JP2007031915A - Treating agent for processing polytrimethylene terephthalate-based fiber and polytrimethylene terephthalate-based fiber treated by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treating agent for processing polytrimethylene terephthalate-based fiber which is a water-dispersed polyester resin improved in compatibility with a polytrimethylene terephthalate-based fiber and excellent in stability and to provide a polytrimethylene terephthalate fiber to which functions excellent in washing resistance and durability, particularly excellent stain-proofing property and water-absorbing property are imparted by using the treating agent. <P>SOLUTION: The treating agent for processing polytrimethylene terephthalate-based fiber is obtained by dispersing a polyester resin obtained by copolymerizing 1,3-propylene glycol with a polyalkylene glycol (A) having 600-6,000 number-average molecular weight as essential components into water. The polytrimethylene terephthalate-based fiber is treated by using the treating agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polytrimethylene terephthalate (hereinafter abbreviated as “PTT”) fiber treatment agent using a water-dispersible polyester resin, and a PTT fiber treated with the treatment agent, particularly for washing durability. It is intended to provide a PTT fiber woven fabric imparted with a high antifouling function and a water absorption function with excellent properties.

  Compared to conventional polyethylene terephthalate (PET) resin and polybutylene terephthalate (PBT) resin, which are representative of thermoplastic polyester resin, PTT resin is particularly excellent in elastic recovery, chemical resistance, weather resistance, electrical properties, etc. Therefore, application to industrial products has been promoted mainly in the field of textile products in recent years. In recent years, applications as films, sheets, and engineering plastics are also being studied. For example, Patent Document 1 discloses that a metal plate is covered with a PTT film for the purpose of imparting impact resistance to the metal plate. Patent Document 2 discloses application to OA equipment parts, home appliance parts, and automobile-related parts. Similarly, Patent Document 3 discloses applications to automobile parts and electric / electronic parts.

  On the other hand, in the textile product field, PTT fibers have an extremely soft texture compared to polyethylene terephthalate fibers, and are excellent in stretchability, drapeability, low-temperature dyeability, weather resistance, etc. Application to applications is being studied. For example, Patent Document 4 proposes a PTT fiber suitable for clothing. Patent Document 5 proposes a PTT filament suitable for screen papermaking and a toothbrush.

  For such PTT fibers, the conventional polyester treatment agent lacks familiarity with the processing substrate, so the durability of the function imparted by the treatment is low, and the washing treatment is repeated. There was a problem that the function was easily lost. Examples of conventional polyester processing agents include flame retardancy imparting agents disclosed in Patent Documents 6 and 7.

  Conventionally, various water-dispersible polyester resins have been proposed as processing agents for textile fabrics. As a method for dispersing these polyester resins in water, for example, the method by introduction of a sulfonic acid metal base described in Patent Document 8 and Patent Documents 6 and 7, the method by introduction of a neutralized salt of a carboxyl group by an amine compound, or the above The method of copolymerizing the polyalkylene glycol described in Patent Document 6 has been common.

However, introduction of a sulfonic acid metal base lowers the water resistance performance of the obtained polyester resin, so that the durability as a treating agent tends to be insufficient. In addition, introduction of amine-neutralized carboxyl groups has problems such as deterioration of working environment due to volatilization of amine components in the processing step. Furthermore, in the method using a polyalkylene glycol copolymer, for example, in a composition in which a large amount of 1,3-propylene glycol is copolymerized in the glycol component, it is difficult to obtain a stable aqueous dispersion. In addition, the previously proposed water-based polyester finishing treatment agent is easy to adapt to polyethylene terephthalate-based polyester fiber fabrics, while it is unacceptable to PTT-based fibers, and was given to the treated fiber fabrics after repeated washing treatments. There was a problem of durability that the function did not last long.
JP-A-11-157007 JP 2004-91710 A JP 2004-3000377 A International Publication No. 00/22210 Pamphlet JP 11-48631 A Japanese Patent Laid-Open No. 55-60524 JP 58-27741 A JP 2004-67910 A

  The present invention has been made to solve the above-mentioned problems, and the object of the present invention is to improve the familiarity with PTT fibers and to be a PTT resin which is a water dispersible polyester resin excellent in stability. It is to provide a processing agent for fibers, and further to provide a PTT fiber imparted with a function excellent in washing durability performance, particularly excellent antifouling property and water absorption performance, by using the processing agent.

