JPH1025664A - Sizing agent for synthetic fiber warp and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sizing agent for synthetic fiber warp, showing sufficiently bundling properties even with a small amount of build-up, excellent in water resistance when weaving by a water jet loom method, not causing removal of sizing and improved in scouring properties. SOLUTION: This sizing agent comprises (A) 20-60wt.% of a structural unit derived from a polyalkylene glycol having 500-2,500 molecular weight, (B) 3-15wt.% of a structural unit derived from a low-molecular weight diol containing a carboxyl group, (C) a structural unit derived from a low-molecular weight diol or triol, except the component B, in an amount of the total of the components B and C of 10-35wt.% and (D) 25-60wt.% of a structural unit of a diisocyanate compound. The content of the atomic group, NHCOO is 10-35wt.%, the unreacted isocyanate group at the molecular end is hindered or forms a hydroxyl group and the carboxyl group is neutralized to form a hydrophilic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic fiber multifilament sizing agent used for weaving polyester or polyamide woven fabrics in a water jet loom system, and particularly to a polyester or polyamide multifilament sizing agent. (Sizing agent) and its manufacturing method.

[0002]

2. Description of the Related Art A water jet loom (WJL) for feeding a weft with jetted water is widely used for weaving a synthetic fiber multifilament yarn. Japanese Patent Publication No. 4-2712, column 1, line 22 to column 2, line 5 and Japanese Patent Publication No. 5-4465, column 1, line 16 to
As pointed out in column 2, line 1, this loom uses a large amount of water during weaving, so that the sizing agent film attached to the warp yarn must be given sufficient water resistance. At the same time, it must be sufficiently desizing in the scouring process,
The conflicting factors of compatibility between water resistance and refining must be satisfied at the same time.

Recently, the weaving speed has been increased to 750 rpm or more, and the degree of friction between the warp and the reed and the heald, or the degree of the friction between the warps due to the vertical movement of the heddle has become greater than before, and the damage to the warp has been increased. It is getting bigger. Furthermore, weaving of high-quality woven fabrics other than standard products such as high-density woven fabrics using a large number of fine yarns is increasing. However, in such a case, the amount of glue falling off the reed or heald increases. For this reason, there is a demand for a sizing agent having excellent abrasion resistance that can cope with high-speed weaving even with a small amount of adhesion.

[0004] As a sizing agent for warp in weaving in WJL, a sizing agent comprising an acrylate-acrylic acid copolymer or a sizing agent using polyvinyl alcohol in combination with the sizing agent has conventionally been used. However, in the case of the acrylate-acrylic acid copolymer paste, its paste film is soft and disadvantages are pointed out in terms of adhesiveness, hygroscopicity and the like. As a result, a large amount of adhesive falling during weaving accumulates in the reeds and healds, causing an adhesive phenomenon, causing damage to the warp yarns, lowering the quality of the woven fabric, and resulting in poor weaving. In order to compensate for the drawbacks of the above-mentioned acrylic resin which forms a hard paste film, a paste in which polyvinyl alcohol is used in combination is used for this purpose, but the sizing property is insufficient due to lack of affinity for synthetic fibers. Thread breakage is more likely to occur as the combined ratio of polyvinyl alcohol increases, resulting in a decrease in weaving efficiency (columns 6 to 10 of JP-B-4-2712 and JP-B-4-2713). Column 3 lines 1-9, column 2 of Japanese Patent Publication No. 5-4465
2 to 6 lines, described in JP-A-59-9274, column 2, line 5 to column 3, line 10).

In water-soluble polyester sizing agents, sufficient convergence can be expected, but the amount used in general is limited to a very small amount due to poor refining properties (Japanese Patent Publication No. 4-2713, column 3, 10). ~
33 lines and column 2 lines 16-23 of Japanese Patent Publication No. 5-4466).

The use of water-soluble urethane paste is disclosed in Japanese Patent Publication Nos. 60-18355 and 5-24268, JP-A-57-147013, and JP-A-4-142385. However, because of the sulfonic acid group as the hydrophilic group, the water resistance is not sufficient, and the concentration of the carboxyl group used for the hydrophilic group is low, so that the refining property is not sufficient. I can't find anything that can handle it. In some cases, a polyester polyol component is used as the main chain in order to increase water resistance and adhesion to synthetic fibers (JP-A-61-47880, JP-B-5-24268). In this case, although the conjugation force can be sufficiently expected, the high adhesiveness adversely affects the refining ability. Recently, there are many cases where a greige set is performed to obtain the width of the fabric before the scouring process, and when the warp sized with the polyester polyurethane undergoes such a high temperature treatment,
Polyester-based polyurethane is fixed between the synthetic fiber multifilaments, and has a significant adverse effect on refining.

[0007] As described above, with the speeding up of the WJL weaving process, the contradictory conditions of being able to be used under severe conditions capable of coping with higher speed weaving with a smaller amount of coating and being excellent in refining ability are satisfied. Although warp sizing agents have been demanded, the current situation is that conventional products cannot adequately cope with them.

[0008]

Since weaving by WJL enables high-speed weaving, weaving efficiency is significantly improved as compared with conventional weaving using a shuttle.

Recently, the weaving speed has been further increased (at a rotation speed of 750 rpm or more) in order to improve the productivity, and the damage to the warp has further increased.

