JP2005023496A - Dyeing assistant for polylactic acid-based formed article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dyeing assistant exhibiting an excellent dispersion and uniform dyeing effects in dyeing a raw material of a polylactic acid-based formed article by using a dispersion dyestuff. <P>SOLUTION: This dyeing assistant for the polylactic acid-based formed article contains one or two or more of compounds expressed by formula (1), one or two or more of compounds expressed by a specific chemical formula and one or two or more of carriers. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a dyeing aid for a polylactic acid-based molded article, and more particularly to a dyeing aid for a polylactic acid-based fiber or a blended and knitted knitted fabric of these fibers and other fibers. More specifically, the present invention relates to a dyeing assistant that exhibits an excellent dispersive leveling effect when a polylactic acid-based molded material is dyed using a disperse dye. The present invention also relates to a polylactic acid-based molded article dyed using the dyeing assistant.

  Conventionally, polyester fibers or polyamide fibers have been widely used as fibers for clothing and the like. However, in recent years, from the viewpoint of global environmental conservation, polylactic acid fibers, which are biodegradable fibers that are friendly to the global environment, are attracting attention as an alternative to these general-purpose plastic products. However, polylactic acid-based fibers are aliphatic polyester fibers, and have the disadvantage of being inferior in hydrolysis resistance compared to aromatic polyester fibers and the like. In addition, when the dyeing process similar to the aromatic polyester fiber is performed for the reason of physical properties such as a lower melting point than the aromatic polyester fiber, the molecular weight and strength of the fiber are greatly decreased, and a sufficient dispersion level is obtained. At present, there are problems such as inability to obtain dyeability. In order to solve this problem, a method of dyeing by selecting a dyeing temperature, a dyeing time, and a dyeing pH so that the fiber molecular weight reduction rate is 20% or less has been proposed (Patent Document 1). However, even though it is possible to suppress the decrease in molecular weight by the above dyeing method, there are problems such as tarring due to poor dispersion of disperse dyes and uneven spots due to uneven dyeing. At present, such a dyed product has not been obtained. Therefore, for dyeing the polylactic acid fiber, an appropriate dyeing technique has not been established, and development of a dyeing assistant that exhibits a good dispersion leveling effect has been desired.

  On the other hand, the present applicant has previously found that when a specific compound is used in dyeing a polyester synthetic fiber, a good dispersion leveling effect can be obtained (Patent Document 2). This is high-temperature dyeing and is intended for aromatic polyester fibers.

JP-A-8-311781 Japanese Patent Publication No.55-35506

It is an object of the present invention to provide a dyeing assistant that helps disperse the dye and exhibits a leveling effect with good reproducibility in order to obtain a dye-free dyeing product in the dyeing of a polylactic acid-based molded article. .

  As a result of intensive studies to achieve the above object, the present inventors have completed the invention of a dyeing aid for a polylactic acid-based molded article that can exhibit an excellent dispersion leveling effect.

［式中、Ｘはナフチル基、または

（但し、Ｒは水素原子またはフェニル基またはベンジル基またはスチリル基または炭素数１〜１２のアルキル基またはモノベンジルフェニル基またはジベンジルフェニル基またはモノスチリルフェニル基またはジスチリルフェニル基またはクミル基またはモノベンジルクミル基またはジベンジルクミル基またはモノスチリルクミル基またはジスチリルクミル基を示す。ｎは１〜３の整数であり、ｎが２、または３の場合はＲの種類は上記のものからそれぞれ独立に選ばれる）であり；Ａ₁はエチレンオキシ基が１０〜３５個結合したポリエチレンオキシ基であるか、またはエチレンオキシ基が９〜３０個およびプロピレンオキシ基が１〜５個結合したポリエチレンオキシポリプロピレンオキシ基であり；ＭはＫ、Ｎａ、ＮＨ₄または炭素数６以下のＮ−アルキルアンモニウムもしくはＮ−アルカノ−ルアンモニウムを示す。］、
（Ｂ）下記一般式（２）、（３）または（４）で示される化合物の一種または二種以上

