction does not proceed, which is not preferable. On the other hand, if the reducing agent exceeds 4% by weight, the water resistance of the film is lowered, which is not preferable.

  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.

  When the chain transfer agent is used, the weight ratio of the chain transfer agent is preferably 2.0% by weight or less, more preferably 1.5% by weight or less, and particularly preferably 1.0% by weight with respect to the polymerizable component a. % By weight or less. When the weight ratio of the chain transfer agent is more than 2.0% by weight, the molecular weight of the copolymer is lowered, and the adhesiveness and conjugation property of the fiber paste are inferior.

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.

  When the reactive surfactant is used, the weight ratio of the reactive surfactant is preferably 10% by weight or less, more preferably 8% by weight or less, and particularly preferably 5% by weight with respect to the polymerizable component a. It is as follows.

  The copolymerization step is a step of emulsifying and dispersing the polymerizable component a in the presence of a water-based medium and an emulsifier from the viewpoint of workability such as solvent removal, and copolymerizing the polymerizable component. preferable. Furthermore, it is preferably a step of emulsifying and dispersing the polymerizable component a in the presence of a water-based medium and an emulsifier, and copolymerizing the polymerizable component using a water-soluble polymerization initiator.

  The polymerization temperature and polymerization time for emulsion polymerization are not particularly limited, and can be performed under the conditions applied to the system. Examples of the copolymerization step include the following methods 1) to 6).

  1) First, the polymerizable component a is stirred and mixed to prepare a mixture. Separately, ion-exchanged water, an emulsifier, a water-soluble polymerization initiator, and a chain transfer agent as necessary are mixed and stirred to prepare a system heated to a predetermined temperature, and the above mixture is added to the system. The mixture is added with stirring over a predetermined time, and further stirred for a predetermined time after completion of the addition, whereby a copolymer can be obtained. Moreover, it can also superpose | polymerize by making a water-soluble polymerization initiator into aqueous solution and dripping for a predetermined time.

  2) Ion-exchanged water, an emulsifier, a water-soluble polymerization initiator, a polymerizable component a, and, if necessary, a chain transfer agent are stirred and mixed to prepare an emulsion. A copolymer can be obtained by heating the emulsion to a predetermined temperature and continuing stirring for a predetermined time. As a similar polymerization method, a water-soluble polymerization initiator can be used as an aqueous solution and dropped by dropping for a predetermined time.

  3) Ion-exchanged water, emulsifier, oxidizing agent, reducing agent, polymerizable component a and, if necessary, a chain transfer agent are stirred and mixed to prepare an emulsion. A copolymer can be obtained by heating the emulsion to a predetermined temperature and continuing stirring for a predetermined time. As a similar polymerization method, an oxidizing agent and / or a reducing agent can be used as an aqueous solution and dropped by dropping for a predetermined time.

  4) Ion-exchanged water, an emulsifier, a water-soluble polymerization initiator, a part of the polymerizable component a, and a chain transfer agent as necessary are stirred and mixed to prepare an emulsion. The emulsion is heated to a predetermined temperature, and stirred for a predetermined time to perform initial polymerization. A copolymer can be obtained by dropping the remaining polymerizable component a into this system under stirring for a predetermined time. As a similar polymerization method, a water-soluble polymerization initiator can be used as an aqueous solution and dropped by dropping for a predetermined time.

  5) Ion-exchanged water, a reactive surfactant, a water-soluble polymerization initiator, a polymerizable component a, and a chain transfer agent as required are stirred and mixed to prepare an emulsion. A copolymer can be obtained by heating the emulsion to a predetermined temperature and continuing stirring for a predetermined time. As a similar polymerization method, an emulsion is prepared by stirring and mixing a polymerizable component a, a reactive surfactant, and a portion of ion-exchanged water, and ion-exchanged water in which a water-soluble polymerization initiator is dissolved at a predetermined temperature. It can also superpose | polymerize by making it dripped at the system heated up.