  The processing agent for PTT fibers of the present invention is obtained by water-dispersing a polyester resin obtained by copolymerizing 1,3-propylene glycol and a polyalkylene glycol (A) having a number average molecular weight of 600 to 6000 as essential components. It is characterized by being.

  Here, the polyester resin was copolymerized in the side chain with a glycol component (B) that forms two or more aromatic rings and / or a dibasic acid component (C) that forms two or more aromatic rings. It is preferable.

  In the PTT fiber processing agent of the present invention, it is preferable that 1,3-propylene glycol of the polyester resin is copolymerized in an amount of 50 to 95 mol% when the total glycol component is 100 mol%. .

  The present invention also provides a PTT fiber treated with the above-described PTT processing agent of the present invention.

  The processing agent for PTT fiber of the present invention is excellent in water dispersibility, and the PTT fiber treated with such a processing agent exhibits a high antifouling function and a water absorbing function. Moreover, the processing agent of this invention is very easy to adapt to a PTT type fiber, and as a result, high washing durability is provided.

  The processing agent for PTT fibers of the present invention is obtained by water-dispersing a polyester resin obtained by copolymerizing 1,3-propylene glycol and a polyalkylene glycol (A) having a number average molecular weight of 600 to 6000 as essential components. is there.

  The polyester resin used in the processing agent for PTT fibers of the present invention contains 1,3-propylene glycol as an essential component, and thus has high affinity for PTT fibers and high washing resistance to PTT fibers. Can be granted. The content (copolymerization ratio) of 1,3-propylene glycol is not particularly limited, but is preferably 50 to 95 mol% copolymerized when the total glycol component is 100 mol%, More preferably, 65 to 95 mol% is copolymerized. When 1,3-propylene glycol is less than 50 mol%, there is a possibility that the washing durability of the PTT fiber obtained by becoming difficult to conform to the PTT fiber substrate may be lowered, and when it exceeds 95 mol% This is because water dispersion may be difficult.

  The processing agent for PTT fibers according to the present invention contains a polyalkylene glycol (A) having a number average molecular weight of 600 to 6000 (preferably 1000 to 3000) as an essential component, so that high hydrophilicity is imparted and stable. Water dispersion can be realized. When the number average molecular weight of the polyalkylene glycol (A) in the present invention is less than 600, the block property of the polyalkylene chain exhibiting hydrophilicity in the polyester molecule becomes insufficient, and a stable aqueous dispersion cannot be formed. Moreover, when the number average molecular weight of polyalkylene glycol (A) exceeds 6000, the reactivity with a dibasic acid component will become low, and the component which is not copolymerized will remain as an oligomer.

  Specific examples of the polyalkylene glycol (A) having a number average molecular weight of 600 to 6000 in the present invention include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Among them, in order to increase the hydrophilicity of the polymer, polyethylene glycol is used. preferable.

  The content (copolymerization ratio) of the polyalkylene glycol (A) in the polyester resin used in the processing agent of the present invention is not particularly limited, but is 5 mol when the total glycol component is 100 mol%. % Or more is preferably copolymerized, and more preferably 10 mol% or more is copolymerized. When the content of the polyalkylene glycol (A) is less than 5 mol%, sufficient hydrophilicity cannot be imparted and a stable aqueous dispersion may not be formed. Further, the upper limit of the content of polyalkylene glycol (A) is not particularly limited, but it is less than 50 mol% in order to maintain the polymerizability of the polyester resin and the mechanical properties of the obtained resin. Preferably, it is 35 mol% or less.

As the glycol component constituting the main chain of the polyester resin in the present invention, in addition to the aforementioned 1,3-propylene glycol and polyalkylene glycol (A), an appropriate glycol component widely used in this field is particularly limited. Can be used without any problem. By appropriately selecting the glycol component constituting the main chain, the mechanical strength of the polyester resin and the texture of the PTT fiber treated with the processing agent of the present invention can be adjusted. Examples of the glycol component include ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 2-methyl-1 , 3-propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,4-diethyl-1,5-pentanediol, 2 -Ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2,2'-dimethyl-3-hydroxypropanoate, 2-n-butyl-2-ethyl-1,3-propanediol 3-ethyl-1,5-pentanediol, 3-propyl-1,5-pentanediol, 2,2-die Aliphatic diols such as ru-1,3-propanediol and 3-octyl-1,5-pentanediol, 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, , 4-bis (hydroxyethyl) cyclohexane, 1,4-bis (hydroxypropyl) cyclohexane, 1,4-bis (hydroxymethoxy) cyclohexane, 1,4-bis (hydroxyethoxy) cyclohexane, 2,2-bis (4 -Hydroxymethoxycyclohexyl) propane, 2,2-bis (4-hydroxyethoxycyclohexyl) propane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane, 3 (4), 8 ( 9) - tricyclo [5.2.1.0 ^2.6] deca Such as alicyclic glycols such as dimethanol and the like. Of course, the main chain may contain a polyglycol component (B) described later.