［式中、Ｒ₁〜Ｒ₉は各々、炭素数５〜１８の高級脂肪酸残基であり；Ａ₂はエチレンオキシ基が３〜２０個結合したポリエチレンオキシ基であるか、またはエチレンオキシ基が５〜２５個およびプロピレンオキシ基が１〜５個結合したポリエチレンオキシポリプロピレンオキシ基であり；Ａ₃〜Ａ₅は全てがポリエチレンオキシ基であるかまたはポリエチレンオキシポリプロピレンオキシ基であり、Ａ₃〜Ａ₅の全てがポリエチレンオキシ基の場合はＡ₃〜Ａ₅が合計９〜６０個のエチレンオキシ基を有し、Ａ₃〜Ａ₅の全てがポリエチレンオキシポリプロピレンオキシ基である場合は、Ａ₃〜Ａ₅が合計１５〜７５個のエチレンオキシ基および合計３〜１５個のプロピレンオキシ基を有し；Ａ₆〜Ａ₉は全てがポリエチレンオキシ基であるかまたはポリエチレンオキシポリプロピレンオキシ基であり、Ａ₆〜Ａ₉の全てがポリエチレンオキシ基の場合は、Ａ₆〜Ａ₉が合計１２〜８０個のエチレンオキシ基を有し、Ａ₆〜Ａ₉の全てがポリエチレンオキシポリプロピレンオキシ基である場合は、Ａ₆〜Ａ₉が合計２０〜１００個のエチレンオキシ基および合計４〜２０個のプロピレンオキシ基を有する。］、および
（Ｃ）キャリアーの一種または二種以上
を含有することを特徴とするポリ乳酸系成形体用染色助剤である。
さらに、本発明は、上記染色助剤を使用して染色されたポリ乳酸系成形体である。 That is, the present invention
(A) One or more compounds represented by the following general formula (1)

[Wherein X is a naphthyl group, or

(However, R is a hydrogen atom, a phenyl group, a benzyl group, a styryl group, an alkyl group having 1 to 12 carbon atoms, a monobenzylphenyl group, a dibenzylphenyl group, a monostyrylphenyl group, a distyrylphenyl group, a cumyl group, or a monovalent group. A benzylcumyl group, a dibenzylcumyl group, a monostyrylcumyl group or a distyrylcumyl group, wherein n is an integer of 1 to 3, and when n is 2 or 3, the type of R is independently selected from the above. A ₁ is a polyethyleneoxy group having 10 to 35 ethyleneoxy groups bonded thereto, or a polyethyleneoxypolypropyleneoxy group having 9 to 30 ethyleneoxy groups and 1 to 5 propyleneoxy groups bonded thereto. M is K, Na, NH ₄ or 6 or more carbon atoms The lower N-alkyl ammonium or N-alkanol ammonium is shown. ],
(B) One or more of the compounds represented by the following general formula (2), (3) or (4)

[Wherein R _{1 to} R ₉ are each a higher fatty acid residue having 5 to 18 carbon atoms; A ₂ is a polyethyleneoxy group having 3 to 20 ethyleneoxy groups bonded thereto, or an ethyleneoxy group is 5 to 25 and a polyethyleneoxypolypropyleneoxy group having 1 to 5 propyleneoxy groups bonded thereto; A _{3 to} A ₅ are all polyethyleneoxy groups or polyethyleneoxypolypropyleneoxy groups, and A _{3 to} A _When all of ₅ are polyethyleneoxy groups, A _{3 to} A ₅ have a total of 9 to 60 ethyleneoxy groups, and when all of A _{3 to} A ₅ are polyethyleneoxypolypropyleneoxy groups, A ₃ to A ₅ has a total of 15 to 75 ethyleneoxy groups and a total of 3 to 15 propyleneoxy groups; A _{6 to} A ₉ are all polyethyleneoxy groups Or when all of A _{6 to} A ₉ are polyethyleneoxy groups, A _{6 to} A ₉ have a total of 12 to 80 ethyleneoxy groups, and A _{6 to} A ₉ If all are polyethyleneoxy polypropyleneoxy group, a ₆ to a ₉ has a total of 20 to 100 ethyleneoxy groups and total 4-20 propylene oxy group. And (C) a dyeing aid for a polylactic acid-based molded article, comprising one or more carriers.
Furthermore, this invention is the polylactic acid-type molded object dye | stained using the said dyeing assistant.

