JP2852475B2 - Warp sizing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a warp sizing method in a weaving preparation process.

[0002]

2. Description of the Related Art Sizing warp yarns for weaving has been generally employed as a means for imparting conjugation properties and bundling properties to warp yarns, reducing the warp of the warp yarns, and improving wear resistance. Beam sizing machines, warper sizing machines, roller sizing machines and the like are used.
In each case, a high-molecular compound such as starch, polyvinyl alcohol, or an acrylic resin is heated and dissolved in water, and if necessary, an oil agent, an antifoaming agent, etc. are added to prepare a size liquid, and the yarn is glued. Immerse in the liquid or contact the rotating roller to apply the size liquid and evaporate the water with a drying chamber or hot air to produce the sizing thread, which is used for innovative looms such as water jet loom and air jet loom Weaving is performed. However, in this method, there is a problem that a large amount of energy is consumed in the heating and drying step, and a sizing method that does not require the heating and drying step has been demanded.

On the other hand, recently, there has been a rise in new synthetic fibers whose heating has been restricted, such as hetero-shrinkage mixed fiber yarns having high performance, and a heat-drying step is not included in order to glue such yarns that cannot be heated. A sizing method is desired.

[0004] As a method for solving the above-mentioned problem of heat drying, a dry sizing method in which a paste is dissolved in an organic solvent for sizing is conventionally known. There are problems such as the necessity of the process, and the problem that the organic solvent emitted in the working process and the heating / drying process deteriorates the working environment and the global environment.

As another solution, a method of weaving by attaching only a wax to a yarn (Japanese Patent No. 828910), and a system of a mineral oil, a fatty acid ester and a nonionic activator and a phosphate triester or phosphite triester are known. Composition comprising rudiorganopolysiloxane (JP-A-52-137)
No. 096), methods which mainly rely on the smoothness of the oil agent have been proposed. However, in these methods, the smoothness of the warp is improved, but sufficient bunching properties cannot be obtained, and the original sizing There were problems such as the purpose not being achieved.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a warp sizing method which does not require a heating and drying step and can produce a sized yarn having excellent weaving properties.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have repeated studies on a warp sizing method which does not require a heating and drying step. And to form a resin film. Even if such a resin film has the desired effect in the weaving process, it needs to be easily neutralized with an alkali agent and completely removed and removed in the scouring process. Therefore, the acrylic monomer has a considerable acid value. It has been found that a half esterified product of a polybasic acid anhydride and a hydroxyalkyl (meth) acrylate is particularly suitable. Further, in order to make the resin film formed on the yarn tough, it is necessary to use an acrylic copolymer composed of (meth) acrylic acid ester having 1 to 18 carbon atoms and (meth) acrylic acid in combination with the above components. It turned out that there was. The sizing composition obtained by adding a photopolymerization initiator to the combination formulation gives a resin film of sufficient performance on the yarn by ultraviolet curing, but when applying this composition to a very delicate yarn with a roller. Due to its high viscosity, uneven adhesion is caused, and it is difficult to uniformly adhere to the yarn as it is, so that a photopolymerizable monomer for dilution that lowers the viscosity of the composition is required. Further turned out.

That is, the warp sizing method according to the present invention comprises: (a) a half esterified product of a polybasic acid anhydride and hydroxyalkyl (meth) acrylate;
Acrylic copolymers obtained by copolymerizing a monomer containing 60% by weight or more of (meth) acrylic acid ester and (meth) acrylic acid of aliphatic alcohols having an acid value of 30 or more, An ultraviolet curable sizing composition comprising c) a photopolymerizable monomer and (d) a photopolymerization initiator is attached to the yarn before the beaming step, and is cured by irradiation with ultraviolet light.

In the present invention, (meth) acrylate is acrylate and / or methacrylate, (meth) acrylate is acrylate and / or methacrylate, and (meth) acrylic acid is It means acrylic acid and / or methacrylic acid, respectively.

In the above component (a), polybasic acid anhydrides include, for example, phthalic anhydride, tetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhydrophthalic anhydride,
-Methyl hexahydrophthalic anhydride, hymic anhydride, dodecylsuccinic anhydride, trimellitic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride and the like can be used. Examples of the hydroxyalkyl (meth) acrylate that forms a semi-esterified product with the polybasic acid anhydride include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. And at least one of polypropylene glycol mono (meth) acrylate and polybutylene glycol mono (meth) acrylate.