  As the dibasic acid component constituting the main chain of the polyester resin in the present invention, an appropriate dibasic acid component widely used in this field can be used without particular limitation. By appropriately selecting the dibasic acid component constituting the main chain, it is possible to adjust the mechanical strength of the polyester resin and the texture of the PTT fiber treated with the processing agent of the present invention. Dibasic acid components include, for example, aromatic dibasic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, oxalic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, etc. Aliphatic dibasic acids or alicyclic dibasic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid can be used. Of course, a dibasic acid component (C) described later may be contained in the main chain. Of these dibasic acid components, terephthalic acid and isophthalic acid are more versatile and preferred.

The polyester resin in the processing agent of the present invention contains a glycol component (B) that forms two or more aromatic rings and / or a dibasic acid component (C) that forms two or more aromatic rings in the side chain. A polymerized one is preferred. In other words, the polyester resin in the present invention is formed by copolymerizing the glycol component (B) and / or the dibasic acid component (C) to form a side chain having two or more aromatic rings. It is preferable. The water dispersion stability by the above-mentioned polyethylene glycol (A) is obtained by copolymerizing the glycol component (B) and / or the dibasic acid component (C) forming a side chain with the polyester resin in the present invention. It is possible to obtain an aqueous dispersion having a further enhanced effect. Although the glycol component (B) and / or the dibasic acid component (C) itself does not have any hydrophilic performance, the reason why the above effect is exhibited by using these is not clear, By forming the side chain by copolymerizing the glycol component (B) and / or the dibasic acid component (C) described above, a very bulky (bulky) structure can be formed on the side chain of the polyester resin, This structure hinders the flexibility of the main chain of the polyester resin, and the segment composed of polyethylene glycol (A), which is a hydrophilic part, is held in a structurally extended state, so that the entire polyester resin is stable in water dispersion. It is presumed that the function of polyethylene glycol (A) to be converted is enhanced. The fact that the above-mentioned glycol component (B) and / or dibasic acid component (C) are copolymerized with the polyester resin in the processing agent to form a side chain is, for example, ¹ H-NMR or ¹³ C. -It can be confirmed by NMR analysis or the like.

  The glycol component (B) used in the present invention is not particularly limited as long as it forms two or more aromatic rings. For example, 4,4 ′-(9-fluorenylidene) bis (2- Phenoxyethanol), 9H-fluorene-9,9-dimethanol, trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol, and the like. Among these, 4,4 '-(9-fluorenylidene) bis (2-phenoxy) ethanol is preferable from the viewpoint of versatility.

  When the glycol component (B) is copolymerized, the content (copolymerization ratio) is not particularly limited, but it is 5 mol% or more when the total glycol component is 100 mol%. Is preferable, and it is more preferable that it is 15 mol% or more. This is because when the glycol component (B) is less than 5 mol%, the water dispersion stability in the processing agent tends to be lowered. Moreover, although there is no restriction | limiting in particular in the upper limit of content of a glycol component (B), when all the glycol components shall be 100 mol% from the balance with 1, 3- propylene glycol and a polyalkylene glycol component (A). It is preferably 30 mol% or less, and more preferably 25 mol% or less.