The dyeing assistant of the present invention helps dye dispersibility in dyeing a polylactic acid-based molded article, exhibits a leveling effect and a dark color effect with high reproducibility, and can obtain a dyed product having no stain. .

  Examples of the X group of the compound (A) represented by the general formula (1) in the present invention include a naphthyl group; a phenyl group; and a substituted phenyl group such as a monophenylated phenyl group, a diphenylated phenyl group, and triphenyl. Phenyl group, monobenzylated phenyl group, dibenzylated phenyl group, tribenzylated phenyl group, monostyrylated phenyl group, distyrylated phenyl group, tristyrylated phenyl group, tert-butylphenyl group, nonylphenyl group, dinonylphenyl group, Octylphenyl group, cumylphenyl group, monophenylated nonylphenyl group, diphenylated nonylphenyl group, monobenzylated nonylphenyl group, dibenzylated nonylphenyl group, monostyrylated nonylphenyl group, distyrylated nonylphenyl group, monophenylated octyl Ruphenyl group, diphenylated octylphenyl group, monobenzylated octylphenyl group, dibenzylated octylphenyl group, monostyrylated octylphenyl group, distyrylated octylphenyl group, monobenzylphenylated phenyl group, dibenzylphenylated phenyl group, monostyryl Examples thereof include phenylated phenyl group, distyrylphenylated phenyl group, monobenzyl cumylated phenyl group, dibenzyl cumylated phenyl group, monostyryl cumylated phenyl group, and distyryl cumylated phenyl group. Phenyl group, dibenzylated phenyl group, tribenzylated phenyl group or monostyrylated phenyl group, distyrylated phenyl group, tristyrylated phenyl group, monostyrylated octylphenyl group, distyryl It is preferred in terms of effect octyl phenyl group. The position of the substituent in the substituted phenyl group is not particularly limited.

In the general formula (1), A ₁ is a polyethyleneoxy group in which 10 to 35, preferably 10 to 30, more preferably 15 to 25, and particularly preferably 15 to 20 ethyleneoxy groups are bonded. Alternatively, it is a polyethyleneoxypolypropyleneoxy group having 9 to 30 ethyleneoxy groups, preferably 15 to 25, and 1 to 5, preferably 1 to 4 propyleneoxy groups bonded together. In the latter case, the total number of ethyleneoxy groups and propyleneoxy groups is 10 to 35, preferably 10 to 30, more preferably 15 to 25, and particularly preferably 15 to 20. When A ₁ is a polyethyleneoxypolypropyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be a block bond or a random bond. When A ₁ is a polyethyleneoxy group, if the number of ethyleneoxy groups is less than 10, the dye transfer effect is reduced and the dispersibility of the dye is not necessarily improved. If the number exceeds 35, what can be considered to inhibit dyeing? It is not preferable because it causes a problem of foaming or foaming. These are problems not found in aromatic polyester, and the cause is not clear, but it is considered that the crystal structure and dyeing temperature peculiar to polylactic acid are lower than those of polyester fibers. Similarly, when A ₁ is a polyethyleneoxypolypropyleneoxy group, if the sum of the number of ethyleneoxy groups and the number of propyleneoxy groups is less than 10, the dye transfer effect is reduced and the dispersibility of the dye is also reduced. Not necessarily improved. If the number exceeds 35, what can be considered to inhibit dyeing? Occurrence or foaming problems are the same as when A ₁ is a polyethyleneoxy group.