The semi-esterified product of the polybasic acid anhydride and hydroxyalkyl (meth) acrylate is used in an amount of 90% by weight or less based on the total amount of the sizing composition so that the resin film formed on the yarn is not brittle. It is preferable to suppress.

In the above component (b), the number of carbon atoms is 1 to 18.
Examples of the aliphatic alcohol acrylate include methyl, propyl, isopropyl, normal butyl, isobutyl, cetyl, stearyl, oleyl, β-
There are acrylates of alcohols such as ethoxyethyl and the like, and methacrylates of aliphatic alcohols having 1 to 18 carbon atoms, for example, methyl, ethyl,
Propyl, isopropyl, normal butyl, isobutyl, t-butyl, hexyl, octyl, 2-ethylhexyl, lauryl, cetyl, stearyl, oleyl, β-
Examples thereof include methacrylates of alcohols such as ethoxyethyl.

The (meth) acrylic acid ester of an aliphatic alcohol having 1 to 18 carbon atoms may be used alone or in combination of two or more of acrylic acid and / or methacrylic acid and an alcohol solvent or a mixed solvent of water and the solvent. After the completion of the polymerization, the solvent is removed by distillation to obtain a required copolymer. It is necessary that the copolymer has an acid value of 30 or more in order to secure refining properties in the subsequent step, and it is particularly preferable that the copolymer has an acid value of 50 or more. In order to suppress an increase in the viscosity of the paste and to secure uniform adhesion to the yarn, it is preferable to suppress the viscosity to 60% by weight or less based on the total amount of the sizing composition. In the copolymerization, the monomer composed of the (meth) acrylic acid ester and the (meth) acrylic acid is contained in an amount of 60% by weight or more based on the total amount of the monomer in order to impart toughness to the resin film. Need to be done.

As the photopolymerizable monomer in the component (c), an acrylate ester monomer which dissolves an acrylic copolymer is preferable. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Acrylate, polyethylene glycol mono (meth) acrylate, polybutylene glycol (meth) acrylate, polycaprolactone mono (meth) acrylate, cellosolve (meth) acrylate, methyl cellosolve (meth) acrylate, carbitol (meth) acrylate, methyl carbitol ( (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylamide and It can be used at least one from such Takuriruamaido. The photopolymerizable monomer used for adjusting the viscosity of the sizing composition is preferably suppressed to 40% by weight or less based on the total amount of the sizing composition in order to easily remove the resin film in the scouring step. preferable.

In the above component (d), the photopolymerization initiator for polymerizing the photopolymerizable monomer includes, for example, benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin-n-butyl ether, benzoin-isobutyl Ether, benzophenone, diacetyl, acetophenone, anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 1,4-isopropylphenyl-2-hydroxy-2 -Methylpropan-1-one and 2-hydroxy-
Known materials such as 2-methyl-1-phenylpropan-1-one can be used. The photopolymerization initiator is usually used in an amount of 1 to 5 parts by weight based on 100 parts by weight of the photopolymerizable monomer.

The ultraviolet-curable sizing composition used in the present invention is prepared by blending the above-mentioned components. When sizing, for example, 100
A roller is brought into contact with a roller immediately before winding into a beam and a sizing composition is attached to the raw yarn ran at a yarn speed of ~ 400 m / min. The composition may be cured, and the obtained sized yarn is subjected to weaving without passing through heat drying, successively through beaming, twilling and warping. 1 for UV curing
Ultraviolet rays in the wavelength region of 50 to 500 nm, preferably 300 to 450 nm are effective, and as a light source that emits ultraviolet rays, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp,
Carbon arc lamps, metal halide lamps and the like can be suitably used.

The warp sizing method according to the present invention can be suitably applied to various weaving preparation steps as described below, and enables good weaving. (B) Yarn → glue → UV irradiation → twist → beaming →
Twilling → threading → weaving (b) Raw yarn → twisted yarn → gluing → UV irradiation → beaming →
Twilling → threading → weaving (c) Raw yarn → false twist → gluing → UV irradiation → coning → beaming → twilling → threading → weaving (d) Raw yarn → twisted yarn → gluing → ultraviolet irradiation → repetition → beaming → twilling → warping Threading → weaving (e) yarn → warper sizing → ultraviolet irradiation → beaming → twilling → threading → weaving

In the case where smoothness is particularly required in weaving, an additive such as a wax emulsion and a dimethylsiloxane-based silicone release agent may be used in combination with the above-mentioned paste composition. After-waxing,
Processing such as after oiling can also be performed.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.

