JP4392716B2 - Treatment agent for biodegradable polyester moldings - Google Patents

Description

The present invention relates to a treatment agent for a biodegradable polyester-based molded body and a biodegradable polyester-based molded body obtained using the same. Specifically, for the purpose of providing darkness, fastness, flexibility and antistatic properties of biodegradable polyester-based molded products such as polylactic acid fibers or fibers for blended and woven fabrics of these fibers with other fibers It relates to the treating agent.

In the dyeing process and finishing process of natural fibers or synthetic fibers, surfactants are used as treatment agents in various applications for the purpose of imparting dispersibility, level dyeability, darkness, flexibility and antistatic properties. ing. In recent years, polylactic acid fiber has attracted attention as a biodegradable fiber friendly to the global environment, and various surfactants have been proposed, but there are few that exhibit sufficient effects. In particular, in the dyeing process of polylactic acid fiber, there is a serious disadvantage that the dye is not sufficiently dyed as compared with other synthetic fibers and natural fibers, and the color depth and sharpness of the dyed product are inferior.

Conventionally, as a method for darkening synthetic fibers, particularly polyester fibers, a method for imparting fine irregularities to the fiber surface and a method for treating with a low refractive index resin have been proposed. Regarding the former method by imparting fine irregularities to the fiber surface, chemical erosion method, physical etching method, etc. are known, but there are problems such as requiring special equipment and complicated process (For example, refer to Patent Documents 1 and 2). On the other hand, regarding the method of treating with the latter low refractive index resin, a method using a urethane resin, a fluororesin, a silicone resin, an acrylic resin or the like is known (for example, see Patent Document 3). However, even when these methods are applied to biodegradable polyester fibers, the darkness and durability are insufficient, and the user's satisfaction has not yet been obtained.

Japanese Patent Laid-Open No. 54-120728 JP-A-61-97490 JP 2001-288683 A

The present invention improves the fastness of the biodegradable polyester-based molded body, particularly the polylactic acid-based fiber dyeing process without improving the darkness of the molded body without special equipment or complicated processes. It is an object to provide a treatment agent that can efficiently impart flexibility and antistatic properties.

As a result of intensive studies to achieve the above object, the present inventors have improved the color fastness of the biodegradable polyester-based molded article and at the same time improved the fastness, imparted flexibility and antistatic properties, etc. The invention of a processing agent that can be improved has been completed.

That is, in the present invention, a polyamide polyamine (X) obtained by reacting a polyalkylene polyamine with a dibasic carboxylic acid and / or a derivative thereof in a molar ratio of 1: 0.5 to 2 is converted from epichlorohydrin to 1: 0 to 2. It is the processing agent for polylactic acid fiber characterized by having as a main component the polyamide polyamine-epichlorohydrin resin (Y) obtained by making it react by the molar ratio.

  In another embodiment of the present invention, the polyamidopolyamine (X) is added by adding 1 to 40 moles of alkylene oxide having 2 to 4 carbon atoms to 1 mole of the imino group. Has an oxyalkylene chain.

  In addition, the present invention also provides a biodegradable polyester-based molded article obtained using the above-described treatment agent.

The treatment agent of the present invention is very useful for improving darkness of a biodegradable polyester-based molded article and at the same time efficiently improving fastness, imparting flexibility and antistatic properties.

Conventionally, no treatment agent capable of exhibiting an excellent dark color effect in dyeing biodegradable polyester-based molded articles, particularly polylactic acid fibers, has been proposed and can be said to be an extremely useful invention. The reason why the treatment agent of the present invention is excellent has not been fully elucidated, but the treatment agent is adsorbed on the biodegradable polyester fiber, and the negatively colored dye particles are adsorbed there, so that darkness is reduced. At the same time, it is presumed that fastness improvement, flexibility and antistatic properties are imparted.