  The dibasic acid component (C) used in the present invention is not particularly limited as long as it forms two or more aromatic rings in the side chain. For example, 4,4 ′-(9-fluorenylidene) Bis (2-phenoxyacetic acid), 9H-fluorene-9,9-bisacetic acid, trans-9,10-dihydro-9,10-ethanoanthracene-11,12-bisacetic acid, 9,10-dihydro-9- And an addition reaction product of oxa-10-phosphaphenanthrene-10-oxide and itaconic acid (see the following chemical formula). In the present specification, the “dibasic acid component” includes the above-mentioned 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid addition reaction product, acid anhydride, It also includes an ester compound that forms a structure similar to that derived from a dibasic acid component in a copolymerized polyester resin. Among the above, the dibasic acid component (C) is composed of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid because of the polymerization stability and availability of the polyester resin. The addition reaction product of As a method of copolymerizing an addition reaction product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid with a polyester resin, both reaction products are synthesized in advance, A method in which the reaction product is added and polymerized before and after the transesterification (chemical conversion) reaction can be mentioned. Alternatively, a method may be employed in which both are separately added before and after the transesterification (chemical conversion) reaction, and the addition reaction is completed in the reaction system before polymerization.

  When the dibasic acid component (C) is copolymerized, the content (copolymerization ratio) is not particularly limited, but it is 5 mol% when the total dibasic acid component is 100 mol%. It is preferable that it is above, and it is more preferable that it is 15 mol% or more. This is because when the dibasic acid component (C) is less than 5 mol%, the water dispersion stability in the processing agent tends to be lowered. Further, the upper limit of the content of the dibasic acid component (C) is not particularly limited, but from the viewpoint of the polymerization stability of the polyester resin, 50 mol% or less when the total dibasic acid component is 100 mol%. It is preferable that it is 35 mol% or less.

  In the polyester resin of the present invention, the glycol component (B) and the dibasic acid component (C) described above may be copolymerized together to form a side chain. Since the glycol component (B) and the dibasic acid component (C) are copolymerized together to form a side chain, the further effect that the water dispersion stability is further improved is exhibited. In this case, the glycol component (B) and the dibasic acid component (C) have a total copolymerization ratio of 5 mol% or more when the total of all glycol components and all acid components is 100 mol%. Is preferable, and it is more preferable that it is 10 mol% or more. This is because if the sum of the copolymerization ratios is less than 5 mol%, a sufficient effect for stably dispersing the polyester resin in water may not be obtained. Moreover, although there is no restriction | limiting in particular in the upper limit of the sum of the said copolymerization ratio, From a viewpoint of the polymerization stability of a polyester resin, it is preferable that it is 30 mol% or less, and it is more preferable that it is 20 mol% or less.

  The processing agent of the present invention is obtained by dispersing the above-described polyester resin in water. The solid content concentration in the processing agent of the present invention is not particularly limited, but is preferably 2% by weight or more, and more preferably 10 to 20% by weight. When the solid content concentration is less than 2% by weight, there is a tendency that the amount of processing agent necessary for the PTT fiber cannot be found, and when it is less than 10% by weight, the processing in the processing step. This is because the efficiency tends to deteriorate. Moreover, when the said solid content concentration exceeds 20 weight%, there exists a tendency for a processing agent to be permeated more than necessary or for water dispersion stability to fall. The solid content concentration refers to a value calculated by, for example, weighing a certain amount of the processing agent and weighing the remaining solid content after drying with a hot air dryer at 170 ° C. for 1 hour.

  Although the processing agent of this invention can be used as it is, you may mix | blend and use antioxidant, an ultraviolet absorber, the amino resin which is a crosslinking agent, an epoxy compound, an isocyanate compound, etc. as needed. A small amount of a solvent may be used in combination in order to improve wettability and dispersion stability.

  The processing agent of the present invention is suitably used for processing a PTT fiber. The PTT fiber processing method using the processing agent of the present invention can be applied to the PTT fiber by an arbitrary method such as a spray method, a pad method, or an exhaust method. In this case, the basis weight of the processing agent is usually 0.01% by weight or more, preferably 0.1 to 10% by weight.

  The present invention also provides a PTT fiber treated with the above-described processing agent of the present invention. The processing agent of the present invention can be applied to various PTT-based molded article substrates such as PTT-based textile fabric products, films, synthetic papers, etc., and exhibits an antifouling function with excellent durability. When used in textile fabric products, it exhibits high antifouling function and good water absorption function with excellent washing durability.

  Hereinafter, the present invention will be described in detail by experimental examples. However, the present invention is not limited thereby. In the experimental examples, “parts” means parts by weight. Various measurements in the examples were performed by the following methods.