Compound (A) can be obtained by a known method. That is, after adding a predetermined amount of alkylene oxide to naphthol or unsubstituted or substituted phenol using an alkali catalyst such as caustic soda and caustic potash at 120 to 170 ° C. under pressure, chlorosulfonic acid, sulfuric anhydride or sulfamic acid is added. Etc., and can be obtained by sulfation. In the case of sulfation with chlorosulfonic acid or sulfuric anhydride, neutralization with an alkali compound such as caustic soda or caustic potash is further performed.

The compound (B) in the present invention is represented by the general formula (2), (3) or (4). In these formulas, R _{1 to} R ₉ are each a higher fatty acid residue having 5 to 18 carbon atoms. For example, caproic acid, caprylic acid, capric acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearin Mention may be made of acid, oleic acid and isostearic acid residues. Stearic acid and oleic acid residues are preferred.

In the general formula (2), A ₂ is a polyethyleneoxy group having 3 to 20, preferably 5 to 15 ethyleneoxy groups, or 5 to 25, preferably 7 to 20 ethyleneoxy groups and propyleneoxy. A polyethyleneoxypolypropyleneoxy group having 1 to 5, preferably 1 to 3 groups bonded thereto. In the general formula (3), all of A _{3 to} A ₅ are polyethyleneoxy groups or polyethyleneoxypolypropyleneoxy groups, and when all of A _{3 to} A ₅ are polyethyleneoxy groups, A _{3 to} A ₅ are A total of 9 to 60, preferably 15 to 45 ethyleneoxy groups, and when all of A _{3 to} A ₅ are polyethyleneoxypolypropyleneoxy groups, A _{3 to} A ₅ are 15 to 75 in total, Preferably it has 21-60 ethyleneoxy groups and a total of 3-15, preferably 3-9 propyleneoxy groups. In the general formula (4), A _{6 to} A ₉ are all polyethyleneoxy groups or polyethyleneoxypolypropyleneoxy groups, and when all of A _{6 to} A ₉ are polyethyleneoxy groups, A _{6 to} A ₉ Is a total of 12 to 80, preferably 20 to 60 ethyleneoxy groups, and when all of A _{6 to} A ₉ are polyethyleneoxypolypropyleneoxy groups, A _{6 to} A ₉ are a total of 20 to 100 Preferably 24 to 80 ethyleneoxy groups and a total of 4 to 20, preferably 4 to 12 propyleneoxy groups. When A _{2 to} A ₉ are polyethyleneoxypolypropyleneoxy groups, the ethyleneoxy group and the propyleneoxy group may be block bonds or random bonds.

  Specific examples of the compound represented by the general formula (2) include dicaproic acid polyalkylene glycol, dicaprylic acid polyethylene glycol, dicapric acid polyethylene glycol, dilauric acid polyethylene glycol, dimyristic acid polyethylene glycol, dipalmitic acid polyethylene glycol, distearic acid. Examples include, but are not limited to, acid polyethylene glycol, dioleic acid polyethylene glycol, diisostearic acid polyethylene glycol, dilauric acid polyethylene polypropylene glycol, and dioleic acid polyethylene polypropylene glycol.

  Specific examples of the compound represented by the general formula (3) include polyoxyethylene glycerol tricaprate, polyoxyethylene glycerol tricaprylate, polyoxyethylene glycerol trilaurate, polyoxyethylene glycerol trimyristate, polyoxyethylene. Glycerol tripalmitate, polyoxyethylene glycerin tristearate, polyoxyethylene glycerin trioleate, polyoxyethylene glycerin triisostearate, polyoxyethylene polyoxypropylene glycerin tristearate, polyoxyethylene polyoxypropylene glycerin trioleate, etc. However, it is not limited to these.

Specific examples of the compound represented by the general formula (4) include polyoxyethylene diglycerin tetracaprate, polyoxyethylene diglycerin tetracaprylate, polyoxyethylene diglycerin tetralaurate, polyoxyethylene diglycerin tetramillirate. State, polyoxyethylene diglycerin tetrapalmitate, polyoxyethylene diglycerin tetrastearate, polyoxyethylene diglycerin tetraoleate, polyoxyethylene diglycerin tetraisostearate, polyoxyethylene polyoxypropylene diglycerin tetracaprate, Examples thereof include polyoxyethylene polyoxypropylene diglycerin tetraoleate, but are not particularly limited thereto.