The present invention will be described in detail below.
The polyamide polyamine (X) according to the present invention is obtained by reacting a polyalkylene polyamine with a dibasic carboxylic acid and / or a derivative thereof. Here, the polyalkylene polyamine is a compound having two amino groups and an alkylene group that may contain an imino group between them. Specific examples include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, alkylenediamines such as hexamethylenediamine, and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobispropylamine. And polyalkylene polyamines such as 3-azahexane-1,10-diamine. Among these, diethylenetriamine and triethylenetetramine are industrially advantageous. These polyalkylene polyamines can be used alone or in combination of two or more.

The dibasic carboxylic acid in the dibasic carboxylic acid and / or derivative thereof is a compound having two carboxyl groups in the molecule, and may be any of aliphatic, aromatic, and alicyclic. Specifically, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid and fumaric acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, tetrahydrophthalic acid Hexahydrophthalic acid, cyclohexane-1,3- or 1,4-dicarboxylic acid, cyclopentanedicarboxylic acid, alicyclic dicarboxylic acid such as 3- or 4-methylhexahydrophthalic acid, etc. In particular, adipic acid is particularly preferable. Examples of the derivatives of dibasic carboxylic acids include esters such as mono- or diesters with lower alcohols, and acid anhydrides (intramolecular dehydration condensates). A dibasic carboxylic acid or its derivative can be used individually or in combination of 2 or more types.

The reaction molar ratio of the polyalkylene polyamine and the dibasic carboxylic acid and / or derivative thereof is 1: 0.5 to 2, preferably 1: 0.8 to 1.4. When the reaction molar ratio is less than 1: 0.5, the dark color effect is inferior, and when it exceeds 1: 2, the dark color effect is also inferior. The reaction temperature is usually 120 to 180 ° C, preferably 140 to 170 ° C. If it is less than 120 degreeC, reaction time will become long, and if it exceeds 180 degreeC, a reaction byproduct will increase and it is unpreferable. After completion of the reaction, water is added to form a 10 to 80% by weight aqueous solution of polyamide polyamine. In addition, although the said reaction reacts without a catalyst, you may use hydrochloric acid, a sulfuric acid, benzenesulfonic acid, and p-toluenesulfonic acids as a reaction catalyst.

The polyamide polyamine-epichlorohydrin resin (Y) according to the present invention can be obtained by reacting the polyamide polyamine (X) obtained above with epichlorohydrin. The reaction molar ratio of the polyamide polyamine and epichlorohydrin is 1: 0 to 2, preferably 1: 0.5 to 2, more preferably 1: 0.8 to 1.6 with respect to the imino group in the polyamide polyamine. . When the reaction molar ratio exceeds 1: 2, the dark color effect is inferior, which is not preferable.

The reaction between the polyamide polyamine (X) and epichlorohydrin is carried out at a temperature of 20 to 100 ° C, preferably 40 to 70 ° C. This reaction is performed until the viscosity reaches 20 to 1000 mPa · s (25 ° C.). If the viscosity is less than 20, the dark color effect is insufficient, and if it exceeds 1000, the storage stability of the final product is remarkably inferior and gelation is not preferable. When the reaction reaches a predetermined viscosity range, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid or an organic acid such as formic acid or acetic acid is added to adjust the pH to 1 to 7, preferably 2 to 5. To do. Next, the reaction product is adjusted to an aqueous solution of 10 to 80% by weight to obtain a final product.

The polyamide polyamine (X) may have a (poly) oxyalkylene chain. This is obtained by adding an alkylene oxide having 2 to 4 carbon atoms to the imino group of the polyamide polyamine (X). C2-C4 alkylene oxide is ethylene oxide, propylene oxide, or butylene oxide. These alkylene oxides may be used alone or in combination of two or more. The added mole number of alkylene oxide is 40 moles or less, preferably 20 moles or less with respect to 1 mole of imino group in the polyamide polyamine (X). When the added mole number exceeds 40 moles, the dark color effect is inferior. This addition reaction is performed by adding an alkylene oxide while keeping the polyamide polyamine aqueous solution at 40 to 60 ° C.