(1) Number average molecular weight Using water permeation gel permeation chromatography (GCP) 150C, tetrahydrofuran was used as a carrier solvent and measured at a flow rate of 1 ml / min. Three columns, Shodex KF-802, KF-804, and KF-806, manufactured by Showa Denko KK were connected, and the column temperature was set to 30 ° C. A polystyrene standard was used as the molecular weight standard sample.

(2) Acid value After 0.2 g of resin was dissolved in 20 ml of chloroform, phenolphthalein was measured with a 0.1N NaOH ethanol solution as an indicator, and the measured value was shown as an equivalent in 1 ton of resin solid content.

(3) Polyester resin composition The resin was dissolved in chloroform-D, and the resin composition ratio was determined by ¹ H-NMR using a nuclear magnetic resonance analyzer (NMR) “Gemini-200” manufactured by Varian.

<Synthesis example of polyester resin (1)>
A flask equipped with a thermometer, stirring rod, Liebig condenser, 157 parts of dimethyl terephthalate, 110 parts of 1,3-propylene glycol, 400 parts of polyethylene glycol # 2000 and 0.1 part of tetrabutyl titanate as a catalyst, stable As an agent, 0.6 part of “Irganox 1330” manufactured by Ciba-Gaigi Co., Ltd. was charged and subjected to a transesterification reaction at 190 to 230 ° C. for 3 hours, and the resulting methanol was distilled out of the system. Next, 37 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 26 parts of itaconic acid, and 0.1 part of tributylamine as a catalyst were injected into the reaction system, and the resulting condensed water was added. While being distilled off, the reaction temperature was raised to 250 ° C. over 1 hour. Depressurization was started while the temperature of the reaction system was further raised, the reaction was carried out at 0.5 Torr or less for 1 hour, and the reaction was completed at a final temperature of 265 ° C. Table 1 shows the measured number average molecular weight, acid value, and composition of the obtained polyester resin-1.

<Synthesis example of polyester resin (2)>
165 parts of dimethyl terephthalate, 129 parts of 1,3-propylene glycol, 300 parts of polyethylene glycol # 1000 and 0.1 part of tetrabutyl titanate as a catalyst, stable in a flask equipped with a thermometer, stirring bar and Liebig condenser As an agent, 0.6 part of “Irganox 1330” manufactured by Ciba-Gaigi Co., Ltd. was charged and subjected to a transesterification reaction at 190 to 230 ° C. for 3 hours, and the resulting methanol was distilled out of the system. Next, 28 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 21 parts of itaconic acid, and 0.1 part of tributylamine as a catalyst were injected into the reaction system, and the resulting condensed water was added. While being distilled off, the reaction temperature was raised to 250 ° C. over 1 hour. Depressurization was started while the temperature of the reaction system was further raised, the reaction was carried out at 0.5 Torr or less for 1 hour, and the reaction was completed at a final temperature of 265 ° C. Table 1 shows the measured number average molecular weight, acid value, and composition of the obtained polyester resin-2.

<Synthesis example of polyester resin (3)>
In a flask equipped with a thermometer, a stir bar, and a Liebig condenser, 196 parts of dimethyl terephthalate, 118 parts of 1,3-propylene glycol, 450 parts of polyethylene glycol # 3000 and 4,4 ′-(9-fluoridene) bis (2 -Phenoxyethanol) 37 parts, 0.1 part of titanic acid tetrabutyl ester as catalyst, 0.6 part of “Irganox 1330” manufactured by Ciba-Gaigi Co., Ltd. as a stabilizer was charged, and a transesterification reaction was carried out at 190-230 ° C. for 3 hours to produce Methanol was distilled out of the system. The temperature of the reaction system was further raised, and when the temperature reached 250 ° C., pressure reduction was started, the reaction was carried out at 0.5 Torr or less for 1 hour, and the reaction was completed at a final temperature of 265 ° C. Table 1 shows the measured number average molecular weight, acid value, and composition of the obtained polyester resin-3.

