JP2016023386A - Fiber paste, sizing thread and manufacturing method of fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber paste capable of reducing starch removal while dividing a sizing thread and excellent in making fabric and removal property of sizing agent, a sizing thread and a manufacturing method of fabric capable of simply providing a fabric.SOLUTION: There is provided a fabric paste containing a vinyl alcohol-based polymer (A) with a ratio of a weight average molecular weight (Mw(A)) to a number average molecular weight (Mn(A)) of the vinyl alcohol-based polymer (A) (Mw(A)/Mn(A)) of 3 to 8 and a ratio of a weight average molecular weight (Mw(B)) to a number average molecular weight (Mn(B)) of the vinyl alcohol-based polymer (B) obtained by treating the vinyl alcohol-based polymer (A) in a sodium hydroxide solution at 40°C for 1 hours (Mw(B)/Mn(B)) of 2 or more and less than 3. The fiber paste further preferably contains wax.SELECTED DRAWING: None

Description

  The present invention relates to a fiber sizing agent, a gluing thread, and a method for producing a woven fabric.

  A vinyl alcohol polymer (hereinafter sometimes abbreviated as “PVA”) is a water-soluble polymer, can be stored for a long time without being spoiled, and has excellent dry film strength. Used as a reinforcing glue.

  However, when the fiber sizing agent is glued to the raw yarn bundle and the glued yarns are divided one by one after drying (divide), thread breakage may occur due to the high film strength. In order to reduce this thread breakage, if the PVA concentration in the fiber glue is lowered, the strength of the glue thread is lowered and the weaving property is lowered, or the fiber glue solidified when the glue thread is divided is removed from the glue thread. There is a tendency for the amount of glue to fall off to increase. Furthermore, the fiber sizing agent containing PVA has a disadvantage that it is inferior in the desizing property after weaving the glued yarn.

  In response to the above inconveniences, fiber sizing agents containing various modified PVAs have been developed. As such a fiber paste, for example, a fiber paste containing ethylene-modified PVA and starch as main ingredients (see JP-A-9-31849), a carboxylate-modified PVA such as alkyl acrylate, and the like. (See WO95 / 23254).

  However, these sizing agents for fibers do not sufficiently satisfy both the weaving property of the sizing yarn, the desizing property, and the glue removal during the divide.

JP 9-31849 A WO95 / 23254

  The present invention has been made on the basis of the above-described circumstances, and can reduce the amount of glue removal during the divide of the glued yarn, and can be easily used as a fiber glue, glued yarn, and woven fabric excellent in weaving and desizing properties. It aims at providing the manufacturing method of the textile fabric which can be provided.

  The invention made to solve the above-mentioned problems is a fiber paste containing a vinyl alcohol polymer (A), the number average molecular weight (Mn (A)) of the vinyl alcohol polymer (A). The ratio (Mw (A) / Mn (A)) of the weight average molecular weight (Mw (A)) to 3 is 8 to 3, and the vinyl alcohol polymer (A) is added at 40 ° C. in a sodium hydroxide solution. The ratio (Mw (B) / Mn (B)) of the weight average molecular weight (Mw (B)) to the number average molecular weight (Mn (B)) of the vinyl alcohol polymer (B) obtained by treating for 1 hour is 2. It is less than 3.

  In the fiber paste, the ratio (Mw (A) / Mn (A)) of the vinyl alcohol polymer (A) contained therein and the vinyl alcohol polymer (A) are alkali-treated under specific conditions. When the ratio (Mw (B) / Mn (B)) of the vinyl alcohol polymer (B) obtained in the above range is in the above range, the glue is removed when the glued yarn using the fiber paste is divided. Is reduced, and weaving and desizing properties are excellent.

  The vinyl alcohol polymer (A) is obtained by polymerizing a vinyl ester monomer in the presence of the monomer (a), followed by saponification and heat treatment, and the monomer (a ) Is a carboxylic acid having an unsaturated double bond, an alkyl ester of a carboxylic acid having an unsaturated double bond, an acid anhydride of a carboxylic acid having an unsaturated double bond, a carboxylic acid having an unsaturated double bond. It may be at least one selected from the group consisting of a salt and a silyl compound having an unsaturated double bond. Thus, the vinyl alcohol polymer (A) is obtained by polymerizing a vinyl ester monomer in the presence of the monomer (a), whereby a vinyl alcohol polymer (A ) Has a hydrophilic carboxyl group or silyl group derived from the monomer (a). Thereby, the hydrophilic property of the fiber paste containing the vinyl alcohol polymer (A) is improved, and as a result, the desizing property after weaving of the paste yarn using the fiber paste is further improved. In addition, at least partially due to an ester bond or silanol bond between the carboxyl group or silyl group contained in the vinyl alcohol polymer (A) and the hydroxyl group contained in the vinyl alcohol polymer (A) by heat treatment. A cross-linked structure is formed, and a branched structure can be formed as a whole. Therefore, the film made of the vinyl alcohol polymer (A) has high strength. As a result, it is possible to obtain a fiber sizing agent in which glue removal during divide of the sizing yarn is reduced and the sizing yarn is excellent in weaving property and desizing property.