Therefore, there is a demand for a sizing agent having excellent bunching properties so that the film adhered to the warp not only achieves both water resistance and refining properties, but also can be used in high-speed weaving.

The conventional acrylic acid ester-acrylic acid polymer-based sizing agent has a drawback in that a large amount of paste is removed during weaving and accumulates in reeds and heald portions. In addition, PVA lacks convergence, and it is difficult to respond to the recent increase in the speed of the weaving process. Although a sizing agent mainly composed of a polyester resin or a polyester-based polyurethane resin has a good conjugation force, it has a large defect in scourability as compared with an acrylate-acrylic acid polymer sizing agent.

The present invention shows sufficient convergence even with a small amount of adhesion, is excellent in water resistance at the time of weaving in WJL, and has no falling paste.
Another object of the present invention is to provide a sizing agent for synthetic fiber warp having excellent refining properties and a method for producing the same.

[0013]

The sizing agent for a synthetic fiber warp according to claim 1 of the present invention comprises an aqueous system comprising the following structural units (A) to (D) and having the features of (a) to (c). It contains a urethane resin as a main component.

(A) 20 to 60% by weight of a structural unit derived from a polyalkylene glycol having a molecular weight of 500 to 2500, and (B) 3 to 3 structural units derived from a low molecular weight diol having at least one pendant carboxyl group.
15% by weight, (C) 15 to 35% by weight of a structural unit derived from a low molecular weight diol or triol other than the component (B) in total with the component (B), and (D) a diisocyanate compound Structural unit of 25 to 60% by weight.

(A) Atomic group NH forming a urethane bonding portion
(C) the content of COO is 20 to 35% by weight, and (B) the unreacted isocyanate group at the molecular terminal of the oligomer is substantially blocked by a blocking agent or forms a hydroxyl group. The carboxyl group is neutralized to form a hydrophilic group.

The sizing agent for a synthetic fiber warp according to claim 2 is the sizing agent for a synthetic fiber warp according to claim 1, wherein
A wax emulsion comprising a nonionic and / or anionic surfactant is contained, and the weight percentage of the wax emulsion relative to the total weight of the aqueous urethane resin and the wax emulsion is 40% by weight or less.

The method for producing a sizing agent for a synthetic fiber warp according to claim 3 is a method for producing a sizing agent for a synthetic fiber warp having the following structures (A) to (E). ) Is provided.

(A) 20 to 60% by weight of a structural unit derived from a polyalkylene glycol having a molecular weight of 500 to 2500, (B) 3 to 15% by weight of a structural unit derived from a low molecular weight diol having a pendant carboxyl group,
(C) 15 to 35% by weight of a structural unit derived from a low molecular weight diol or triol other than the component (B) in total with the component (B), and (D) a structural unit 25 derived from a diisocyanate compound. ~ 60% by weight and (E)
Content of atomic group NHCOO forming urethane binding part 20
~ 35% by weight.

(D) When the equivalent ratio of isocyanate group / hydroxyl group is 1.0 or more, unreacted isocyanate group is 0.3
After mixing and reacting so as to remain to 2.5% by weight, the unreacted isocyanate groups are substantially blocked by a blocking agent. When the equivalent ratio of isocyanate groups / hydroxyl groups is less than 1.0, the hydroxyl value is reduced. (E) Neutralization is performed so that the pendant carboxyl groups derived from the component (B) in the oligomer form a hydrophilic salt.

That is, the urethane resin, which is the main component of the synthetic fiber warp sizing agent of the present invention, uses (1) a polyether diol which is a soft segment and is oxidatively decomposed during high-temperature heat treatment as a long-chain diol component. That
(2) A special water-soluble urethane composed of a urethane oligomer whose main feature is to use a low molecular weight polyol within a specific range in order to distribute urethane bonds at a high density, and which is obtained by performing a predetermined treatment. Resin.

In the case of a polyurethane having a polyether diol as a main chain, it has been pointed out that the water resistance is deteriorated and the adhesion to synthetic fibers is reduced. However, the urethane bond content is increased by using a low molecular weight polyol. By doing so, it was possible to improve the adhesiveness to synthetic fibers and the water resistance, and film properties almost equivalent to those of polyester-based polyurethane were obtained. Since polyether diol is the main chain, the ether bond is oxidatively decomposed when high temperature treatment (180 ° C. × 1 to 2 minutes) such as setting before scouring is not excessively strong in adhesiveness to synthetic fibers. It is characterized in that scourability is greatly improved as compared with polyester-based polyurethane. Further, since no polyester polyol component is used, there is no danger that the physical properties will be reduced due to the hydrolysis over time.

For this reason, the above specific water-soluble urethane resin is insoluble in cold water and is soluble in hot alkali, so that it has excellent water resistance, thereby reducing the contamination of the loom during weaving and at the same time refining the woven fabric. It is possible to improve the performance. Even if the woven fabric is set before scouring, scouring properties equivalent to those of an acrylic paste can be obtained.

Further, since the warp for weaving treated with this sizing agent exhibits excellent sizing properties, smoothness, abrasion resistance and agglutination resistance, it prevents fuzzing and yarn breakage due to mechanical friction during weaving. , 750 rpm and higher speed WJL. Furthermore, since sufficient bunching properties are exhibited even with a small amount of adhesion, it becomes possible to weave a high-density woven fabric that uses a large number of fine yarns as warps at high speed. Furthermore, by blending the wax emulsion in a specific ratio together with the urethane resin, more excellent convergence,
Improvements in smoothness, scratch resistance and agglutination resistance are achieved.