<Synthesis example of polyester resin (4)>
In a flask equipped with a thermometer, a stir bar, and a Liebig condenser, 170 parts of dimethyl terephthalate, 125 parts of 1,3-propylene glycol, 500 parts of polyethylene glycol # 2000, 4,4 ′-(9-fluoridene) bis (2 -Phenoxyethanol) 24 parts, 0.1 parts of titanic acid tetrabutyl ester as a catalyst, 0.6 parts of "Irganox 1330" manufactured by Ciba-Gaigi Co., Ltd. as a stabilizer, and a transesterification reaction at 190 to 230 ° C for 3 hours to form Methanol was distilled out of the system. Next, 15 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 13 parts of itaconic acid, and 0.05 part of tributylamine as a catalyst are added to the reaction system, and the resulting condensed water is added. While being distilled off, the reaction temperature was raised to 250 ° C. over 1 hour. Depressurization was started while the temperature of the reaction system was further raised, the reaction was carried out at 0.5 Torr or less for 1 hour, and the reaction was completed at a final temperature of 265 ° C. Table 1 shows the measured number average molecular weight, acid value, and composition of the obtained polyester resin-4.

<Synthesis example of polyester resin (5)>
In a flask equipped with a thermometer, a stir bar, and a Liebig condenser, 170 parts of dimethyl terephthalate, 61 parts of 1,3-propylene glycol, 400 parts of polyethylene glycol # 2000, 62 parts of ethylene glycol and tetrabutyl titanate as a catalyst 0 .1 part, 0.6 part of “Irganox 1330” manufactured by Ciba-Gigi Co., Ltd. was added as a stabilizer, and a transesterification reaction was carried out at 190 to 230 ° C. for 3 hours, and the resulting methanol was distilled out of the system. Next, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (22 parts), itaconic acid (17 parts), and tributylamine (0.05 parts) as a catalyst were added to the reaction system, and the resulting condensed water was added. While being distilled off, the reaction temperature was raised to 250 ° C. over 1 hour. Depressurization was started while the temperature of the reaction system was further raised, the reaction was carried out at 0.5 Torr or less for 1 hour, and the reaction was completed at a final temperature of 265 ° C. Table 1 shows the measured number average molecular weight, acid value, and composition of the obtained polyester resin-5.

<Synthesis example of polyester resin (6)>
194 parts of dimethyl terephthalate, 133 parts of 1,3-propylene glycol, 500 parts of polyethylene glycol # 2000, 62 parts of ethylene glycol, and tetrabutyl titanate as a catalyst were added to a flask equipped with a thermometer, a stir bar and a Liebig condenser. .1 part, 0.6 part of “Irganox 1330” manufactured by Ciba-Gigi Co., Ltd. was added as a stabilizer, and a transesterification reaction was carried out at 190 to 230 ° C. for 3 hours, and the resulting methanol was distilled out of the system. The temperature of the reaction system was further increased, and when the temperature reached 250 ° C., pressure reduction was started, the reaction was carried out at 0.5 Torr or less for 1 hour, and the reaction was completed at a final temperature of 265 ° C. Table 1 shows the measured number average molecular weight, acid value, and composition of the obtained polyester resin-6.

<Comparative synthesis example of polyester resin (1)>
In a flask equipped with a thermometer, a stir bar, and a Liebig condenser, 170 parts of dimethyl terephthalate, 129 parts of 1,3-propylene glycol, 120 parts of polyethylene glycol # 400, and 0.1 part of tetrabutyl titanate as a catalyst, As a stabilizer, 0.6 part of “Irganox 1330” manufactured by Ciba-Gaigi Co., Ltd. was charged and subjected to a transesterification reaction at 190 to 230 ° C. for 3 hours, and produced methanol was distilled out of the system. Next, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (22 parts), itaconic acid (17 parts), and tributylamine (0.05 parts) as a catalyst were added to the reaction system, and the resulting condensed water was added. While being distilled off, the reaction temperature was raised to 250 ° C. over 1 hour. Depressurization was started while the temperature of the reaction system was further raised, the reaction was carried out at 0.5 Torr or less for 1 hour, and the reaction was completed at a final temperature of 265 ° C. Table 1 shows the measured number average molecular weight, acid value, and composition of the obtained polyester resin-7.