  The fiber sizing agent may further contain a wax. By containing the wax in this manner, the glue removal during the divide of the glued yarn using the fiber paste is further reduced, and the weaving property is further improved.

  Another invention made in order to solve the above-mentioned problem is a gluing yarn comprising a raw yarn and a binder impregnated in the raw yarn, wherein the binder is formed from the fiber sizing agent. And By containing the fiber paste, the glued yarn has less detachment at the time of divide and is excellent in weaving and desizing.

  Yet another invention made to solve the above problems is a method for manufacturing a woven fabric including a step of weaving the glued yarn. According to the method for producing a woven fabric, since the glued yarn is used, there is little glue removal when the glued yarn divides, the weaving property and the desizing property are excellent, and as a result, the fabric can be provided simply.

  As described above, the fiber glue of the present invention can reduce glue removal at the time of divide, and can provide a glued yarn excellent in weaving property. Moreover, the gluing yarn of the present invention can give a woven fabric excellent in degutting property. Furthermore, since the manufacturing method of the fabric of the present invention uses the glued yarn, the fabric can be provided simply.

<Glue paste>
The fiber paste contains a vinyl alcohol polymer (A) containing a vinyl alcohol unit (hereinafter, the vinyl alcohol polymer may be abbreviated as “PVA”). Moreover, it is preferable to further contain a wax. In addition, the paste for fibers may contain other components such as starch as long as the effects of the present invention are not hindered.

[PVA (A)]
PVA (A) has a ratio of weight average molecular weight (Mw (A)) to number average molecular weight (Mn (A)) (Mw (A) / Mn (A)) of 3 or more and 8 or less. The lower limit of the ratio is preferably 3.2, more preferably 3.4, further preferably 3.6, and the upper limit of the ratio is preferably 6 and more preferably 5.

  The PVA (A) is treated in a sodium hydroxide solution at 40 ° C. for 1 hour to obtain PVA (B). As this treatment, the method of complete saponification described in the column of average degree of polymerization in JIS-K6726: 1994 can be adopted, and specifically, it is obtained as follows. That is, about 10 g of PVA (A) was weighed into a 500 mL common conical Erlenmeyer flask, and after adding 200 mL of methanol, 12.5 mol / L sodium hydroxide solution was added to a saponification degree of PVA (A) of 97 mol%. In the above case, 3 mL is added. When the degree of saponification of PVA (A) is less than 97 mol%, 10 mL is added and stirred. Next, after heating in a water bath at 40 ° C. for 1 hour, phenolphthalein is added as an indicator, and sodium hydroxide is removed by washing with methanol until no alkaline reaction is observed. Finally, it can be obtained by transferring to a watch glass and drying at 105 ° C. for 1 hour until methanol is exhausted.

  The PVA (B) has a ratio of the weight average molecular weight (Mw (B)) to the number average molecular weight (Mn (B)) (Mw (B) / Mn (B)) of 2 or more and less than 3. The lower limit of the ratio is preferably 2.1, more preferably 2.2, and the upper limit of the ratio is preferably 2.9 and more preferably 2.8.

  The PVA (A) contained in the fiber paste of the present invention is such that (Mw (A) / Mn (A)) and (Mw (B) / Mn (B)) are in the above range. A) is considered to form a branched structure by bonds in which the PVA chains are cut under alkaline conditions. And it is thought by this branched structure that the paste for fibers containing PVA (A) can reduce glue removal at the time of divide and can obtain a glued yarn excellent in weaving property and desizing property.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) in the above PVA (A) and PVA (B) are determined by gel permeation chromatography using hexafluoroisopropanol as a mobile phase and a differential refractive index detector. It can obtain | require as a polymethylmethacrylate conversion value by a graphic (GPC) measurement, As a more concrete method, the following can be employ | adopted.
GPC column: 2 “GHH _HR (S)” manufactured by Tosoh Corporation Mobile phase: hexafluoroisopropanol Flow rate: 0.2 mL / min Sample concentration: 0.100 wt / vol%
Sample injection volume: 10 μL
Detector: Differential refractive index detector Standard material: Polymethyl methacrylate (for example, “EasiVial PMMA 4 mL tri-pack” manufactured by Agilent Technologies)

  It is preferable to add a salt such as sodium trifluoroacetate to hexafluoroisopropanol used as the mobile phase in order to suppress the adsorption of the sample to the GPC column filler. The lower limit of the salt concentration is preferably 1 mmol / L, and more preferably 5 mmol / L. On the other hand, the upper limit of the salt concentration is preferably 100 mmol / L, more preferably 50 mmol / L.