[0024]

Next, the present invention will be described in detail.

The above-mentioned special water-soluble urethane resin uses a urethane oligomer in which the urethane bond (—NHCOO—) content of the urethane oligomer obtained using a specific component and amount is set to a specific range, and this urethane oligomer is used. It is obtained by processing in a specific way.

The urethane oligomer has a molecular weight of 500 to 500.
2500 polyalkylene glycol (component A) and diol having a pendant carboxyl group (component B)
And a pendant carboxyl group derived from the B component of the urethane oligomer obtained by using a low molecular weight polyol (C component) other than the above (B) component and a diisocyanate (D component). It is obtained by treating all or most of the reactive isocyanate groups with a blocking agent.

[0027] The reaction weight ratio of the raw material components in producing the oligomer of the water-soluble urethane resin having a special composition, which is the main component of the present invention, is as follows: high molecular weight polyether diol (A) / chain extender (B) and ( Each component of C) / diisocyanate (D)
They are respectively 20 to 60/15 to 35/25 to 60% by weight, particularly preferably 35 to 50/20 to 35/30 to 60% by weight, respectively.

The polyalkylene glycol component (A) includes:
Polyethylene glycol, polypropylene glycol (PPG), or polyethylene / polypropylene copolymer glycol, polytetramethylene glycol (P
TMG) and the like.

Among these polyalkylene glycols, polytetramethylene glycol is preferred in consideration of water resistance.
A mixture of tetramethylene glycol and polypropylene glycol, a mixture of polytetramethylene glycol and a copolymer glycol of polyethylene glycol / polypropylene glycol, and the like are preferable. The average molecular weight of the high molecular weight polyether diol is preferably from 500 to 2,500, particularly preferably from 700 to 1,600. Average molecular weight 5
If it is less than 00, the content of the soft segment in the oligomer becomes small, so that the obtained film becomes brittle and the weaving efficiency deteriorates. When the molecular weight exceeds 2,500, the urethane bond content in the oligomer is reduced, so that the water resistance and the film strength are reduced, and the effects obtained in the present invention cannot be expected.

The chain extender used in the present invention can be roughly classified into a pendant carboxyl group-containing chain extender (B) as an essential component and a low molecular polyol chain extender (C) having two or more hydroxyl groups in one molecule. .

Examples of the pendant carboxyl group-containing chain extender component (B), which is an essential component, include glycol carboxylic acids such as dimethylolacetic acid, dimethylolpropionic acid, and dimethylolvaleric acid. The component (B) imparts hydrophilicity to the resin to give it a self-emulsifying property, and at the same time controls the water resistance and scourability of the film. Chain extender component
The amount of (B) is preferably 3 to 15% by weight in the oligomer,
Particularly preferably, it is 5 to 10% by weight. If the amount is less than 3% by weight, the water resistance of the film is deteriorated, and if it exceeds 15% by weight, the emulsion stability and the refining property of the film are deteriorated.

The low molecular weight polyol chain extender component (C) having two or more hydroxyl groups in one molecule includes, for example, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5 -Aliphatic diols such as pentanediol, 3-methyl-1,5-pentadiol and 1,6-hexanediol, alicyclic diols such as 1,4-cyclohexanedimethanol, and ethylene oxide (EO) addition of bisphenol A Diols such as adducts or propylene oxide (PO) adducts, and aliphatic triols such as trimethylolpropane, trimethylolethane, hexanetriol, and glycerin.
These chain extender components (C) may be used alone or in combination of two or more. Among them, 1,4
-Butanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentadiol alone or in combination, or in combination with trimethylolpropane,
It is preferable from the viewpoints of water resistance, scratch resistance, and emulsion stability of the obtained film.

The total amount of the chain extender components (B) and (C) is preferably from 10 to 35% by weight in the oligomer, and particularly preferably.
15 to 25% by weight. If the compounding amount is less than 10% by weight, the urethane content in the obtained oligomer is also low, so that the adhesive and sizing properties of the obtained paste are reduced.
If the amount is more than 35% by weight, the urethane content in the oligomer will also be high, so that the flexibility of the resulting paste film will decrease and become brittle, which will worsen the weaving efficiency.

Diisocyanate component used in the present invention
As (D), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4- and 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4 '-Diphenylmethane diisocyanate, xylene diisocyanate, tetramethylene xylylene diisocyanate, 1,5-
Naphthalene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-
Aromatic, alicyclic and aliphatic diisocyanates such as biphenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like. These diisocyanate components may be used alone or in combination of two or more. Among the above diisocyanates, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate in a weight ratio of 80/20 and 65/35 (TDI-80 and TDI-65, respectively), 4,4 '-Diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexyl diisocyanate (H12MDI), hexamethylene diisocyanate (HMDI), and isophorone diisocyanate (IPDI) are more preferable. 65, MDI is more preferred. The content of diisocyanate in the oligomer is preferably from 25 to 60% by weight, particularly preferably from 30 to 50% by weight. If the amount is less than 25% by weight, the water resistance and sizing properties of the paste obtained later will be adversely affected, and if it exceeds 60% by weight, the refining properties of the film obtained later will deteriorate and the control of the reaction may be difficult.