The treatment agent of the present invention is a plasticizer, an antioxidant, a lubricant, a colorant, an ultraviolet absorber, a light stabilizer, a pigment, an inorganic filler, and other various additives, modifiers, and the like within a range not impairing the object of the present invention. Fillers can be included as additional components, or they can be used with the treating agents of the present invention.

The treatment agent of the present invention can be used, for example, as a dyeing aid for the purpose of imparting dark color. In this case, the treatment agent of the present invention can be added at the time of dyeing or before dyeing. When the treatment agent of the present invention is added and used at the time of dyeing, the purpose of the present invention is not impaired in order to improve dispersibility, leveling property, penetrability, flexibility in bath, low foaming property, etc. Various additives such as dispersants, leveling agents, penetrants, bath softeners, antifoaming agents, etc. can be used together as optional components, dyes used in dyeing baths, acids for adjusting pH, chelating agents Etc. can also be used as usual. The polylactic acid-based molded body is preferably dyed at a temperature of 100 to 120 ° C. and a pH of 4 to 6. This is to prevent a decrease in molecular weight due to hydrolysis of polylactic acid.

When the treatment agent of the present invention is used before dyeing, the treatment agent is adsorbed on the molded body at a treatment temperature of 20 to 120 ° C. and a treatment time of 5 to 60 minutes. After the treatment, it may be dyed by a usual dyeing method, and at the time of dyeing, the object of the present invention is lost in order to improve dispersibility, leveling property, penetrability, flexibility in bath, and low foaming property as described above. Various additives such as a dispersant, a leveling agent, a penetrating agent, a bath softener, and an antifoaming agent may be used as optional components as long as they are not included.

The treatment agent of the present invention can also be used after dyeing for the purpose of improving fastness, imparting flexibility and antistatic properties. In this case, it can be applied to the molded body by an immersion method, a padding method, a spray method or the like. After applying the treatment agent, in order to improve durability such as improvement of fastness, flexibility and antistatic property on the molded body, heat treatment may be performed by combined use of preliminary drying and heat treatment.

The use amount of the treatment agent of the present invention is usually 0.01 to 10 g / liter, preferably 0.2 to 5.0 g / liter with respect to the dyeing bath or aqueous solution as a solid content. Further, it may be used after being diluted with a solvent such as isopropyl alcohol and butyl cellosolve in order to improve solubility and stability and to lower the viscosity. Usually, the bath ratio of the treatment bath is 1: 5 to 1:30, and the dyeing method may be any of dip dyeing, printing, continuous dyeing and the like.

  The biodegradable polyester-based molded product in the present invention includes fibers, fabrics, fasteners, buttons and the like produced from the biodegradable polyester, and the treatment agent of the present invention is excellent in dyeing any molded product. Have Hereinafter, a polylactic acid fiber will be described as a preferred example of a biodegradable polyester molded body in which the treatment agent of the present invention is used. However, the biodegradable polyester molded body in the present invention is limited to the fiber. It is not something.

The polylactic acid fiber may be a polylactic acid fiber alone or a blend of polylactic acid fiber and other natural, regenerated or synthetic fibers, a knitted fabric, a woven fabric, or the like. Moreover, as long as it is a form, what is recognized as fiber structures, such as a thread | yarn, a knitted fabric, a textile fabric, a nonwoven fabric, a rope, a net | network, should just be.

The polylactic acid fiber is an aliphatic polyester fiber having a repeating unit mainly composed of L-lactic acid and / or D-lactic acid.

  The polylactic acid used in the production of the polylactic acid fiber uses L-lactic acid, D-lactic acid, L-lactide, D-lactide, which is a dimer of lactic acid, or meso-lactide as a raw material. In order to increase the crystallinity of the polylactic acid fiber and increase the strength, the polylactic acid preferably has an L-form ratio of 95% or more, more preferably 98% or more.