Example 1 A three-necked flask equipped with a stirrer and a condenser was charged with hexahydrophthalic anhydride.
54 kg (10 mol) and 1.16 kg (10 mol) of 2-hydroxyethyl acrylate were charged, and 0.1 g of hydroquinone monomethyl ether was added.
The reaction was carried out at 00 ° C. for 6 hours to obtain component (a) hexahydroxyphthalic acid monoacryloylhydroxyethyl ester.

On the other hand, another three-necked flask equipped with a stirrer and a condenser was charged with isopropyl alcohol 1000.
g, butyl acrylate 300 g, methyl methacrylate 400 g, stearyl methacrylate 200 g and acrylic acid 100 g.
g was added thereto and polymerization was carried out for 4 hours while refluxing at 85 ° C., followed by cooling, and the diluting solvent was removed under reduced pressure to obtain a copolymer of component (b). The acid value of this copolymer was 79.

600 g of the copolymer of component (b) is added to 600 g of hydroxyethyl methacrylate of component (c).
After heating to 0 ° C. to dissolve and cool, the component (a) is added thereto.
Was added, and 40 g of benzoin ethyl ether and 60 g of 2-ethylanthraquinone as the component (d) were further added to obtain an ultraviolet-curable sizing composition.

The sizing composition was adhered to a polyester yarn (50 denier / 24 filaments, 50 / m with interlace) using a high speed warper “Tsudakoma TW-N” (manufactured by Tsudakoma), and a high-pressure mercury lamp (80 W / (2 lamps), the running yarn was irradiated with ultraviolet rays, and the glue composition on the yarn was cured to prepare a glued yarn.

For comparison, a comparative sizing method including a heating and drying step was used as Comparative Example 1, and an acrylic sizing agent “Plus Size J-96” adjusted to a sizing agent concentration (pure content) of 10% was used. "Tsudakoma KS-200", a warper sizing machine using polyester yarn (50 denier / 24 filaments, no interlacing) with (Yoryo Chemical Industry)
(Made by Tsudakoma Co., Ltd.) and dried by heating in a drying chamber and a drying cylinder. Furthermore, the case of the oil replenishment method was used as Comparative Example 2, and an oil agent (oil) -based oiling agent "Sitex S-571" (manufactured by Kyogo Chemical Industry Co., Ltd.) was used as a polyester yarn (50 denier / 24 filaments, 50 yarns / m with interlace). With a high speed warper "Tsudakoma TW-N" (manufactured by Tsudakoma).

Next, using the yarns according to Example 1 and Comparative Examples 1 and 2, a loom "Tsudakoma ZW-313" was used.
100 × 77 pieces / inch taffeta were woven by a “type” (manufactured by Tsuda Koma). The results are shown in Table 1 below.

In Example 1 according to the present invention, compared with Comparative Example 1, the heating and drying step is unnecessary, so that the energy consumption is small, and a large yarn speed can be selected, so that the productivity is improved, and the weaving step is also improved. The desired weaving efficiency was obtained.
In Comparative Example 2, the heating and drying step was unnecessary, and a high yarn speed could be selected. However, the number of causes of stopping in the weaving step was large, and smooth weaving was not obtained.

[0027]

[Table 1]

Example 2 In the same manner as in Example 1, 1.54 kg (10 mol) of phthalic anhydride was reacted with 1.20 kg (10 mol) of 2-hydroxyethyl methacrylate to obtain the component (a). Monomethacryloyl hydroxyethyl phthalate was obtained.

On the other hand, 600 g of the same copolymer as the component (b) in Example 1 was dissolved in 600 g of the hydroxypropyl acrylate of the component (c) by heating to 50 ° C., and after cooling, the component (a) was added thereto. ), 600 g of monomethacryloyl hydroxyethyl phthalate, and 40 g of benzoin ethyl ether and 60 g of 2-ethylanthraquinone as the component (d) were further added to obtain an ultraviolet-curable paste composition.

The above-mentioned paste composition is mixed with a polyester yarn (60 denier / 48 filaments, twisted 3
(00 times / m) using the same high-speed warper as in Example 1, irradiating the running yarn with a high-pressure mercury lamp (80 W / 2 lamps) with ultraviolet rays, curing the glue composition on the yarn, and gluing. A yarn was made.