  The ratio of the weight average molecular weight (Mw (A)) of the PVA (A) to the weight average molecular weight (Mw (B)) of the PVA (B) (Mw (A) / Mw (B)) is not particularly limited. Is preferably 1.4, and more preferably 1.5. On the other hand, the upper limit of the ratio (Mw (A) / Mw (B)) is preferably 3.0, and more preferably 2.5. When the said ratio (Mw (A) / Mw (B)) is less than the said minimum, there exists a possibility that the paste removal at the time of the divide of the glue thread using the said paste for fibers may increase. On the other hand, when the ratio (Mw (A) / Mw (B)) exceeds the upper limit, the weaving property of the glued yarn using the fiber paste may be lowered.

  As PVA (A), what is obtained by saponifying a vinyl ester polymer can be used. Although PVA (A) may consist only of a vinyl alcohol unit, it is preferable that the unit derived from a monomer (a) is further included.

  The vinyl ester monomer used for the production of the vinyl ester polymer is not particularly limited. For example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate , Vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate and the like. Among these, vinyl acetate is preferable from the economical viewpoint.

  The monomer (a) includes a carboxylic acid having an unsaturated double bond, an alkyl ester of the carboxylic acid, an acid anhydride of the carboxylic acid, a salt of the carboxylic acid, and a silyl compound having an unsaturated double bond. At least one monomer selected from the group consisting of:

  Examples of the carboxylic acid having an unsaturated double bond, an alkyl ester of the carboxylic acid, an acid anhydride of the carboxylic acid, and a salt of the carboxylic acid include maleic acid, maleic acid monomethyl ester, maleic acid dimethyl ester, and maleic acid. Acid monoethyl ester, maleic acid diethyl ester, maleic anhydride, citraconic acid, citraconic acid monomethyl ester, citraconic acid dimethyl ester, citraconic acid diethyl ester, citraconic anhydride, fumaric acid, fumaric acid monomethyl ester, fumaric acid dimethyl ester, fumaric acid Acid monoethyl ester, fumaric acid diethyl ester, itaconic acid, itaconic acid monomethyl ester, itaconic acid dimethyl ester, itaconic acid monoethyl ester, itaconic acid diethyl ester, itaconic anhydride, Acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, and ethyl methacrylate.

  Examples of the silyl compound having an unsaturated double bond include compounds having an unsaturated double bond and a trialkoxysilyl group such as vinyltrimethoxysilane and vinyltriethoxysilane.

  Among these monomers (a), maleic acid monomethyl ester, citraconic acid monomethyl ester, itaconic acid monomethyl ester, methyl acrylate, methyl methacrylate, vinyltrimethoxysilane are preferred, maleic acid monomethyl ester, methyl acrylate, More preferred are methyl methacrylate and vinyltrimethoxysilane.

  As a minimum of the content rate of the unit derived from the monomer (a) in PVA (A), 0.02 mol% is preferable based on the number-of-moles of all the monomer units which comprise PVA (A), 0 0.05 mol% is more preferable, and 0.1 mol% is more preferable. On the other hand, the upper limit of the content of units derived from the monomer (a) in PVA (A) is preferably 5 mol% based on the number of moles of all monomer units constituting PVA (A), 2 mol% is more preferable and 1 mol% is further more preferable. When the said content rate is less than the said minimum, there exists a possibility that the weaving property of the glue thread using the said paste for fibers may fall. On the other hand, when the content exceeds the upper limit, the desizing property of the glued yarn using the fiber paste may be lowered.

  Moreover, PVA (A) may contain the unit derived from other monomers other than the unit derived from a vinyl alcohol unit and a monomer (a) in the range which does not impair the meaning of this invention. Examples of the unit derived from the other monomer include α-olefins such as ethylene, propylene, n-butene and isobutylene; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, vinyl ethers such as i-butyl vinyl ether, t-butyl vinyl ether, 2,3-diacetoxy-1-vinyloxypropane; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride Units derived from vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate, 2,3-diacetoxy-1-allyloxypropane and allyl chloride; isopropenyl acetate and the like. The content rate of the unit derived from the said other monomer in PVA (A) can be made into 15 mol% or less, for example based on the number-of-moles of all the monomer units which comprise PVA (A).

  There is no particular limitation on the order of arrangement of the vinyl alcohol unit, the unit derived from the monomer (a) and the unit derived from the other monomer in PVA (A), and any of random, block, and alternating Also good.

The primary structure of PVA (A) can be quantified by ¹ H-NMR.

  The degree of saponification of PVA (A) (the molar fraction of hydroxyl groups relative to the total of hydroxyl groups and ester bonds in PVA (A)) is measured according to JIS-K6726: 1994. As a minimum of saponification degree, 20 mol% is preferable, 60 mol% is more preferable, 70 mol% is further more preferable, 80 mol% is especially preferable, and 87 mol% is the most preferable. When the degree of saponification of PVA (A) is not less than the above lower limit, the desizing property of the glued yarn using the fiber paste is further improved.