Compound (B) can be easily obtained by a known method. That is, compound (2) may be esterified with higher fatty acid in the presence of an alkali catalyst after adding alkylene oxide to polyalkylene glycol, and compound (3) or (4) may be glycerin, What is necessary is just to esterify similarly after adding an alkylene oxide to diglycerin.

Examples of the alkylene oxide for obtaining the compound (A) represented by the general formula (1) and the compound (B) represented by the general formula (2), (3) or (4) include ethylene oxide and propylene oxide. . These alkylene oxides can be used alone or in a mixed system. When used in a mixed system, addition of alkylene oxide may be either block addition or random addition. In the absence of addition of alkylene oxide, the dye transfer effect is reduced and the dispersibility of the dye is not necessarily improved.

The carrier (C) is known in the field of dyeing, for example, phenylphenols, halogenated benzenes such as mono, di and trichlorobenzene, naphthalenes such as methylnaphthalene, dimethylnaphthalene and naphthol, phenol, cresol and the like. Phenols, halogenated phenols, benzoic acid derivatives such as benzoic acid and benzoic acid esters, salicylic acid derivatives such as salicylic acid and salicylic acid esters, diphenyl derivatives and other aromatic organic compound derivatives include, but are not limited to these Is not to be done. In the dyeing assistant of the present invention, one or more of these carriers (C) can be used.

  The weight ratio of compound (A), compound (B) and carrier (C) is in the range of (A) :( B) :( C) = (0.01-10) :( 0.01-10): 1. Preferably, (A) :( B) :( C) = (0.1-1) :( 0.1-1): 1. When the blending amount of (A), (B) or (C) is increased or decreased from this range, any of dispersibility deterioration, transferability deterioration or foaming property increase, dark color effect cannot be obtained The phenomenon occurs, and an undesirable result is given as a dyeing aid intended by the present invention.

  Various additives such as an antifoaming agent, a penetrating agent, and a softening agent in the bath can be added as optional components to the dyeing aid for the polylactic acid-based molded article of the present invention as long as the object of the present invention is not impaired. .

  The gist of the present invention is that the compound (A) represented by the general formula (1) of the present invention is represented by the general formula (2), (3) or (4) in the dyeing of the polylactic acid-based molded article. The combination of the compound (B) and the carrier (C) is to obtain an excellent dyed product that exhibits excellent dispersibility and leveling and has no stain spots.

  Conventionally, a dyeing assistant capable of exhibiting excellent dyeing performance in dyeing a polylactic acid-based molded article has not been proposed, and can be said to be an extremely useful invention. The reason why the dyeing assistant used in the present invention is excellent in dyeability has not been completely clarified, but the polyethyleneoxy group having a specific length in the compounds (A), (B) and (C) according to the present invention. It is presumed that the polyethyleneoxypolypropyleneoxy group and / or the specific hydrophobic group act and exert an effect.

  The polylactic acid-based molded product in the present invention includes fibers, fabrics, fasteners, buttons, etc. produced from a polylactic acid-based resin, and the dyeing aid of the present invention has an excellent effect in dyeing any molded product. . Hereinafter, fibers will be described as a preferable example of a molded body in which the dyeing assistant of the present invention is used. However, the polylactic acid-based molded body in the present invention is not limited to fibers.

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, and 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 mass or less, preferably 0.3% by mass or less, particularly preferably 0.2% by mass 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 mass, 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 problematic 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.

  When dyeing polylactic acid-based molded articles using the dyeing assistant of the present invention, conventional dyeing machines can be used as they are, and dyes used in dyeing baths, acids for adjusting pH, chelating agents, etc. are used as usual. Can be used. 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 greatly different from the dyeing of the aromatic polyester-based molded product being performed at a temperature of 130 ° C. to 140 ° C. and a pH of about 4.5. This is because when a polylactic acid-based molded product is dyed under these conditions, hydrolysis occurs and a decrease in molecular weight is inevitable.