  The polylactic acid used at this time preferably has a relative viscosity in the range of 2.5 to 3.5, more preferably in the range of 2.7 to 3.2, from the viewpoints of yarn production and drawing characteristics. . The polylactic acid used has a monomer content of 0.5% by weight or less, preferably 0.3% by weight or less, particularly preferably 0.2% by weight or less. The monomer is a component having a molecular weight of 1000 or less calculated by GPC analysis described later. If the monomer content exceeds 0.5% by weight, thread breakage or the like may occur in the spinning / drawing process, and the operability may be significantly reduced. This is considered because the heat resistance of polylactic acid is lowered because the monomer component is decomposed by heat.

  The single yarn fineness of the polylactic acid fiber is preferably 0.50 to 25 dtex (decitex), and more preferably 0.75 to 10 dtex. Examples of the polylactic acid fiber include a multifilament drawn yarn, a multifilament false twist yarn, and a staple fiber. For example, a multifilament drawn yarn is obtained by spinning at a spinning speed of 3000 m / min or more, drawing at a drawing temperature of 100 to 125 ° C, 1.3 times or more, and then heat setting at 125 to 150 ° C. . The drawn yarn preferably has a tensile strength of 3.5 cN / dtex (centinewton / dtex) or more and a boiling water shrinkage of 15% or less.

  The production method of the multifilament false twist yarn is not particularly limited as long as it is a normal drawing simultaneous false false twist method, and can be used in false twist machines such as a belt type, a pin type, and a friction type. The false twisting speed is preferably 500 m / min or more in consideration of productivity. The false twisted yarn preferably has a tensile strength of 2.65 cN / dtex or more.

  Furthermore, the staple fiber can be obtained by spinning at a spinning speed of 2000 m / min or less, drawing at a drawing temperature of 60 to 98 ° C., 4.0 times or more, and then heat setting at 105 to 135 ° C. The staple fiber tensile strength is preferably 3.0 cN / dtex or more.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these examples.

A four-necked flask equipped with a thermometer, a cooler, a stirrer, and a nitrogen introduction tube is charged with 103 g (1.0 mol) of diethylenetriamine and 146 g (1.0 mol) of adipic acid. Next, a dehydration reaction is performed at 150 to 160 ° C. under a nitrogen stream for 6 hours. Next, it was cooled to 90 ° C. and hot water was added to adjust the solid content to 30% to obtain a polyamide polyamine aqueous solution. Using this as a treating agent, a fabric composed of polylactic acid fiber was treated, and tests for darkness, fastness to friction, flexibility and antistatic property were conducted according to the following methods. The results are shown in Table 1.

Into a four-necked flask equipped with a thermometer and a stirrer was charged 385 g (0.5 mol) of the polyamide polyamine aqueous solution obtained in Example 1, 46 g (0.5 mol) of epichlorohydrin was added, and the reaction was carried out at 40-50 ° C. After the viscosity reached 300 mPa · s (25 ° C.), water was added to adjust the solid content to 20%, and further adjusted to pH 4 with 60 wt% sulfuric acid to obtain a polyamide polyamine-epichlorohydrin resin aqueous solution. Using this as a treating agent, a fabric composed of polylactic acid fiber was treated, and tests for darkness, fastness to friction, flexibility and antistatic property were conducted according to the following methods. The results are shown in Table 1.

A four-necked flask equipped with a thermometer, a cooler, a stirrer, and a nitrogen inlet tube is charged with 103 g (1.0 mol) of diethylenetriamine and 175 g (1.2 mol) of adipic acid. Next, a dehydration reaction is performed at 150 to 160 ° C. under a nitrogen stream for 6 hours. Next, it was cooled to 90 ° C. and hot water was added to adjust the solid content to 30% to obtain a polyamide polyamine aqueous solution. Using this as a treating agent, a fabric composed of polylactic acid fiber was treated, and tests for darkness, fastness to friction, flexibility and antistatic property were conducted according to the following methods. The results are shown in Table 1.