  6) Ion-exchanged water, reactive surfactant, oil-soluble polymerization initiator, polymerizable component a, and, if necessary, a chain transfer agent are stirred and mixed to prepare an emulsion. A copolymer can be obtained by heating the emulsion to a predetermined temperature and continuing stirring for a predetermined time. As a similar polymerization method, an ion exchange is carried out by mixing a polymerizable component a, an oil-soluble polymerization initiator, a reactive surfactant, and a part of ion-exchanged water with stirring to prepare an emulsion and raising the temperature to a predetermined temperature. It can also superpose | polymerize by making it dripped at water.

  In any of the above methods, the acid component of the polymerizable component a can be neutralized with an alkali component and copolymerized.

  The acid value of the copolymer obtained in the copolymerization step is preferably 100 to 230, more preferably 120 to 210, and still more preferably 130 to 190. When the acid value is less than 100, the water-solubility of the paste component A is low, and even if it is neutralized in a later neutralization step, it may not become an aqueous solution. On the other hand, when it exceeds 230, the viscosity of the neutralized product tends to increase and handling tends to be difficult. 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. The obtained composition containing paste component A and water (paste component liquid A) 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 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 of 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 (fiber paste) 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%, the water solubility of the paste component A is so low that it may not be an aqueous solution. 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. 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, the viscosity of the paste component A becomes high, and handling becomes difficult, which is not preferable.

  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, handling becomes difficult, which is not preferable.

  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 this average molecular weight. For example, number average molecular weight, weight average molecular weight, z 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 10,000 to 200,000, more preferably 20,000 to 150,000, and particularly preferably 30,000 to 100,000. When the weight average molecular weight exceeds 200,000, refining may be poor. On the other hand, when the weight average molecular weight is less than 10,000, adhesion and conjugation properties may be inferior.

  The fiber paste of the present invention is obtained by the production method of the present invention, and is a polymerizable component containing (meth) acrylic acid, a (meth) acrylic acid ester monomer and a styrene monomer. A neutralized product of the copolymer obtained by copolymerizing a by emulsion polymerization (paste component A) and water are contained as essential components. 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. The fiber paste of the present invention may further contain a paste component other than the paste component A together with the paste component A and water.

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

  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, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, carboxymethyl cellulose, synthetic paste ((meth) acrylic acid) Polymer, (meth) 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.) Can be mentioned.

In addition to the glue component, the fiber glue of the present invention imparts flexibility and smoothness to the warp and is suitable for waxes, surfactants and glued yarns to cope with adhesive problems such as poor opening during weaving. Produced by weaving antistatic agent for preventing peeling and triboelectric charge, penetrating agent for assisting penetration of fiber paste into yarn, antifoaming agent for suppressing foaming of fiber paste, weaving It may contain other components such as antibacterial agents for preventing microbial contamination of raw machinery. Among other components, it is preferable to contain a wax.
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. In the manufacturing method of the fiber paste of this invention, it is preferable to further include the process of adding a wax to the obtained paste component A separately from a copolymerization process and a neutralization process.

Examples of the wax include petroleum waxes such as paraffin wax and microcrystalline wax; synthetic waxes 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. 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.
As the step of adding the wax, for example, a step of separately preparing an aqueous dispersion of wax, adding the aqueous dispersion of wax to the paste component obtained in the above neutralization step, and mixing and stirring them Etc.

  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.

  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 45% by weight of the wax, more preferably 8 to 40% by weight, and particularly preferably 10 to 35% by weight.

  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. If 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 for adhesion and conjugation to be inferior. On the other hand, when the weight concentration of the solid content exceeds 18%, the amount of the adhesive for fiber during sizing increases, which may cause adhesion 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 9.5, 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, 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.