  The use amount of the dyeing assistant of the present invention is usually 0.01 to 5.0 g / liter, preferably 0.1 to 1.0 g / liter, based on the dyeing bath in solid content. Further, it may be used after being diluted with a solvent such as isopropyl alcohol or 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 method such as dip dyeing, printing or continuous dyeing.

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

(1) Production of compound (A):
In a four-necked flask equipped with a thermometer, a dropping device, and a stirrer, 94 g of phenol and 0.6 g of anhydrous aluminum chloride were added, the temperature was raised to 95 ° C., and 250 g of benzyl chloride was added dropwise gradually over about 4 hours. Stirring was continued for about 5 hours at the same temperature, then the mixture was transferred to a pressure reactor, 2 g of caustic potash was added, and 660 g of ethylene oxide was added at 160 to 170 ° C. over about 6 hours to obtain a reddish brown oily substance. This was neutralized, dehydrated and filtered, and 468 g was taken in a separate four-necked flask, and 59 g of chlorosulfonic acid was slowly added dropwise at 40 ° C. or lower for about 3 hours, and then nitrogen gas was introduced for about 4 hours. Hydrochloric acid was removed, and the resulting sulfate was neutralized with a caustic potash solution.
(2) Production of compound (B):
In a four-necked flask equipped with a thermometer, moisture receiver, and stirrer, put 880 g of polyethylene glycol having an average molecular weight of 880, 3 g of caustic potash, and 560 g of oleic acid, raise the temperature to 220 ° C., and esterify at that temperature for about 8 hours. Reaction was performed. The obtained esterified product was neutralized with an acetic acid solution.
(3) Production of dyeing aid:
In a beaker, take 20 g of the product obtained in (1), 20 g of the product obtained in (2), and 60 g of methylnaphthalene as carrier (C), and stir for about 30 minutes. 1 dyeing assistant was obtained.
The obtained dyeing assistant was tested for the dark color effect, dispersibility, and transferability according to the following method. The results are shown in Tables 3 and 4.

(1) Production of compound (A):
In a four-necked flask equipped with a thermometer, a dropping device, and a stirring device, 220 g of nonylphenol and 1.2 g of anhydrous aluminum chloride were added, and the temperature was raised to 95 ° C., and 250 g of benzyl chloride was gradually added dropwise over about 4 hours. After stirring for about 5 hours at the same temperature, the mixture was transferred to a pressure reactor, 1.6 g of caustic potash was added, and 880 g of ethylene oxide was added at 160 to 170 ° C., which took about 7 hours to obtain a reddish brown oily substance. It was. This was neutralized with catalyst, dehydrated and filtered, and 640 g was taken in another four-necked flask, and 59 g of chlorosulfonic acid was slowly added dropwise at 40 ° C. or below for about 3 hours, and then nitrogen gas was introduced for about 4 hours. Hydrochloric acid was removed, and the resulting sulfate was neutralized with a caustic potash solution.
(2) Production of compound (B):
In a pressure reactor, 92 g of glycerin and 2.6 g of caustic potash are added, and 1188 g of ethylene oxide is added at 160 to 170 ° C. in about 5 hours, and then aged. Next, 640 g of this product, 2.1 g of caustic potash, and 420 g of stearic acid are placed in a four-necked flask equipped with a thermometer, a moisture receiver and a stirrer, heated to 220 ° C., and esterified at that temperature for about 8 hours. The reaction was carried out. The obtained esterified product was neutralized with an acetic acid solution.
(3) Production of dyeing aid:
In a beaker, take 20 g of the product obtained in (1), 25 g of the product obtained in (2), and 55 g of trichlorobenzene as the carrier (C), and stir for about 30 minutes. An agent was obtained.
The obtained dyeing assistant was tested for the dark color effect, dispersibility, and transferability according to the following method. The results are shown in Tables 3 and 4.

Reaction was carried out in the same manner as in Examples 1 and 2 to obtain the dyeing assistants of Examples 3 to 6 shown in Table 1. The obtained dyeing assistant was tested for the dark color effect, dispersibility, and transferability according to the following method. The results are shown in Tables 3 and 4.