Into a four-necked flask equipped with a thermometer and a stirrer was charged 430 g (0.5 mol) of the polyamide polyamine aqueous solution obtained in Example 3, 55 g (0.6 mol) of epichlorohydrin was added, and the reaction was carried out at 40-50 ° C. After the viscosity reached 500 mPa · s (25 ° C.), water was added to adjust the solid content to 20%, and further adjusted to pH 4 with 60% by weight sulfuric acid to obtain a polyamide polyamine-epichlorohydrin resin aqueous solution. Using this as a treating agent, a fabric composed of polylactic acid fiber was treated, and tests for darkness, fastness to friction, flexibility and antistatic property were conducted according to the following methods. The results are shown in Table 1.

Comparative Example 1
Using a commercially available dyeing assistant (Carriersol 150, manufactured by Satorita Chemical Co., Ltd., 50% trichlorobenzene emulsion) as a treating agent, fabrics made of polylactic acid fiber are treated to give deep color and friction fastness. The degree, flexibility and antistatic properties were tested according to the following method. The results are shown in Table 1.

Comparative Example 2
A four-necked flask equipped with a thermometer, a cooler, a stirrer, and a nitrogen inlet tube is charged with 103 g (1.0 mol) of diethylenetriamine and 365 g (2.5 mol) of adipic acid. Next, a dehydration reaction is performed at 150 to 160 ° C. under a nitrogen stream for 6 hours. Next, it was cooled to 90 ° C. and hot water was added to adjust the solid content to 30% to obtain a polyamide polyamine aqueous solution. Using this as a treating agent, a fabric composed of polylactic acid fiber was treated, and tests for darkness, fastness to friction, flexibility and antistatic property were conducted according to the following methods. The results are shown in Table 1.

Comparative Example 3
A four-necked flask equipped with a thermometer and a stirrer was charged with 300 g (0.2 mol) of the polyamide polyamine aqueous solution obtained in Comparative Example 2, and 93 g (1.0 mol) of epichlorohydrin was added, followed by reaction at 40 to 50 ° C. After the viscosity reached 500 mPa · s (25 ° C.), water was added to adjust the solid content to 20%, and the pH was adjusted to 4 with 60 wt% sulfuric acid to obtain an aqueous polyamide polyamine-epichlorohydrin resin solution. Using this as a treating agent, a fabric composed of polylactic acid fiber was treated, and tests for darkness, fastness to friction, flexibility and antistatic property were conducted according to the following methods. The results are shown in Table 1.

<Processing conditions>
Dye: Trial Blue 02 1% owf
Treatment agent: 1.0 g / L (in terms of solid content)
80% acetic acid: 0.3 ml / L
Bath ratio: 1:20
Temperature and time: 110 ° C. × 30 minutes Dyeing machine: Color Master 12 (manufactured by Sakurai Dyeing Machine Industry)
A fabric made of polylactic acid fiber was treated under the above conditions, and after washing and drying, the darkness, friction fastness, flexibility and antistatic property of the treated fabric were tested as follows.

(A) Darkness <Determination method>
The L value of the treated cloth was measured with a color difference meter (COLOR ACE MODEL TCA-1) manufactured by Tokyo Denshoku. The L value means the lightness index, and the smaller the numerical value, the better the dark color effect.

(B) Friction fastness <Determination method>
The treated fabric was subjected to a friction fastness test. The friction fastness test was conducted according to JIS L-0849 using the above-mentioned treated cloth left in a constant temperature room at 20 ° C. and 40% RH for 24 hours.

(C) Flexibility <Determination method>
The flexibility of the treated fabric was determined by the tactile sensation method.
○ ・ ・ ・ Excellent △ ・ ・ ・ Inferior × ・ ・ ・ Defect

(D) Antistatic property <Determination method>
Frictional static electricity (V) after 1 minute was measured using a rotary static tester in accordance with JIS L-1094 using a treated cloth that was left in a constant temperature room at 20 ° C. and 40% RH for 24 hours.