The PVA (A) has a viscosity average degree of polymerization (P) of 30 ° C. for PVA (A) containing units derived from the monomer (a) after completely saponifying and purifying the PVA (A). Intrinsic viscosity [η] (unit: liter / g) was measured in an aqueous sodium solution (0.5 mol / L), and PVA (A) containing no unit derived from monomer (a) was 30 ° C. Intrinsic viscosity [η] (unit: liter / g) is measured in an aqueous solution. From this intrinsic viscosity [η], the viscosity average degree of polymerization (P) of PVA (A) is obtained by the following formula.
P = ([η] × 10 ⁴ /8.29) ^{(1 / 0.62)}

  As an upper limit of the viscosity average polymerization degree of PVA (A), 5,000 is preferable and 4,000 is more preferable. On the other hand, as a minimum of the viscosity average degree of polymerization of PVA (A), 100 is preferred, 500 is more preferred, and 1,000 is still more preferred. When the viscosity average polymerization degree of PVA (A) is not less than the above lower limit, the weaving property of the glued yarn using the fiber paste is further improved. On the other hand, when the viscosity average polymerization degree of PVA (A) is not more than the above upper limit, the productivity of PVA (A) is improved, and PVA (A) can be produced at a lower cost.

  Moreover, since PVA (B) is obtained by treating PVA (A) in a sodium hydroxide solution at 40 ° C. for 1 hour, the viscosity average polymerization degree of PVA (B) is the viscosity of PVA (A). The average polymerization degree is substantially the same value.

[wax]
The wax further improves the weaving property of the glued yarn, improves the fixing property of the fiber glue to the original yarn, and further reduces the amount of glue removed when the glued yarn is divided.

  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. Only 1 type may be used for the said wax and it may use 2 or more types together. Of these, petroleum wax is preferred as the wax. By using petroleum wax, the smoothness of the glued yarn is improved.

  The wax is usually used as an aqueous dispersion emulsified with a surfactant such as a nonionic surfactant or an anionic surfactant.

  The upper limit of the wax content relative to the total solid content in the fiber paste is preferably 20% by mass, more preferably 15% by mass, still more preferably 12% by mass, and particularly preferably 10% by mass. On the other hand, as a minimum of the above-mentioned content, 0.5 mass% is preferred, 1 mass% is more preferred, 2 mass% is still more preferred, and 3 mass% is especially preferred. By setting the content of the wax within the above range, the amount of paste removed at the time of dividing the glued yarn using the fiber paste is further reduced, and the weaving property is further improved.

[Other ingredients]
Examples of other components that the fiber paste may contain include water-soluble polymers such as starch, water-soluble cellulose compounds, and water-soluble acrylic pastes, antifoaming agents, antistatic agents, antiseptics, and antifungal agents. Agents and the like.

  Examples of the starch include raw starches such as corn, potato, tapioca, and wheat, and processed starches thereof. Examples of the processed starch include pregelatinized (gelatinized) starch, oxidized starch, esterified starch, etherified starch, grafted starch, carboxymethylated starch, dialdehyde starch, and cationized starch. Among these, processed starch is preferable from the viewpoint of easy gelatinization and preparation of a paste liquid. As a minimum of mass ratio (PVA (A) / starch) of the above-mentioned PVA (A) and the above-mentioned starch, 1/99 is preferred, 30/70 is more preferred, and 50/50 is still more preferred. On the other hand, the upper limit of the mass ratio is preferably 90/10, more preferably 80/20, and even more preferably 75/25.

  Examples of the water-soluble cellulose compound include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and the like.

  When the fiber paste is used for a spun yarn, the viscosity of the fiber paste at a general pasting temperature of 70 ° C. to 95 ° C. is preferably 50 mPa · s to 200 mPa · s. By setting the viscosity of the sizing agent for fibers within the above range, the fluffiness of the sizing yarn is improved. Moreover, the solid content concentration of the fiber paste is not particularly limited, but is preferably 3% by mass or more and 15% by mass or less.

<Manufacturing method of fiber paste>
Although it does not specifically limit as a manufacturing method of the said paste for fibers, For example, the process of mixing arbitrary components, such as a wax, with the process of manufacturing PVA (A) and PVA (A), is provided.

[Production of PVA (A)]
Examples of the process for producing the PVA (A) include a process for polymerizing a monomer containing a vinyl ester monomer (hereinafter also referred to as “polymerization process”), and a vinyl ester heavy polymer obtained by this polymerization process. And a step of saponifying the coalescence (hereinafter also referred to as “saponification step”). In addition, it is preferable to further include a step of heating the vinyl ester polymer or the saponified PVA (hereinafter also referred to as “heating step”).

(Polymerization process)
In this step, a monomer containing a vinyl ester monomer is polymerized to synthesize a vinyl ester polymer. As described above, the monomer containing the vinyl ester monomer includes only the vinyl ester monomer, and as described above, the vinyl ester monomer, the monomer (a) and / or Or it may contain either the said other monomer.