For comparison, the case of the conventional sizing method including a heating and drying step is referred to as Comparative Example 3, and an acrylic paste "Plus Size J-97" prepared to a paste concentration (pure content) of 13%. (Manufactured by Ryo Kagaku Kogyo Kogyo Co., Ltd.) was adhered to the same polyester yarn by the same warper sizing machine as in Example 1, and dried by heating in a drying chamber and a drying cylinder. Further, the case of the oil replenishment method was used as Comparative Example 4, and an oil agent (wax) -based soft wax agent “Citex GLO-1400” (manufactured by Kyogo Chemical Industry Co., Ltd.) was applied to the same twisted polyester yarn as described above and the same as in Example 1. Attached with a high speed warper.

Next, using the yarns according to Example 2 and Comparative Examples 3 and 4, a loom "Tsudakoma ZW-303" was used.
Using a "type" (manufactured by Tsuda Koma), satin having a total of 9738 warp yarns was woven on 100 bridges each. The results are shown in Table 2 below.

In Example 2 according to the present invention, compared with Comparative Example 3, the heating and drying step is unnecessary, so that the energy consumption is small, and the hetero-shrinkage mixed fiber with limited heating is well glued and large. Since the yarn speed can be selected, the productivity was improved, and the desired weaving efficiency was obtained also in the weaving process. In Comparative Example 4, the heating and drying step was unnecessary, and a high yarn speed could be selected. However, the number of causes for stopping in the weaving step was large, and smooth weaving was not obtained.

[0034]

[Table 2]

Example 3 In Example 1, maleic anhydride 9 was used instead of 1.54 kg of hexahydrophthalic anhydride.
An ultraviolet-curable sizing composition was obtained in exactly the same manner as in Example 1 except that 80 g was used.

The sizing composition was applied to a nylon yarn (70 denier / 18 filaments) using an improved warper sizing machine, and the running yarn was irradiated with ultraviolet light by a high-pressure mercury lamp (80 W / 2 lamps) and the yarn was irradiated onto the yarn. The sizing composition was cured to prepare a sizing thread. On the other hand, for comparison, the case of the conventional sizing method including the heating and drying step is referred to as Comparative Example 5, and an acrylic paste “Plus Size J-96” prepared at a paste concentration (pure content) of 8% (Kyogaku Kagaku Co., Ltd.) Industrial) to the same nylon yarn as above with a warper sizing machine “Kawamoto EX
-D "(manufactured by Kawamoto Seiki) and dried by heating in a drying chamber and a drying cylinder.

Next, using each of the yarns according to Example 3 and Comparative Example 5, a loom "Nissan LW-53" (manufactured by Nissan Motor Co., Ltd.)
As a result, weaving was carried out on 100 twigs of 190 pieces / inch each. The results are shown in Table 3 below.

In Example 3 according to the present invention, compared to Comparative Example 5, the heating and drying step is unnecessary, so that the energy consumption is small, and the nylon yarn which dislikes heating is glued well, and the desired weaving efficiency is improved. Obtained. In Comparative Example 5, the nylon yarn caused a difference in expansion and contraction due to the heating, and worms were generated on the beam surface, whereby the quality of the woven fabric was deteriorated.

[0039]

[Table 3]

[0040]

As described above, the warp sizing method according to the present invention does not require a heating and drying step.
It contributes to energy saving and productivity improvement and can be suitably applied to synthetic fiber spun yarn and synthetic fiber spun yarn with limited heating, excellent in weaving properties such as conjugation properties, bunching properties and blocking resistance, and excellent in refining properties. Glued yarn can be manufactured, and an effect such as obtaining a high-quality woven fabric can be obtained.

Claims (1)

(57) [Claims] 1. A semi-esterified product of (a) a polybasic acid anhydride and hydroxyalkyl (meth) acrylate, (b)
Acrylic copolymer having an acid value of 30 or more, obtained by copolymerizing a monomer containing 60% by weight or more of (meth) acrylic acid ester of aliphatic alcohol having 1 to 18 carbon atoms and (meth) acrylic acid. (C) a photopolymerizable monomer and (d)
A warp sizing method comprising: adhering an ultraviolet-curable sizing composition comprising a photopolymerization initiator to a yarn before a beaming step;