In order to produce the oligomer, a solvent can be used if necessary. Solvents that can be used must be inert and hydrophilic with respect to isocyanates, ketones such as methyl ethyl ketone and acetone, ethers such as tetrahydrofuran and dioxane, esters such as cellosolve acetate, ethyl acetate, and methyl propionate. However, it is more preferable to use a solvent having a boiling point lower than that of water so that the solvent can be recovered by vacuum distillation after hydrophilizing the urethane resin.

In order to produce an oligomer, a high molecular diol component (A) and a low molecular diol component as a chain extender
(B) and (C), a method of simultaneously mixing and reacting the diisocyanate component (D) or reacting the polymer diol component (A) with the diisocyanate component (D) to form an oligomer,
A method of adding the chain extender components (B) and (C) is exemplified. The reaction temperature for oligomerization is preferably in the range of about 65 to 130 ° C.

When the NCO / OH equivalent ratio is 1.0 or more, the end point of the reaction is judged by the concentration of the unreacted isocyanate, and is preferably in the range of 0.3 to 2.5% by weight, particularly preferably 0.5 to 2.0% by weight in the oligomer. Let the reaction proceed until it subsides. When the NCO / OH equivalent ratio is 1.0 or less, the hydroxyl value (OH
value) is preferably 5 to 40, particularly preferably 10
The reaction is allowed to proceed until it falls within the range of 2020.

The characteristic of the urethane oligomer obtained here is that the content of the atomic group NHCOO constituting the urethane binding portion is preferably 20 to 35% by weight, particularly preferably 20 to 30% by weight. Has a composition not found in the water-soluble urethane paste. If the urethane bond content contained in the oligomer is less than 20% by weight, the strength of the film obtained later will decrease, and the convergence and water resistance will deteriorate. If the urethane bond content exceeds 35% by weight, the film loses flexibility and becomes brittle, which in turn lowers the weaving property. In any case, the effects of the present invention cannot be obtained. The average molecular weight of the oligomer obtained here is not limited, but is preferably from 3,000 to 50,000, particularly preferably from 5,000 to 20,000. Average molecular weight of 3,000
If the average molecular weight exceeds 50,000, the sizing and scouring properties of the film may be adversely affected.

When the thus obtained oligomer has an NCO / OH equivalent ratio of 1.0 or more, the unreacted isocyanate is allowed to react until it becomes 2.5% by weight or less as -NCO in order to obtain a stable aqueous solution or aqueous emulsion. Preferably, all or most of the unreacted isocyanate is treated with a blocking agent. Unreacted isocyanate to be treated with the blocking agent is 0.3 to 2.5 as -NCO.
%, Particularly preferably 0.5 to 2.0% by weight. 0.3
If it is less than 10% by weight, the molecular weight of the oligomer will increase, which will adversely affect the refining properties. On the other hand, if it is 2.5% or more, the molecular weight becomes too small, the film strength is reduced, and the conjugation force obtained in the present invention cannot be expected. In addition, it is necessary that the treated blocking agent does not dissociate from the isocyanate group within the operating temperature range and does not regenerate the active isocyanate group at the time of forming the film in the drying step after the treatment of the filament or setting the greige machine.
When the isocyanate group is regenerated, the resin is polymerized by a cross-linking reaction, and although the water resistance of the film is improved, the scourability may be significantly deteriorated. For this reason, it is necessary to suppress the dissociation of the blocking agent from the isocyanate group at the time of drying or setting the greige before scouring, and it is necessary that the dissociation temperature of the blocking agent is higher than the use temperature. Depending on the type of isocyanate used as the blocking agent, C1-18 aliphatic alcohols such as methanol, ethanol, isopropyl alcohol, or lauryl alcohol, monoamines such as dimethylamine, diethylamine, methylethylamine, phenol, cresol, etc. Known blocking agents such as phenols and lactams such as ε-caprolactam are exemplified. Oxime-based blocking agents such as methyl ethyl ketoxime and cyclohexanone oxime have relatively low dissociation temperatures and are therefore not preferred for use in this application. Further, a substance having one amino group and one carboxyl group or a sulfone group in one molecule, for example, glycine, aliphatic monoaminomonocarboxylic acid such as alanine, alicyclic monoaminomonocarboxylic acid such as aminocyclohexanecarboxylic acid, An aliphatic monoaminomonosulfonic acid such as aminoethanesulfonic acid (taurine) can also be used as a terminal isocyanate group blocking agent. If some unreacted isocyanate groups remain even when the NCO / OH equivalent ratio is 1.0 or less, it is preferable to treat with the above-mentioned blocking agent.

Next, in order to emulsify the resin, it is necessary to neutralize the pendant carboxyl groups to make them hydrophilic. Examples of the base to be neutralized include ammonia and organic amines such as trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, methyldiethanolamine, and dimethylethanolamine. Considering the water resistance of the finally obtained film,
It is preferable that the base easily volatilizes by heat at the time of forming the film, and ammonia, trimethylamine, and triethylamine are preferable.

The water-soluble urethane oligomer obtained above is emulsified in water by mechanical shearing force such as stirring. Thereafter, the solvent is preferably recovered by distillation under reduced pressure using an evaporator or the like.