A method for producing a fabric made of polylactic acid-based fibers and a method for analyzing physical properties used in the above treatment are as follows.
Production Method L Spinning and stretching were performed using polylactic acid having a L-form ratio of 98.8%, a relative viscosity of 3.08, and a monomer content of 0.28% by weight. The resulting multifilament drawn yarn 56dtex (decitex) / 48f (filament) had a tensile strength of 4.73 cN / dtex, an elongation of 28.7%, and a boiling water shrinkage of 11.6%.
Using the filament as a raw material, an interlock was prepared with a 28-inch circular knitting machine at 28 gauge.

Analysis method The physical properties of the raw material polymer (polylactic acid) and the drawn yarn obtained by drawing the polymer were analyzed by the following methods.
<Monomer content>
The polymer was dissolved in chloroform to a concentration of 10 mg / mL. GPC analysis was performed using chloroform as a solvent, and the molecular weight was measured. The detector was RI, and polystyrene was used as a molecular weight standard. The monomer content in the polymer was calculated from the proportion of components having a molecular weight of 1000 or less.

<Relative viscosity: ηrel>
The polymer was dissolved in a mixed solvent of phenol / tetrachloroethane = 60/40 (weight ratio) to a concentration of 1 g / dL, and the relative viscosity was measured at 20 ° C. using an Ubbelohde viscometer.

<Measurement of L-body ratio>
The polymer was hydrolyzed, and the ratio of L form was determined using high-performance liquid chromatography (HPLC: LC10AD, manufactured by Shimadzu Corporation) using 1.0 mol / L methanolic sodium hydroxide solution as a solvent.

<Measurement of strong elongation>
Using a tensile tester (manufactured by Shimadzu Corporation, RTM-100), a tensile test was performed at a sample length of 20 cm and a speed of 20 cm / min. The breaking strength was taken as tensile strength, and the breaking elongation was taken as elongation.

<Boiling water shrinkage>
A sample with an initial value of 50 cm was immersed in boiling water for 15 minutes under an initial load of 200 mg, air-dried for 5 minutes, and then the boiling water shrinkage was determined by the following equation.
Boiling water shrinkage rate (%) = (initial sample length−sample length after shrinkage) / initial sample length × 100

＜総合評価判定基準＞
○…処理剤が濃色性、摩擦堅牢度、柔軟性、帯電防止性の全ての性能を満たしている。
△…処理剤が濃色性、摩擦堅牢度、柔軟性、帯電防止性のいずれかの性能を満たしている。
×…処理剤が濃色性、摩擦堅牢度、柔軟性、帯電防止性の全ての性能を満たしていない。

<Comprehensive evaluation criteria>
○: The treatment agent satisfies all the performances of dark color, fastness to friction, flexibility, and antistatic properties.
Δ: The treating agent satisfies any of the characteristics of dark color, fastness to friction, flexibility, and antistatic properties.
X: The treatment agent does not satisfy all the performances of dark color, fastness to friction, flexibility and antistatic property.

  From the above results, the treatment agent mainly composed of the polyamide polyamine (X) or the polyamide polyamine-epichlorohydrin resin (Y) of the present invention is excellent in dark color effect, and at the same time, improved fastness and flexibility. It was also confirmed that the antistatic effect was imparted.

Claims (5)

A polyamide polyamine (X) obtained by reacting a polyalkylene polyamine with a dibasic carboxylic acid and / or a derivative thereof in a molar ratio of 1: 0.5 to 2 is reacted with epichlorohydrin in a molar ratio of 1: 0 to 2. A processing agent for polylactic acid fibers , characterized in that it comprises a polyamide polyamine-epichlorohydrin resin (Y) obtained as a main component. The polyamide polyamine (X) has a (poly) oxyalkylene chain by adding an alkylene oxide having 2 to 4 carbon atoms in a proportion of 1 to 40 mol with respect to 1 mol of the imino group. The treating agent according to claim 1. The treatment agent according to claim 1 or 2, wherein the treatment is a treatment for darkening, improving fastness, imparting flexibility or imparting antistatic properties. The processing agent according to any one of claims 1 to 3, which is used as a dyeing auxiliary agent imparting dark color. The polylactic acid fiber obtained using the processing agent of Claims 1-4 .