[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 -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 filament yarn composed of polyester having an aromatic skeleton because of good adhesion and conjugation properties with the fiber paste. The filament yarn composed of polyester having an aromatic skeleton is preferably substantially composed of polyethylene terephthalate, but is also good for polyesters having other aromatic skeletons and polyamides having aromatic skeletons. Shows 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 thickness of the yarn is not limited, but for filament yarn, it is preferably 1000 dtex or less, more preferably 470 dtex or less, and particularly preferably 167 dtex or less. The spun yarn (spun yarn) is preferably 20 to 100, more preferably 20 to 90, and particularly preferably 20 to 80.

  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, 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.

  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.

  As the weaving step, for example, 4,000 to 20,000 glued yarns described above as warps and polyester filament yarns (11 to 167 dtex, 5 to 144 filaments) as wefts are prepared, and the weaving machine 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 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) Weight average molecular weight It measured by the gel permeation chromatography method (GPC) using the calibration curve by the standard substance polystyrene (Tosoh Corp.).
(Measurement condition)
Equipment used: High Performance Liquid Chromatography HLC-8020 (Tosoh Corporation)
Column: TSKgelGMHXL × 2 (Tosoh Corporation)
Solvent: THF (tetrahydrofuran) (for 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

(5) Appearance of glue component In a 20 ° C atmosphere, 80 g of 25% glue ingredient was added to a 100 ml beaker, and the sample was visually observed from the horizontal direction.
<Evaluation criteria for appearance of glue component>
○: Transparent △: Slightly cloudy ×: Cloudy

(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 (polyester filament yarn 33 dtex 24 filaments 180 g / 20 (= 9 g / y), 56 dtex 24 filaments 200 g / 20 (= 10 g / y) Measured in)

(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.
Yarn tension: 0.2-0.6 g / dtex per yarn (measured at 6 g for polyester filament yarn 33 dtex 24 filament, 10 g for 56 dtex 24 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 of dry and wet paste-fastening 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) Wrinkle-adhering paste properties (Evaluation of paste properties in practical weaving tests)
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

(10) Scourability Polyester taffeta (10cm x 10cm square) is 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%, and then squeezed with a roller and dried. . The taffeta obtained by drying is scoured for 30 seconds under the following two scouring conditions, and washed with water. Then, it is immersed in rhodamine dyeing (Wako Pure Chemical Industries, Ltd.) 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 (Wako Pure Chemical Industries, Ltd.) 0.5 g / L, POE 10 mol addition nonylphenol ether (Wako Pure Chemical Industries, Ltd.) 0.5 g / L
Scouring temperature: 85 ℃
Bath ratio: 100 times (scouring condition 2)
Scouring liquid: Caustic soda (Wako Pure Chemical Industries, Ltd.) 2 g / L, POE 10 mol addition nonylphenol ether (Wako Pure Chemical Industries, Ltd.) 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

[Production Example of Paste Component A1]
(Copolymerization process by emulsion polymerization)
A polymerizable component (type and amount are shown in Table 1) and 2 g of n-dodecyl mercaptan were mixed with stirring to obtain a mixture, which was transferred to a dropping funnel. A four-necked flask equipped with a dropping funnel, thermometer, stirrer, condenser and nitrogen gas blowing port was charged with 1500 g of ion exchange water and 20 g of sodium dodecylbenzenesulfonate as an emulsifier, and the temperature was raised to 70 ° C. while blowing nitrogen gas. did. Next, 5 g of ammonium persulfate, which is a water-soluble polymerization initiator, was added to the four-necked flask while stirring, and the mixture was added dropwise from the dropping funnel to the four-necked flask at 75 ° C. for 2 hours. After completion of the dropwise addition, copolymerization was carried out for 1 hour, and 0.5 g of ammonium persulfate was further added, followed by post-polymerization aging for 3 hours to obtain a reaction mixture containing the copolymer.
(Neutralization process)
After the copolymerization, 74 g of 16% aqueous ammonia is gradually added to the reaction mixture to neutralize the copolymer (pH 7 to 10), cool to room temperature, and paste component A1 comprising a copolymer neutralized product is added. A paste component liquid A1 was obtained.
The viscosity of the aqueous solution adjusted to a weight concentration of 25% of the solid content contained in the paste component liquid A1 (viscosity of the paste component liquid 1-1) was 225 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 8.5. For dilution for pH measurement, ion-exchanged water was used as in the viscosity measurement. Further, after naturally drying the paste component liquid A1, it is dissolved in THF (tetrahydrofuran) (Wako Pure Chemical Industries, Ltd., for liquid high-speed chromatography) so that the concentration becomes 0.5 mg / ml, and the weight average of the paste component A1 The molecular weight was measured.