<Comparative synthesis example of polyester resin (2)>
A flask equipped with a thermometer, a stir bar, and a Liebig condenser was charged with 170 parts of dimethyl terephthalate, 152 parts of 1,3-propylene glycol, and 0.1 part of tetrabutyl titanate as a catalyst at 190 to 230 ° C. for 3 hours. A transesterification reaction was carried out, and the produced methanol was distilled out of the system. Next, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (22 parts), itaconic acid (17 parts), and tributylamine (0.05 parts) as a catalyst were added to the reaction system, and the resulting condensed water was added. While being distilled off, the reaction temperature was raised to 250 ° C. over 1 hour. Depressurization was started while the temperature of the reaction system was further raised, the reaction was carried out at 0.5 Torr or less for 1 hour, and the reaction was completed at a final temperature of 265 ° C. Table 1 shows the measured number average molecular weight, acid value, and composition of the obtained polyester resin-8.

<Comparative synthesis example of polyester resin (3)>
A flask equipped with a thermometer, a stir bar, and a Liebig condenser is charged with 155 parts of dimethyl terephthalate, 99 parts of ethylene glycol, 400 parts of polyethylene glycol # 1000, and 0.1 part of tetrabutyl titanate as a catalyst. The transesterification reaction was carried out for 3 hours, and the resulting methanol was distilled out of the system. Next, 37 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 20 parts of itaconic acid, and 0.05 part of tributylamine as a catalyst are added to the reaction system, and the resulting condensed water is added. While being distilled off, the reaction temperature was raised to 250 ° C. over 1 hour. Depressurization was started while the temperature of the reaction system was further raised, the reaction was carried out at 0.5 Torr or less for 1 hour, and the reaction was completed at a final temperature of 265 ° C. Table 1 shows the measured number average molecular weight, acid value, and composition of the resulting polyester resin-9.

<Comparative synthesis example of polyester resin (4)>
A flask equipped with a thermometer, a stir bar, and a Liebig condenser is charged with 155 parts of dimethyl terephthalate, 147 parts of 1,3-propylene glycol, 600 parts of polyethylene glycol # 10000, and 0.1 part of tetrabutyl titanate as a catalyst. The transesterification was carried out at 190 to 230 ° C. for 3 hours, and the produced methanol was distilled out of the system. Next, 37 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 20 parts of itaconic acid, and 0.05 part of tributylamine as a catalyst are added to the reaction system, and the resulting condensed water is added. While being distilled off, the reaction temperature was raised to 250 ° C. over 1 hour. Depressurization was started while the temperature of the reaction system was further raised, the reaction was carried out at 0.5 Torr or less for 1 hour, and the reaction was completed at a final temperature of 265 ° C. Table 1 shows the measured number average molecular weight, acid value, and composition of the obtained polyester resin-10.

The abbreviations shown in Table 1 represent the following compound names.
PEG # 400: Polyethylene glycol, number average molecular weight 400
PEG # 1000: Polyethylene glycol, number average molecular weight 1000
PEG # 2000: Polyethylene glycol, number average molecular weight 2000
PEG # 3000: Polyethylene glycol, number average molecular weight 3000
PEG # 10000: Polyethylene glycol, number average molecular weight 10,000
T: terephthalic acid OPP-IA: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid addition reaction product IA: itaconic acid 1,3-PG: 1,3-propylene Glycol EG: Ethylene glycol BPEF: 4,4 ′-(9-fluorenylidene) bis (2-phenoxyethanol)
In addition, the polyester resin-5 obtained by the synthesis example (5) is a case where the copolymerization ratio with respect to all the glycol components of 1, 3- propylene glycol is less than 50 mol%, The polyester obtained by the synthesis example (6) Resin-6 does not contain a glycol component (B) and a dibasic acid component (C). Moreover, the polyester resin-7 obtained by the comparative synthesis example (1) is a case where the molecular weight of the polyalkylene glycol (component A) is out of the range of 600 to 6000. The polyester obtained by the comparative synthesis example (2) Resin-8 is a case where polyalkylene glycol (component A) is not included. Polyester resin-9 obtained in Comparative Synthesis Example (3) is a case where 1,3-propylene glycol is not copolymerized. Moreover, polyester resin-10 obtained by the comparative synthesis example (4) is a case where the number average molecular weight of polyalkylene glycol (A component) remove | deviates from the range of 600-6000.

<Experimental Example 1: Stability test of aqueous dispersion liquid>
100 parts of each of polyester resins-1 to 10 obtained in Synthesis Examples and Comparative Synthesis Examples were put into 1 L of hot water at 80 ° C., stirred at the same temperature for 1 hour, and then returned to room temperature to confirm the state. The confirmation judgment results are shown as follows. The results are shown in Table 2.