The water-soluble urethane thus obtained is the main component in the resin component. Of course, this water-soluble urethane resin can be used for all of the resin components, or it can be a conventional acrylic ester-acrylic acid copolymer or PVA.
May be partially incorporated within a range that does not impair the effects of the present invention. As various additives, foaming inhibitors (defoaming agents) when recovering the solvent after the resin is made aqueous, weathering agents and yellowing inhibitors (such as hindered amines and hindered phenols) after solvent recovery, A fungicide may be added.

Further, a certain amount of a smoothing agent component may be added to such a resin component mainly composed of water-soluble urethane. Natural wax is mainly used as a smoothing agent component, but a synthetic wax may be used in some cases. As natural wax, candelilla wax in vegetable wax,
Carnauba wax, rice wax, wood wax, etc., animal beeswax, lanolin (wool wax), etc.,
As the mineral wax, montan wax is used, and as the petroleum wax, paraffin wax is used. Examples of the synthetic wax include a polyethylene wax and a fatty acid ester. As fatty acid esters, monohydric alcohols,
Or polyhydric alcohols such as ethylene glycol, butanediol, hexanediol, trimethylolpropane, glycerin, pentaeslit, sorbitan and the number of carbon atoms
Esters with 12-20 fatty acids. Specifically, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, ethyl laurate, ethyl myristate, ethyl palmitate, ethyl stearate, ethyl oleate, glycerin monolaurate, glycerin monolaurate Examples include stearates, glycerin monostearate, pentaeslit monostearate, sorbitan monostearate, and sorbitan monooleate.

When actually used, an emulsion obtained by emulsifying these waxes with a nonionic activator and / or an anionic activator is used. Among these, use of a vegetable wax is particularly preferred, and use of an emulsion of a plant wax or an emulsion of a mixed wax of a plant wax / animal wax / a mineral wax is more preferred in terms of imparting smoothness. Emulsifiers include, as nonionic activators, ethylene oxide adducts of higher alcohols such as lauryl alcohol, cetyl alcohol, oleyl alcohol, and stearyl alcohol, and ethylene oxide adducts of phenols alkylated with octyl, nonyl, and dodecyl groups. No. Anionic surfactants include sulfates and phosphates based on ethylene oxide adducts of higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, and oleyl alcohol, and benzene sulfonates alkylated with a dodecyl group. No.

The solid content ratio of the resin component / smoothing agent component is as follows:
It is 100/0 to 60/40, preferably 98/2 to 70/30. If the solids content of the resin component is less than 60%, the convergence between filaments is reduced, and fluffing or yarn breakage may occur during weaving.

The synthetic fiber multifilament for treating the warp sizing agent obtained by the present invention is not limited, and examples thereof include raw denier yarn of 50 denier / 24 filament to 75 denier / 96 filament of polyester or nylon. The yarn may be an entangled yarn, a processed yarn, or a twisted yarn.

As a method for supplying the warp sizing agent obtained in the present invention to the synthetic fiber multifilaments, a usual sizing method, that is, sizing is applied in a roughly wound beam state,
A method of sizing at a speed of 100 to 150 m / min in the process of roll squeeze, non-touch drying, drum drying,
In the process of winding from krill to beam using direct warper, glue is adhered by roll touch,
After drying with a non-touch dryer, it can also be used with the `` simple sizing '' method of winding immediately on a beam (speed 200 to 400
m / min). In the present invention, the adhesion amount of the warp sizing agent to synthetic fibers is preferably 2.0 to 10.0% by weight, particularly preferably 4.0 to 9.0% by weight for raw yarn. When the yarn is an entangled yarn, a processed yarn, or a twisted yarn, the adhesion amount is preferably 0.5 to 5.0% by weight, and particularly preferably 1.0 to 3.0% by weight. If the amount of adhesion is less than the predetermined amount, the convergence between filaments is reduced, and fluff is likely to occur during weaving. If the amount of adhesion exceeds a predetermined amount, when the wound yarn is unwound, sticking may occur between the yarns, causing breakage of the yarn, and furthermore, glue may drop off during weaving, causing loom contamination.

The blend of the resin component and the smoothing agent component mainly composed of water-soluble urethane thus obtained is excellent in sizing and adhesiveness to synthetic fibers, and has both sufficient water resistance and scouring property, and Shows good smoothness.

The method for evaluating the warp size of the present invention is described below.

<Gluing Test> (1) Lab Processing Gluing processing was performed in a laboratory, and five points of adhesive adhesion amount, embracing force test, water resistance test, scouring test, and adhesion test were evaluated.

Equipment used KHS universal sizer manufactured by Kakinoki Co., Ltd. Gluing speed 250 m / min (2) Actual machine processing (2-1) Gluing processing Equipment used Sizer KS-200 manufactured by Tsudakoma Kogyo Co., Ltd. Drying conditions 2-chamber, 2-drum (chamber 120-1
(30 ℃, drum 100 ℃), Speed 120m / min (2-2) Weaving Equipment Tsudakoma Kogyo Co., Ltd. Water Jet Loom ZW-303 Weaving speed 750 (rpm) <Gluing yarn evaluation method> (1) Adhesion Amount The glued yarn and the glued yarn are scoured in a 100-fold amount of scouring bath (scouring agent / scum dispersant / sodium hydroxide = apparent 2.0 (g / l) /0.5
(composition of (g / l) /0.5 (g / l)) After repeating twice at 90 ° C for 10 minutes, wash with hot water, wash with water and dry, measure the yarn weight, glue yarn and desizing yarn And the weight difference between the glued yarn and the blank yarn were used to determine the amount of adhesion.