  As a polymerization method of a monomer including a vinyl ester monomer, any of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization may be used. As the polymerization method, any known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method can be employed. Among these, a bulk polymerization method or a solution polymerization method in which polymerization proceeds in a solvent-free or solvent such as alcohol is usually employed. In order to obtain a vinyl ester polymer having a high degree of polymerization, one of the options is to employ an emulsion polymerization method. The solvent for the solution polymerization method is not particularly limited, and examples thereof include alcohol. The alcohol used as the solvent for the solution polymerization method is, for example, a lower alcohol such as methanol, ethanol, or n-propanol. A solvent may be used individually by 1 type, or may use 2 or more types together. What is necessary is just to select the usage-amount of the solvent in a polymerization system in consideration of the chain transfer of a solvent according to the polymerization degree etc. of the target PVA (A). For example, when the solvent is methanol, the lower limit of the mass ratio {= (solvent) / (total monomer)} between the solvent and all monomers contained in the polymerization system is preferably 0.01, and 0.05 More preferred. On the other hand, the upper limit of the mass ratio is preferably 10, and more preferably 3.

  The polymerization initiator used for such polymerization may be appropriately selected from known polymerization initiators such as azo initiators, peroxide initiators, redox initiators and the like according to the polymerization method. Examples of the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2,4). -Dimethylvaleronitrile) and the like. Examples of peroxide initiators include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, α- Perester compounds such as cumylperoxyneodecanate and t-butylperoxydecanate; acetyl peroxide; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate and the like. The initiator may be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like. Examples of the redox initiator include a combination of the above peroxide initiator and a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.

  The amount of the polymerization initiator used varies depending on the polymerization catalyst and the like and cannot be determined unconditionally, but may be appropriately selected according to the polymerization rate. For example, when 2,2′-azobisisobutyronitrile or acetyl peroxide is used as the polymerization initiator, the lower limit of the content of the polymerization initiator is 0.01 mol% relative to the vinyl ester monomer. Preferably, 0.02 mol% is more preferable. On the other hand, as an upper limit of content of a polymerization initiator, 0.2 mol% is preferable and 0.15 mol% is more preferable.

  As a minimum of temperature in a polymerization process, 0 ° C is preferred and 30 ° C is more preferred. As an upper limit of polymerization temperature, 200 degreeC is preferable and 140 degreeC is more preferable. When the polymerization temperature is equal to or higher than the above lower limit, the polymerization rate is improved. On the other hand, when the polymerization temperature is not more than the above upper limit, for example, even when the monomer (a) is used, the content of units derived from the monomer (a) in the PVA (A) is kept at an appropriate ratio. It becomes easy. As a method of controlling the polymerization temperature within the above range, for example, by controlling the polymerization rate, a method of balancing the heat generated by the polymerization and the heat release from the surface of the reactor, or using an appropriate heating medium Although the method etc. which control by an external jacket are mentioned, the latter method is preferable from a viewpoint of safety.

  The polymerization may be carried out in the presence of a chain transfer agent as long as the gist of the present invention is not impaired. Examples of chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; halogenated hydrocarbons such as trichloroethylene and perchloroethylene; sodium phosphinate Examples thereof include phosphinic acid salts such as monohydrate. Of these, aldehydes and ketones are preferred. The amount of chain transfer agent added to the polymerization system can be determined according to the chain transfer coefficient of the chain transfer agent to be added, the degree of polymerization of the target PVA (A), etc., and is generally a vinyl ester monomer. 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts.

  In addition, when the said polymerization is performed under high temperature, coloring etc. of PVA (A) resulting from decomposition | disassembly of a vinyl ester-type monomer may be seen. In this case, an antioxidant such as tartaric acid may be added to the polymerization system for the purpose of preventing coloring from about 1 ppm to 100 ppm with respect to the vinyl ester monomer.

(Saponification process)
In this step, the vinyl ester polymer is saponified. By saponifying this polymer, the vinyl ester unit in the polymer is converted into a vinyl alcohol unit.

  Although it does not restrict | limit especially as reaction used for the saponification of a vinyl ester polymer, The well-known alcoholic decomposition reaction or hydrolysis reaction performed in the state which the said polymer melt | dissolved in the solvent is employable.

  Examples of the solvent used for saponification include lower alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene. These solvents may be used alone or in combination of two or more. Among these, methanol and a mixed solution of methanol and methyl acetate are preferable.

  Examples of the catalyst used for saponification include alkali catalysts such as alkali metal hydroxides (potassium hydroxide, sodium hydroxide, etc.), sodium alkoxides (sodium methoxide, etc.); acids such as p-toluenesulfonic acid and mineral acids. A catalyst etc. are mentioned. Among these, it is preferable to use sodium hydroxide because it is simple.

  Although it does not specifically limit as temperature which performs saponification, 20 to 60 degreeC is preferable. When a gel-like product precipitates as saponification progresses, it is preferable to pulverize the product and further promote saponification. Then, saponification is complete | finished by neutralizing the obtained solution, and it can wash | clean and dry and can obtain PVA. As a saponification method, not only the method mentioned above but a well-known method is employable.

(Heating process)
In this step, the vinyl ester polymer or the saponified PVA is heated. Specifically, the vinyl ester polymer is heated by heating simultaneously with the saponification step, or the PVA obtained after the saponification step is heated. PVA (A) in which a branched structure is formed by this heating can be easily obtained, and the weaving property and desizing property of the glued yarn using the fiber paste are further improved. The heat treatment is preferably performed in an air or nitrogen atmosphere. Moreover, it is preferable that a heating process is performed with respect to PVA after saponification.