A: A uniform dispersion that does not change even after being left for 2 days. Δ: A uniform dispersion that precipitates when left for several hours. X: A uniform dispersion is not formed. thing.

<Experimental example 2: processing test>
As for polyester resins -1 to 6 and 9 which formed a uniform and stable dispersion in the stability test of the aqueous dispersion liquid, "Solo" fiber fabric manufactured by Asahi Kasei Co., Ltd. using the 10% aqueous dispersion prepared in the above test. The actual processing was performed using 4% by weight. Processing is performed using a dyeing tester LABORATORY MACHINES HD-12E (manufactured by Sakurai Dyeing Machine Co., Ltd.), with a bath ratio of 1:15 as the amount of water relative to the weight of the dough, and a dispersion leveling agent New Levelin RD-10E (Takamatsu Oil & Fat Co., Ltd.) (Manufactured by the company) 0.5 g / l added, pH adjusted to 4.5 with acetic acid, the temperature was raised from 30 ° C. to 110 ° C. at a rate of 2 ° C./min. Performed by exhaustion. Moreover, the same evaluation was also performed using the normal polyethylene terephthalate fiber fabric using the polyester resin-1. The following evaluation tests were performed on each treated woven fabric.

(1) Antifouling test (1-1) Dirt removal (SRM)
One drop of A, C heavy oil (1: 1) mixed heavy oil is dropped onto a work cloth with a 1 ml pipette, left for 24 hours, and then washed (JIS L0271 103 method) to examine the removability of the A, C mixed heavy oil. Judgment is made in 5 grades of 1 to 5 grades, and judgment is made with an antifouling gray scale. Grade 5 indicates complete removal.

(1-2) Recontamination (SRD)
The processed cloth is treated in the following dirt bath, and the contamination state of the processed cloth is determined to 1 to 5 grade by the gray scale for contamination.

<Conditions for dirty bath>
・ Contaminant 0.3% soln.
-Powdered soap (JIS K-3300) 0.1% soln.
・ Bath ratio 1:50
・ Temperature × Time 40 ° C. × 16 minutes ・ After rotation of the roundometer, washed with water, dehydrated, and air-dried <Contaminant composition>
Dry pollutant (1) and dry pollutant (2) are mixed in a weight ratio of 1: 1. Composition of dry pollutant (1) Kanuma soil 30%, Akadama soil 30%, Industrial Portland cement 15%, Aerosil # 380 (Nippon Aerosil Co., Ltd.) 15%, n-decane (reagent grade 1) 8%, ferric oxide (reagent grade 1) 1%, carbon black MA-100 (Mitsubishi Chemical Industry Co., Ltd.) 1 % For 4 hours in a ball mill.

-Composition of dry pollutant (2) Stearic acid (industrial) 15%, oleic acid (industrial) 15%, beef tallow oil (melting point 58-59 ° C) 15%, olive oil 15%, cetyl alcohol (industrial) 15%, 125 ° F paraffin (industrial) 15%, cholesterol (reagent grade 1) 5%, carbon black MA-100 (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 5% are melted and mixed.

(2) Water absorption test The water absorption test was done by the dropping method based on JIS 1096 6.26.1 A method.

(3) Washing durability A household washing machine was used. A washing durability test was performed by a method according to JIS L2017 103 method using “Attack” (0.75 g / L) manufactured by Kao Corporation as a detergent.

  Tables 3 and 4 show the antifouling performance, water absorption performance and washing durability of the resulting fabric.

Claims (4)

  A processing agent for polytrimethylene terephthalate fibers, in which a polyester resin obtained by copolymerizing 1,3-propylene glycol and a polyalkylene glycol (A) having a number average molecular weight of 600 to 6000 as essential components is dispersed in water. .   The polyester resin is obtained by copolymerizing a side chain with a glycol component (B) that forms two or more aromatic rings and / or a dibasic acid component (C) that forms two or more aromatic rings. The processing agent for polytrimethylene terephthalate fibers according to claim 1.   The polytrimethylene according to claim 1 or 2, wherein 1,3-propylene glycol of the polyester resin is copolymerized in an amount of 50 to 95 mol% when the total glycol component is 100 mol%. Processing agent for terephthalate fiber.   A polytrimethylene terephthalate-based fiber that has been treated using the processing agent for polytrimethylene terephthalate-based fiber according to claim 1.