(2) Tying force test In a 20 ° C., 75% RH atmosphere, using a TM-type tying force tester, a load of 100 g per sized yarn was applied, and friction was applied until yarn breakage occurred. The number was counted.

(3) Water resistance test The glued yarn was stirred in 100 times the volume of tap water (20 ° C.) for 10 minutes, and then the amount of glue removed was measured from the weight of the glued yarn. × 100 was used as an index of water resistance as a water bath desizing ratio.

(4) Refining test The glued yarn and the blank yarn were subjected to a 100-fold amount of a refining bath [refining agent /
Scum dispersant / sodium hydroxide = apparent 2.0 (g / l) / 0.
5 (g / l) /0.5 (g / l)], stir at 90 ° C for 1 minute, measure the amount of sizing from the weight of the sizing thread, and also consider the weight difference between the sizing thread and the blank thread. , (Amount of glue / Amount of adhesion) ×
100 was used as an index of scouring ability as a scouring bath desizing ratio. (5) Adhesive The glued yarn is wound on a bobbin at a yarn speed of 50 m / min and a running tension of 30 (g), and left for 24 hours at 25 ° C. × 75 RH. Judgment was made based on the feel of the hands when solving the problem and visual observation. Thereby, ◎: no tackiness,
：: almost no stickiness, Δ: slightly sticky,
X: It was determined in four stages of "high adhesion".

(6) Desizing Property The degree of degleasing when weaving the polyester taffeta in a water jet loom at a speed of 750 rpm for 10,000 m was determined by tactile sensation and visual observation. As a result, ◎: no paste removal, ○: almost no paste removal,
.DELTA .: There was little paste removal, and X: There were many paste removals.

(7) A reciprocity ratio The ratio of the A reciprocal ratio in the woven fabric when weaving the polyester taffeta in a water jet loom at 10,000 rpm traveling at a speed of 750 rpm was expressed in%.

(8) Operating rate The percentage of the actual weaving time, which is obtained by subtracting the time during which the loom stagnated due to a trouble during weaving from the total time required for weaving in the water jet loom, is expressed as a percentage.

[0058]

EXAMPLES Next, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following examples, and may be appropriately modified within a range that can be adapted to the gist of the preceding and following descriptions. The present invention can be implemented, and all of them are included in the technical scope of the present invention. The parts in the examples are parts by weight.

<Example 1> (Production of water-based polyurethane resin) In a four-necked reactor equipped with a thermometer, a nitrogen gas inlet tube, a stirrer and a reflux condenser,
While introducing nitrogen gas, polytetramethylene glycol (number average molecular weight 1,000, PTMG manufactured by Mitsubishi Chemical Corporation)
-1000) 100 parts, 1,4-cyclohexanedimethanol (1,4-CHDM) 14 parts, tolylene diisocyanate (TD
I-80) 57 parts, 113 parts of methyl ethyl ketone were charged,
After reacting at 75 ° C. for 45 minutes, 13 parts of dimethylolpropionic acid (DMPA) is added and reacted for about 1 hour to synthesize a urethane oligomer containing about 1% by weight of unreacted isocyanate (the urethane bond content in the oligomer, that is, , The content of the atomic group NHCOO forming the urethane binding portion is 21%),
After cooling to 50 ° C., 3.1 parts of butanol was added, and 9.8 parts of triethylamine (TEA) was further added. 42 more water
After adding 0 parts and mixing and emulsifying, the solvent was removed by an evaporator at 50 ° C., and the solid content was adjusted to 30% to obtain a milky white water-soluble urethane resin A.

(Preparation of wax emulsion) Carnauba wax 25 parts, beeswax 25 parts, montan wax 20 parts,
A wax consisting of 5 parts of sorbitan monooleate was melted, and 15 parts of a nonionic activator of ethylene oxide adduct of oleyl alcohol (polyoxyethylene oleyl ether) and 5 parts of a phosphate ester of dinonylphenol ethylene oxide were added as emulsifiers. The resulting mixture was diluted with warm water and maintained at an emulsifying temperature of 80 ° C. to dilute the solid content to 20% to obtain a wax emulsion E1. Similarly, a wax emulsion E2 was obtained from the raw materials shown in Table 6.

(Weaving and evaluation) Polyester multifilament yarn (50d / 24fil; non-twisted yarn) was blended with a water-soluble urethane resin A at a solid content of 8.5% and a wax emulsion E1 at a solid content of 1.5%. % Of the paste was glued to the polyester yarn using a KHS universal sizer. First, the properties (adhesion amount measurement, embracing power, water resistance, scourability, and tackiness) of this glued yarn were evaluated.
As a result, this sized yarn has both good water resistance and scouring property, and also has a sufficient embracing power (Table 1). Next, the blended paste having a pure content of 10.0% was similarly glued to a polyester multifilament (50d / 24fil .; non-twisted yarn) using a KHS universal sizer. Using this glued yarn as warp,
Polyester multifilament (50d / 24fi)
l .; Water jet loom (ZW-303 manufactured by Tsuda Koma Kogyo Co., Ltd., 7,200 warp yarns, weaving width 173c)
m), weaved polyester taffeta at a speed of 750 rpm and 50 bridges as one bridge. There was no glue loss during weaving, and there was no fluff, and the A rejection was 99%. Loom operation rate was 99% (Table 1).