  As a minimum of heating temperature in a heating process, 70 ° C is preferred and 90 ° C is more preferred. As an upper limit of the said heating temperature, 170 degreeC is preferable and 150 degreeC is more preferable. The lower limit of the heating time in the heating step is preferably 30 minutes, more preferably 1 hour, and even more preferably 2 hours. The upper limit of the heating time is preferably 10 hours, more preferably 7 hours, and even more preferably 5 hours. By making heating temperature and heating time into the said range, PVA (A) which satisfy | fills the prescription | regulation of this invention can be obtained easily, and the weaving property of the said paste agent for fibers improves more.

[Mixing of optional components]
The paste for fibers can be produced by appropriately mixing the PVA (A) obtained by the above production method and optional components.

  The fiber paste of the present invention can also be effectively used as a textile resin processing, laundry paste, textile paste, felt or nonwoven fabric binder.

<Glued thread>
The gluing yarn of the present invention includes a raw yarn and a binder impregnated in the raw yarn, and the binder is formed from the fiber sizing agent.

  Examples of the raw yarn before gluing include single yarns such as cotton, polyester, rayon, hemp, nylon, wool, and acrylic, and blended yarns thereof.

  The method of pasting the raw yarn is not particularly limited, and examples thereof include simultaneous slasher pasting, partial warping pasting, tape pasting, cheese pasting, and the like.

  The adhesion amount (glue amount) of the binder (gluing agent for fibers) to the raw yarn can be appropriately selected according to the standard of the woven fabric, the equipment of the weaving machine and the gluing machine used, and is usually 5% by mass or more and 25% with respect to the raw yarn. It is below mass%. When the amount of glue is less than the above lower limit, the abrasion resistance of the fiber is lowered, and the fluff on the fiber surface may not be sufficiently reduced, and the yarn breakage during weaving may increase. On the other hand, when the amount of pasting exceeds the above upper limit, there is a risk that the amount of glue dropping at the time of divide increases and the production cost of the fabric may increase. Here, “amount of glue” refers to “parts of fluff that have fallen off at the time of desizing and cleaning” described on pages 299-302 of Kawara Fukada and Teruhiko Ichimi, published by the Japan Textile Machinery Society, 4th edition. It is a value measured by a method for correcting.

  The glued yarn is dried by a cylinder to form a sheet-like glued yarn bundle. The surface temperature of this cylinder is usually 100 ° C. or higher and 150 ° C. or lower. The dried gluing yarn bundle is divided and separated into individual gluing yarns.

<Method for producing woven fabric>
The method for producing a woven fabric according to the present invention includes a step of weaving a yarn that is glued with the fiber paste. Specifically, the glued yarn after the divide is wound around a textile beam and woven by a weaving machine. Examples of the loom include dry looms such as rapier looms and air jet looms, and water jet looms. Among these, air jet looms are preferable.

  The glued yarn glued with the fiber glue may be either a warp or a weft, but is preferably a warp. Since high tension is applied to the warp to improve the opening on the weaving machine, the warp has a large friction with the heel, heald and dropper. Therefore, by using the glued yarn as a warp, the strength of the warp is improved, yarn breakage due to the friction is reduced, and weaving is improved. Furthermore, glue removal during the warp divide is reduced. As the weft, the glued yarn may be used in the same manner as the warp, but it is common to use a raw yarn that is not specially treated.

  Hereinafter, the present invention will be described in detail by way of examples and comparative examples. In the following examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

  About the physical property value of PVA of the following Example and comparative example, it measured in accordance with the following method.

[Degree of polymerization]
In each Example or Comparative Example, the viscosity average degree of polymerization of PVA (A) was determined by the method described in JIS-K6726: 1994.

[Saponification degree]
The degree of saponification of each PVA (A) was determined by the method described in JIS-K6726: 1994.

[Modification rate]
The modification rate of each PVA (the content of the unit derived from the monomer (a) in PVA (A)) is determined by using ¹ H-NMR using a vinyl ester polymer that is a precursor of PVA (A). It was determined by the method used.

For example, when monomethyl maleate is used as the monomer (a), the content is determined by the following procedure. That is, after re-precipitation purification of the vinyl ester polymer that is a precursor of PVA (A) is sufficiently performed three or more times using n-hexane / acetone as a solvent, the purified product obtained was reduced in pressure at 50 ° C. The sample is dried for 2 days to prepare a sample for analysis. This sample is dissolved in CDCl ₃ and measured at room temperature using ¹ H-NMR. Peak α derived from the methine structure of the vinyl ester unit in the vinyl ester polymer (4.7 to 5.2 ppm) and peak β derived from the methyl group of the methyl ester portion of the unit derived from the monomer (a) From (3.6 to 3.8 ppm), the content S of the unit derived from the monomer (a) can be calculated using the following formula.
S (mol%) = {(number of protons of β / 3) / (number of protons of α + (number of protons of β / 3))} × 100

[Preparation of PVA (B)]
About 10 g of PVA (A) is weighed into a 500 mL common conical Erlenmeyer flask, 200 mL of methanol is added, 10 mL of 12.5 mol / L sodium hydroxide solution is added, and the mixture is stirred for 1 hour in a 40 ° C. water bath. Heated. Next, phenolphthalein was added as an indicator, and sodium hydroxide was removed by washing with methanol until no alkaline reaction was observed. Finally, it was transferred to a watch glass and dried at 105 ° C. for 1 hour until methanol disappeared to prepare PVA (B).