Comparative Example 1
In a beaker, 30 g of the compound (B) of Example 1 and 70 g of methylnaphthalene as the carrier (C) were taken and stirred for about 30 minutes to obtain the dyeing aid of Comparative Example 1 (Table 2). The obtained dyeing assistant was tested for the dark color effect, dispersibility, and transferability according to the following method. The results are shown in Tables 3 and 4.

Comparative Example 2
The compound (B) of Example 2 was used alone as a comparative dyeing assistant (Table 2), and the dark color effect, dispersibility and transferability test were conducted according to the following methods. The results are shown in Tables 3 and 4.

Comparative Example 3
The compound (C) of Example 2 was used alone as a comparative dyeing assistant (Table 2), and the dark color effect, dispersibility and transferability test were conducted according to the following methods. The results are shown in Tables 3 and 4.

Test methods in Examples and Comparative Examples are shown below.
(A) Evaluation of dark color effect <Test conditions>
Dye 1: Trial Blue 02 1% o. w. f.
Dyeing assistant: 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 x 30 minutes Dyeing machine: Color Master 12 (manufactured by Sakurai Dyeing Machine Industry)
<Test method>
A fabric made of polylactic acid fiber was dyed under the above conditions, and the dark color effect of the sample fabric was evaluated after washing with water.
<Judgment method>
Measurement of dark color effect of dyed fiber The L value of the dyed fiber was measured and evaluated using 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) Dispersibility test <Test conditions>
Dye 2: Dianix Red FB 2% o. w. f.
Dye 3: Dianix Blue KRN-FS 2% o. w. f.
Dyeing aid: 1.0 g / L (solid content conversion)
80% acetic acid: 0.3 ml / L
Bath ratio: 1:15
Temperature: 100 ° C
Dyeing machine: Color pet 12
<Test method>
Using a color pet 12 (manufactured by Nippon Dyeing Machinery), a fabric made of polylactic acid fiber is dyed by raising the temperature from 60 ° C. to 100 ° C. under the above conditions, and when it reaches 100 ° C., cooling is started immediately. The casing spot on the test cloth was visually judged after washing with water.
<Criteria>
A: Dye spots are hardly seen on the sample cloth.
○: Dye spots can be seen only about 1/4 on the sample cloth.
Δ: Dye spots can be seen up to about 1/2 on the sample cloth.
X: 3/4 or more of dye spots are seen on the sample cloth.

(C) Transferability test <Test condition a>
Dye 4: Dianix Orange B-SE 1% o. w. f.
Dye 5: Dianix KBN-SE 1% o. w. f.
Dye 6: Dianix Blue KBN-FS 1% o. w. f.
80% acetic acid: 0.3 ml / L
Bath ratio: 1:20
Temperature and time: 100 ° C x 30 minutes Dyeing machine: Color Master 12 (manufactured by Sakurai Dyeing Machine Industry)
<Test condition b>
Dyeing aid: 1.0 g / L (solid content conversion)
80% acetic acid: 0.3 ml / L
Bath ratio: 1:20
Temperature and time: 100 ° C x 30 minutes Dyeing machine: Color Master 12 (manufactured by Sakurai Dyeing Machine Industry)
<Test method>
A cloth of polylactic acid fiber dyed in advance under the test condition a is used as the original dyed cloth. The original dyed cloth and a white cloth of the same amount and the same quality as the original dyed cloth were treated in the same bath under the above test condition b, and the dye transfer property of the test cloth was examined after washing with water.
<Judgment method>
The reflectance of the original dyed cloth (1) and the dyed cloth (2) after the dye transfer test was measured with a Hitachi color analyzer 607 type, the K / S value was calculated from the Kubelka Munk equation, and the dye transfer rate was calculated. . Dye 3 has a transfer rate of 55% or more, and Dye 4 and Dye 5 have a transfer rate of 35% or more.
Transfer rate (%) = 100 × ((2) K / S) / ((1) K / S)

The manufacturing method of the fabric which consists of a polylactic acid type fiber used for the above test, and the measuring method of a physical property 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 mass. 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.