[0062]

[Table 1] <Comparative Example 1> A commercially available acrylic sizing agent for water jet loom was diluted to give an aqueous solution having a solid content of 10.0%, and the sizing was first performed using a KHS universal sizer under the same conditions as in Example 1 to determine the properties of the sizing thread. evaluated.

Thereafter, the diluted sizing agent A (10.0% solution) was glued to the yarn using Sizer KS-200. This glued yarn is used as a warp, and a polyester multifilament (50d / 24fil .; non-twisted yarn) is used for the weft, and a water jet loom (ZW-303 manufactured by Tsuda Koma Kogyo Co., Ltd., warp 7,
Polyester taffeta at a speed of 75 with a weave width of 173 cm)
Weaving was performed at 200 rpm with 50 rpm as one bridge at 0 rpm. As a result, a slight amount of glue was found on the reeds and healds, and the A reversion rate was 94% and the loom operating rate was 94% (Table 1).

<Examples 2 to 40> In the same manner as in Example 1, the water-soluble urethane resins B to
Z and ad were obtained. As shown in Tables 2 to 5, any of PTMG-500, -1000, and 2500 (polytetramethylene glycol manufactured by Mitsubishi Chemical Corporation, having a number average molecular weight of about 500, 1000, and 2500, respectively) was used as the polyalkylene glycol. Or PPG -500, -1000, -2500 (Polypropylene glycol manufactured by Daiichi Kogyo Seiyaku Co., Ltd., each having a number average molecular weight of about 50
0, 1000 and 2500), or PTMG-1000 and PPG-10
A mixture with 00 was used at various mixing ratios. Examples of the chain extender having no carboxylic acid include 1,4-cyclohexanedimethanol (1,4-CHDM) and 1,4-butanediol (1,4-B
D), 3-methyl-1,5-pentadiol (MPD), and trimethylolpropane (TMP).

Polyester multifilament (50d / 2
4fil .; non-twisted yarn), water-soluble urethane resins B to d,
The wax emulsions E1 and E2 were glued using a KHS universal sizer as a 10.0% solution of each of the sizing agents shown in Table 4 below. Here, the wax emulsion E2 was prepared from the raw materials shown in Table 6 in the same manner as in E1 in Example 1. The properties (adhesion amount measurement, embracing power, water resistance, scourability, tackiness, hygroscopicity) of this glued yarn were evaluated. The results are shown in Tables 7 to 10.

[0066]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10] <Comparative Examples 2 to 14> The same tests as in Examples 2 to 40 were performed on the paste compositions shown in Table 11. Table 12 shows the results.
Shown in

[0067]

[Table 11]

[Table 12] <Example 41> Polyester multifilament yarn (75
d / 96fil .; wooly yarn), 8.5% of solid content of water-soluble urethane resin F, wax emulsion E2
Used in Example 6 containing 1.5% as a solid content
(Solid content 10.0% solution) was glued using Warping Sizer KS-200. This glued yarn is used as a warp, and a polyester multifilament (75d / 96fil .;
Woolly yarn, water jet loom (ZW-303, Tsuda Koma Kogyo Co., Ltd., 6,690 warp yarns, weaving width 17
3cm), weaving polyester taffeta at 750rpm and 200m per 50m. There was no falling glue during weaving, and there was no fluff, and the A rejection was 99%. Loom operation rate is 99%
(Table 13).

[0068]

[Table 13] Comparative Example 15 A commercially available acrylic paste (a 10.0% solid solution) for water jet loom was glued to a polyester multifilament yarn (75 d / 96 fil; Woolly yarn). Using this glued yarn as warp, polyester multifilament (75d / 96fil .; wooly yarn) as weft, water jet loom (ZW-303, Tsuda Koma Kogyo Co., Ltd., 6,690 warp, 173cm weaving width) Polyester taffeta at 750 rpm and 50 m per bridge 200
Hiki weaved. As a result, falling glue was observed on the reed and heald,
The rejection rate was 94%, and the loom operation rate was 95% (Table 13).

From Table 13, it can be seen that the urethane-based sizing agent of Example 41 (the sizing agent used in Example 6) exhibited a weaving property equal to or greater than that of the acryl-based sizing agent even with about half the adhesion amount. .

<Example 42> 8.5% of a water-soluble urethane resin D as a solid content relative to a nylon multifilament yarn (70d / 24fil; non-twisted yarn), and a wax emulsion E
The sizing machine (solid 10.0% solution) used in Example 4 containing 1.5% as a solid content of No. 2 was dried using a sizing machine KS-500 at a sizing speed of 300 m / min and a chamber temperature of 120 ° C. under drying conditions. After drying, it was wound around a beam and glued in the form of a simple sizing of krill to beam. This glued yarn is used as a warp, and a nylon multifilament (70d / 24fil .; Taslan yarn) is used for the weft, and a water jet loom (KIC966, manufactured by Eki Tekko Co., Ltd., warp 6,690)
Weaving was carried out at a speed of 750 rpm at a speed of 750 rpm and at a length of 50 m. There was no falling glue during weaving and there was no fluff, and the A rejection was 98%. The loom operation rate was 98% (Table 14).