[Number average molecular weight (Mn) and weight average molecular weight (Mw) of PVA (A) and PVA (B)]
It calculated | required as a polymethylmethacrylate conversion value by the gel permeation chromatography (GPC) measurement using the differential refractive index detector, using hexafluoro isopropanol for a mobile phase. Specifically, the following conditions were adopted.
GPC column: 2 Tosoh "GMH _HR (S)" mobile phase: hexafluoroisopropanol (contains sodium trifluoroacetate at a concentration of 20 mmol / L)
Flow rate: 0.2 mL / min Sample concentration: 0.100 wt / vol%
Sample injection volume: 10 μL
Detector: Differential refractive index detector Standard material: Polymethyl methacrylate (for example, “EasiVial PMMA 4 mL tri-pack” manufactured by Agilent Technologies)

[Synthesis Example 1] (Production of PVA-1)
A reactor equipped with a stirrer, reflux condenser, nitrogen inlet, comonomer dropping port and polymerization initiator addition port was charged with 740 parts of vinyl acetate and 260 parts of methanol, and nitrogen was bubbled through the system for 30 minutes. Replaced. Further, monomethyl maleate was selected as monomer (a), and a methanol solution of monomethyl maleate (concentration 20%) was replaced with nitrogen by bubbling nitrogen gas. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 part of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. The methanol solution of monomethyl maleate was dropped into the reactor to polymerize at 60 ° C. for 3 hours while keeping the monomer composition ratio in the polymerization solution constant, and then cooled to stop the polymerization. The total amount of monomer (a) added until the termination of polymerization was 0.9 part, and the solid content concentration at the termination of polymerization was 33.3%. Subsequently, unreacted monomers were removed while sometimes adding methanol under reduced pressure at 30 ° C. to obtain a methanol solution (concentration 35%) of a vinyl ester polymer. Next, 790.8 parts of a methanol solution of a vinyl ester polymer prepared by adding methanol to this methanol solution (200.0 parts of the polymer in the solution) was added to a 10% methanol solution of sodium hydroxide 9. Two parts were added and saponification was carried out at 40 ° C. (25% of the polymer concentration in the saponification solution, 0.01 molar ratio of sodium hydroxide to vinyl acetate units in the polymer). After adding a sodium hydroxide methanol solution, a gel was formed in about 15 minutes. This was pulverized with a pulverizer and further allowed to stand at 40 ° C. for 1 hour to proceed with saponification, and then 500 parts of methyl acetate. Was added to neutralize the remaining alkali. After confirming the completion of neutralization using a phenolphthalein indicator, the mixture was filtered to obtain a white solid. To this white solid, 2,000 parts of methanol was added, and the mixture was left to wash at room temperature for 3 hours. After repeating this washing | cleaning operation 3 times, the white solid obtained by carrying out centrifugation liquid removal was heat-processed at 120 degreeC with the dryer for 4.5 hours, and PVA (A) (PVA-1) was obtained. Table 2 shows the physical properties of PVA-1.

[Synthesis Examples 2 to 17] (Production of PVA-2 to PVA-17)
Polymerization conditions such as the amount of vinyl acetate and methanol charged, the type and amount of monomer (a) used during polymerization, the concentration of vinyl ester polymer during saponification, the molar ratio of sodium hydroxide to vinyl acetate units, etc. Various PVA (A) were produced by the same method as in Synthesis Example 1 except that the saponification conditions; and the heat treatment conditions were changed as shown in Table 1. Table 2 shows the physical properties of each PVA (A) and PVA (B) obtained therefrom. In Synthesis Example 13, after producing two types of PVA (A), PVA-13a and PVA-13b, two types of PVA are used so that 45 parts of PVA-13a and 55 parts of PVA-13b are included. (A) was mixed. Moreover, since PVA-10 and PVA-12 were not completely dissolved in hexafluoroisopropanol, Mn and Mw could not be measured.

[Example 1]
(Preparation, pasting and weaving of fiber paste)
Water was used as a solvent, and a fiber paste was prepared so that the concentration of PVA-1 was 7% by mass and the concentration of wax (“NC-204” from Kanei Sangyo Co., Ltd.) was 0.7% by mass.