[Production Examples of Paste Components A2 to A7, B1]
(Copolymerization process by emulsion polymerization)
The kinds and amounts of polymerizable components and chain transfer agents shown in Table 1 were placed in a dropping funnel, and ion-exchanged water, a solvent and an emulsifier were added to the four-necked flask used in the production example of the paste component A1. Next, an initiator was further added to the four-necked flask, mixed with stirring, and the temperature was raised to 70 ° C. while blowing nitrogen gas. Next, 5 g of ammonium persulfate, which is a water-soluble polymerization initiator, was added to the four-necked flask while stirring, and the mixture was added dropwise from the dropping funnel to the four-necked flask at 75 ° C. for 2 hours. After completion of the dropwise addition, copolymerization was carried out for 1 hour, and 0.5 g of ammonium persulfate was further added, followed by post-polymerization aging for 3 hours to obtain a reaction mixture containing the copolymer. In addition, the sodium POE alkyl ether sulfate of Table 1 is Kabushiki Lebenol WX.
(Neutralization process)
After copolymerization, an aqueous ammonia solution having a concentration of 16% was gradually added to the reaction mixture to neutralize it, and cooled to room temperature to obtain paste component liquids A2 to A7 and B1 containing paste components A2 to A7. The weight concentration of the solid content contained in the paste component liquids A2 to A7 and B1 was 25%.
Table 1 shows the viscosity and pH of the paste component liquids A2 to A7 and B1 and the weight average molecular weights of the paste components A2 to A7 and B1 measured in the same manner as in the production example of the paste component A1.

[Production Example of Paste Components B2 to B4]
(Copolymerization process by solution polymerization)
The kinds and amounts of the polymerizable components shown in Table 1, the solvent, and ion-exchanged water (medium mainly composed of the solvent) were added to the four-necked flask used in the production example of the paste component A1. Next, benzoyl peroxide, which is an oil-soluble polymerization initiator shown in Table 1, is further added to a four-necked flask, mixed with stirring, and copolymerized at 82 ° C. for 5 hours to obtain a reaction mixture containing the copolymer. It was.
(Neutralization process)
After the copolymerization, an aqueous ammonia solution having a concentration of 16% is gradually added to the reaction mixture for neutralization, cooled to room temperature, ion-exchanged water is added, and the paste component liquid B2 containing paste components B2 to B4 is added. B4 was obtained. The weight concentration of the solid content contained in the paste component liquids B2 to B4 was 25%, respectively.
Table 1 shows the viscosity and pH of the paste component liquids B2 to B4 and the weight average molecular weights of the paste components B2 to B4 measured in the same manner as in Example 1-1.

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 1-1]
Paste component liquid A1 containing paste component A1 obtained in the above production example, 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.) Were mixed to prepare a fiber paste a 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 a was adjusted to 1% (pH of the fiber paste 1) was measured, and the results are shown in Table 2.
Within 12 hours after the preparation of the fiber paste a, a sizing machine is used under the following sizing conditions for polyester filament yarn (33 dtex 24 filament) and polyester filament yarn (56 dtex 24 filament). Then, the paste a for fibers was adhered to obtain a glued yarn a. In addition, the adhesion amount of the fiber paste a in the glued yarn a was 5%.

<Sizing conditions>
Beam-to-beam method Gluing speed: 80m / min
Non-touch hot air drying temperature: 130 ° C
Touch cylinder drying temperature: 100 ° C
Number of touch cylinders: 3 About the obtained glued yarn a, the conjugation force and the paste-removing property in dry and wet processes were evaluated. The scourability of the fiber sizing agent a was evaluated using polyster taffeta. The results are shown in Table 2.