[0071]

[Table 14] <Comparative Example 16> A commercially available acrylic sizing agent for water jet loom (solid solution 10.0% solution) was subjected to sizing by simple sizing in the same manner as described above on a nylon multifilament yarn (70d / 24fil .; non-twisted yarn). Was. This glued yarn was slightly insufficient in drying property. Using this glued yarn as warp,
Nylon multifilament (70d / 24fil .; Taslan yarn) is used for the weft, and water jet loom (KIC966, manufactured by Eki Tekko Co., Ltd., 6,690 warps, 173cm weaving width)
With polyester taffeta at 750 rpm and 50 m as one bridge
Weaved for 200 beaches. As a result, falling glue was observed on the reeds and healds, and the A rejection rate was 92% and the loom operating rate was 93% (Table 1).
4).

From Table 14, it can be seen that the urethane type sizing agent of Example 42 (the sizing agent used in Example 5) shows the same or higher weaving property even with about half the adhesion amount of the acrylic sizing agent. .

[0073]

EFFECT OF THE INVENTION In a urethane having a polyether diol as a main chain, by increasing the urethane bond content by using a low molecular weight polyol as a chain extender, it becomes possible to improve the adhesiveness to synthetic fibers and the water resistance, thereby improving the polyester-based properties. Almost the same film properties as urethane were obtained. Since the polyether diol is the main chain, the adhesiveness to the synthetic fiber is not excessively strong. When a high-temperature treatment (180 ° C. × 1 to 2 minutes) such as setting before scouring is performed, ether bonds are oxidized and decomposed to scour. The properties are greatly improved as compared with polyester-based urethane. In addition, since no polyester polyol component is used, there is no danger of hydrolysis over time and deterioration of physical properties.

Since it is insoluble in cold water and is soluble in hot alkali and has excellent water resistance, it is possible to reduce the contamination of the loom during weaving and to improve the refining property of the woven fabric. Even if the woven fabric is set before scouring, scouring properties equivalent to those of an acrylic paste can be obtained.

Further, since the warp for weaving treated with this sizing agent exhibits excellent bunching, smoothness, abrasion resistance and agglutination resistance, it prevents fluff and yarn breakage due to mechanical friction during weaving. , 750 rpm and higher speed WJL. Furthermore, since sufficient bunching properties are exhibited even with a small amount of adhesion, it becomes possible to weave a high-density woven fabric that uses a large number of fine yarns as warps at high speed. Furthermore, by blending the wax emulsion in a specific ratio together with the urethane resin, more excellent convergence,
Improvements in smoothness, scratch resistance and agglutination resistance are achieved.

Claims (3)

[Claims] 1. A sizing agent for a synthetic fiber warp comprising, as a main component, an aqueous urethane resin comprising the following structural units (A) to (D) and having the characteristics of (a) to (c). (A) 20 to 60% by weight of a structural unit derived from a polyalkylene glycol having a molecular weight of 500 to 2500, and (B) a structural unit 3 to 15 derived from a low molecular weight diol having at least one pendant carboxyl group.
(C) 10 to 35% by weight of a structural unit derived from a low molecular weight diol or triol other than the component (B) in total with the component (B), and (D) a diisocyanate compound-derived component. Structural unit 25-6
0% by weight. (A) the content of the atomic group NHCOO constituting the urethane binding portion is 20 to 35% by weight, and (b) the unreacted isocyanate group at the molecular terminal of the oligomer is substantially blocked by a blocking agent or the hydroxyl group is (C) the pendant carboxyl group is neutralized to form a hydrophilic group. 2. The sizing agent for a synthetic fiber warp according to claim 1, further comprising a wax emulsion comprising a wax and a nonionic and / or anionic surfactant, wherein the total amount of the aqueous urethane resin and the wax emulsion is included. A sizing agent for synthetic fiber warp, wherein the weight% of the wax emulsion is not more than 40% by weight based on the weight. 3. A method for producing a synthetic fiber warp sizing agent having the following structures (A) to (E), comprising the following (d) to (e):
A method for producing a sizing agent for synthetic fiber warp, comprising the steps of: (A) 20 to 60% by weight of a structural unit derived from a polyalkylene glycol having a molecular weight of 500 to 2500; (B) 3 to 15% by weight of a structural unit derived from a low molecular weight diol having a pendant carboxyl group; The structural unit derived from a low molecular weight diol or triol other than the component (B) is 15 to 35% by weight in total with the component (B), and the structural unit 25 to 6 derived from a (D) diisocyanate compound.
0% by weight, and (E) the content of the atomic group NHCOO constituting the urethane binding portion is 20 to 35% by weight. (D) When the equivalent ratio of isocyanate group / hydroxyl group is 1.0 or more, the unreacted isocyanate groups are mixed and reacted so that 0.3 to 2.5% by weight of unreacted isocyanate groups remain, and the unreacted isocyanate groups are blocked. When the equivalent ratio of isocyanate group / hydroxyl group is less than 1.0, it is blended and reacted so that the hydroxyl value becomes 5 to 40. (e) To the component (B) in the oligomer, The pendant carboxyl groups are neutralized so as to form a hydrophilic salt.