Measurement 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 (mass 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-isomer 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>
○…染色助剤が染料の濃色性、分散性および移染性の全ての性能を満たしている。
△…染色助剤が染料の濃色性、分散性および移染性のいずれかの性能を満たしている。
×…染色助剤が染料の濃色性、分散性および移染性の全ての性能を満たしていない。

<Comprehensive evaluation criteria>
○: The dyeing assistant satisfies all the performances of the dark color, dispersibility and dye transfer of the dye.
Δ: The dyeing assistant satisfies the performance of any of the darkness, dispersibility, and transferability of the dye.
X: The dyeing assistant does not satisfy all the performances of the dark color, dispersibility and dye transfer of the dye.

From the above results, the dyeing aid obtained by mixing the compounds (A), (B) and (C) of the present invention at a specific ratio is more effective in the dispersion leveling effect and dark color effect than the comparative dyeing aid. Was confirmed to be excellent.

Claims (5)

(A) One or more compounds represented by the following general formula (1)

[Wherein X is a naphthyl group, or

(However, R is a hydrogen atom, a phenyl group, a benzyl group, a styryl group, an alkyl group having 1 to 12 carbon atoms, a monobenzylphenyl group, a dibenzylphenyl group, a monostyrylphenyl group, a distyrylphenyl group, a cumyl group, or a monovalent group. A benzylcumyl group, a dibenzylcumyl group, a monostyrylcumyl group or a distyrylcumyl group, wherein n is an integer of 1 to 3, and when n is 2 or 3, the type of R is independently selected from the above. A ₁ is a polyethyleneoxy group having 10 to 35 ethyleneoxy groups bonded thereto, or a polyethyleneoxypolypropyleneoxy group having 9 to 30 ethyleneoxy groups and 1 to 5 propyleneoxy groups bonded thereto. M is K, Na, NH ₄ or 6 or more carbon atoms The lower N-alkyl ammonium or N-alkanol ammonium is shown. ],
(B) One or more of the compounds represented by the following general formula (2), (3) or (4)

[Wherein R _{1 to} R ₉ are each a higher fatty acid residue having 5 to 18 carbon atoms; A ₂ is a polyethyleneoxy group having 3 to 20 ethyleneoxy groups bonded thereto, or an ethyleneoxy group is 5 to 25 and a polyethyleneoxypolypropyleneoxy group having 1 to 5 propyleneoxy groups bonded thereto; A _{3 to} A ₅ are all polyethyleneoxy groups or polyethyleneoxypolypropyleneoxy groups, and A _{3 to} A _When all of ₅ are polyethyleneoxy groups, A _{3 to} A ₅ have a total of 9 to 60 ethyleneoxy groups, and when all of A _{3 to} A ₅ are polyethyleneoxypolypropyleneoxy groups, A ₃ to A ₅ has a total of 15 to 75 ethyleneoxy groups and a total of 3 to 15 propyleneoxy groups; A _{6 to} A ₉ are all polyethyleneoxy groups Or when all of A _{6 to} A ₉ are polyethyleneoxy groups, A _{6 to} A ₉ have a total of 12 to 80 ethyleneoxy groups, and A _{6 to} A ₉ If all are polyethyleneoxy polypropyleneoxy group, a ₆ to a ₉ has a total of 20 to 100 ethyleneoxy groups and total 4-20 propylene oxy group. And (C) a dyeing aid for a polylactic acid-based molded article, comprising one or more carriers. The compounding ratio of the compounds (A) to (C) is (A) :( B) :( C) = (0.01-10) :( 0.01-10): 1 by weight ratio. The dyeing aid described. The dyeing assistant according to claim 1 or 2, wherein the polylactic acid-based molded article is a polylactic acid-based fiber. A polylactic acid-based molded article dyed using the dyeing assistant according to claim 1 or 2. The polylactic acid-based molded article according to claim 4, wherein the molded article is a fiber.