Using the prepared fiber sizing agent, sizing was performed under the following conditions.
Gluing machine: 2-box 2-sheet type (Tsudakoma)
Paste temperature: 90 ° C
Drawing roll width: 1800mm
Drawing load: 800 kg / 1800 mm width Warp yarn: Cotton yarn (Toyobo's “Goldfish C40 / 1”)
Warp speed: 60 yards / min Drying temperature: 100 ° C to 130 ° C
Glued yarn length: 5600 yards

Weaving was performed under the following conditions using the glued yarn as a warp.
Weft: Cotton yarn (Toyobo's “Goldfish C40 / 1”)
Warp density: 136 / inch Weft density: 72 / inch Weaving width: 47 inches Total number of warps: 6420 Weaving structure: Broad Weaving machine: Air jet loom ("ZA-209i" by Tsudakoma)
Loom rotation speed: 600rpm

[Examples 2 to 8 and Comparative Examples 1 to 9]
A fiber sizing agent was prepared, glued and woven in the same manner as in Example 1 except that the PVA (A) used was changed to that shown in Table 3. In Comparative Examples 2 and 4, PVA was not completely dissolved in water, and a fiber paste could not be prepared.

<Evaluation>
The following criteria were used to evaluate the glued yarns and fabrics of the above examples and comparative examples. The evaluation results are shown in Table 3.

[Paste removal]
On the loom when the yarn glued by the above method is conditioned at 20 ° C. and 40% RH (relative humidity), and weaving a length of 3000 m under the above-mentioned weaving conditions (such as cocoons, healds, droppers) The degree of detachment of the paste to the eye was visually observed and evaluated according to the following criteria.
A: Very little B: Less C: Many

[Weaving property]
The yarn glued by the above method was conditioned at 20 ° C. and 40% RH (relative humidity), and woven for three days under the above-mentioned weaving conditions. The weaving property at that time was evaluated by average weaving efficiency and warp breakage.

(Average weaving efficiency)
As the average weaving efficiency, a value obtained by dividing the weaving length per unit weaving time by the theoretical weaving length was used.
A: 93% or more B: 85% or more and less than 93% C: Less than 85%

(Warp break)
For the warp breakage, the average number of yarn breaks that occurred per unit weaving time was used.
A: Less than 0.4 times / hour B: 0.4 times / hour or more and less than 1 time / hour C: One time / hour or more

[Desizing]
The woven fabric obtained above was treated in a 0.1% sodium hydroxide aqueous solution at 60 ° C. for 30 minutes, then rinsed with warm water at 40 ° C. for 1 minute, dried, and colored with iodine according to the following criteria. The punchability was evaluated.
A: There was no colored portion on the entire surface.
B: A colored portion was observed in part.
C: The part colored in the spot was seen over the whole surface.

  In Table 3, the value of the amount of glue is “Watted with glue” (Kaeduka Fukada, Teruhiko Ichimi, published by the Textile Machinery Society of Japan, 4th edition), pages 299-302. It is a value measured by a method for correcting.

  As shown in Table 3, it can be seen that the glued yarns using the fiber sizing agents of Examples 1 to 8 have less detachment at the time of divide and are excellent in weaving property and desizing property. On the other hand, it can be seen that the sizing yarn using the fiber sizing agent of Comparative Examples 1 to 9 has a large amount of detachment at the time of divide, and the weaving property and the desizing property are insufficient. In particular, PVA in Comparative Examples 2 and 4 could not be used as a fiber paste.

  As described above, the fiber glue of the present invention can reduce glue removal during the divide of the glued yarn, and is excellent in weaving and desizing. In addition, the glued yarn of the present invention has little glue removal at the time of divide, and is excellent in weaving properties and desizing properties. Furthermore, since the manufacturing method of the fabric of the present invention uses the glued yarn, the fabric can be provided simply.

Claims (5)

A fiber paste containing a vinyl alcohol polymer (A),
The ratio (Mw (A) / Mn (A)) of the weight average molecular weight (Mw (A)) to the number average molecular weight (Mn (A)) of the vinyl alcohol polymer (A) is 3 or more and 8 or less,
Weight average molecular weight (Mw) relative to the number average molecular weight (Mn (B)) of the vinyl alcohol polymer (B) obtained by treating the vinyl alcohol polymer (A) in a sodium hydroxide solution at 40 ° C. for 1 hour. (B)) ratio (Mw (B) / Mn (B)) is 2 or more and less than 3.
Textile glue. The vinyl alcohol polymer (A) is obtained by polymerizing a vinyl ester monomer in the presence of the monomer (a), followed by saponification and heat treatment,
The monomer (a) is a carboxylic acid having an unsaturated double bond, an alkyl ester of a carboxylic acid having an unsaturated double bond, an acid anhydride of a carboxylic acid having an unsaturated double bond, or an unsaturated double bond. The paste for fibers according to claim 1, which is at least one selected from the group consisting of a carboxylic acid salt having a bond and a silyl compound having an unsaturated double bond.   The paste for fibers according to claim 1 or 2, further comprising a wax. A glued yarn comprising a raw yarn and a binder impregnated in the raw yarn,
A glued yarn, wherein the binder is formed from the fiber glue according to any one of claims 1 to 3. A method for producing a woven fabric, comprising a step of weaving the glued yarn according to claim 4.