[Examples 1-2 to 1-8 and Comparative Examples 1-1 to 1-3]
In Example 1-1, except that the type of paste component to be used and the weight ratio of the paste component, the wax, and the surfactant are changed to those shown in Table 2, respectively, in the same manner as in Example 1-1, Each of the fiber pastes b to k was prepared, and the pH was measured in the same manner as in Example 1-1. Next, in the same manner as in Example 1-1, sizing was performed within 12 hours after preparing the fiber paste, and glued yarns b to k were obtained, respectively. In addition, the adhesion amount of the fiber pastes b to k in the respective paste yarns b to k was 5%. The obtained glued yarns b to k were evaluated in the same manner as in Example 1-1 for the conjugation force in the dry type and the wet type, the pasting property and the scouring property. The results are shown in Table 2.

From Table 2, the dry conjugation force and the wet conjugation force are satisfactory in the fiber pastes a to h of the examples obtained by the production method of the present invention. On the other hand, the fiber pastes i and j of comparative examples prepared from the paste components B1 and B2 are inferior. That is, when a polymerizable component not containing a styrene monomer is copolymerized, the dry conjugation force and the wet conjugation force are inferior even in emulsion polymerization or solution polymerization.
Moreover, about the dry paste property and wet paste property, it can be satisfied in the fiber pastes a to h of Examples obtained by the production method of the present invention. In particular, wet sizing properties are excellent in the sizing agents for fibers a to h of the examples because the sizing agent does not fall off and the sizing agent does not adhere to the comb. Therefore, when water jet loom weaving is performed using the fiber pastes a to h of the examples, excellent results without dropping are also obtained. On the other hand, the fiber pastes i and j of comparative examples prepared from the paste components B1 and B2 are inferior. That is, when a polymerizable component that does not contain a styrenic monomer is copolymerized, even if it is emulsion polymerization or solution polymerization, the dry and wet paste properties are poor.
Further, the scourability is excellent in the fiber pastes a to h of Examples obtained by the production method of the present invention. On the other hand, the fiber paste k of the comparative example prepared from the paste component B3 (appearance and slightly cloudy) is inferior. Further, the paste component B4 (appearance cloudy) has low water solubility and cannot be evaluated as a fiber paste. If evaluated, it is obvious that the scourability is inferior. Thus, when the polymerizable component similar to the present application containing a styrene monomer is copolymerized by solution polymerization, the scourability is extremely poor.

Claims (6)

A method for producing a fiber paste containing a neutralized copolymer,
A copolymerization step of copolymerizing a polymerizable component containing (meth) acrylic acid, a (meth) acrylic acid ester monomer and a styrene monomer by emulsion polymerization, and the copolymer obtained in the copolymerization step look including a neutralization step to neutralize the union,
The weight percentage of the styrenic monomer in the polymerizable component is 5 to 40% by weight, the weight percentage of the (meth) acrylic acid is 16 to 30% by weight,
The neutralized product of the copolymer has a weight average molecular weight of 10,000 to 200,000.
A method for producing a fiber paste. The fiber paste according to claim 1, wherein the copolymerization step is a step of emulsifying and dispersing the polymerizable component in the presence of a water-based medium and an emulsifier, and copolymerizing the polymerizable component. Production method. Furthermore, the manufacturing method of the paste for fibers of Claim 1 or 2 including the process of adding a wax. The fiber paste obtained by the production method according to any one of claims 1 to 3 , wherein the pH of the aqueous solution in which the weight concentration of solids contained in the fiber paste is adjusted to 1% is 7 to A paste for fibers in the range of 10. A glued yarn obtained by sizing a fiber paste obtained by the production method according to any one of claims 1 to 3 into a yarn. A method for producing a woven fabric, comprising a step of weaving a warp and a weft comprising the glued yarn according to claim 5 using a weaving machine.