TWI545241B - Dyeing composition and dyeing method using the same - Google Patents

Description

Dyeing composition and dyeing method using same

The present invention relates to a dyeing composition and a dyeing method, and more particularly to a dyeing composition for a polylactic acid fiber material and a dyeing method using the same.

Synthetic polymer materials have long been used as the main materials for various materials in daily life. However, since synthetic polymer materials may cause many problems, such as resource consumption and environmental problems such as pollution, the use of green materials instead of synthetic polymer materials has become an inevitable trend.

Polylactic acid (PLA) is a green material. The polylactic acid fiber material can be obtained by mixing starch extracted from corn or cassava, sugar extracted from sugar cane or sugar beet, and cellulose extracted from straw, and subjected to fermentation, dehydration, or the like. Further, the polylactic acid fiber material is a linear aliphatic thermoplastic polyester which is resistant to sterilization and easy to process, and is non-toxic, non-irritating and biodegradable. (biodegradable) and good biocompatibility. The polylactic acid fiber material has a glass transition temperature of about 60 ° C, a crystallization temperature of about 110 ° C, and a melting point of about 160 ° C. Products made from polylactic acid fiber materials have a smooth surface and are not harmful to the human body, so they are often used in the manufacture of clothing.

However, the polylactic acid fiber material has a low glass transition temperature, so the polylactic acid fiber material is not suitable for the high temperature dyeing technique at a temperature of about 130 ° C in the conventional garment manufacturing process. In addition, the conventional dyes have low dye uptake or leveling property on the polylactic acid fiber material, which causes the dyed polylactic acid fiber material to have a problem that the dye remains on the surface, thereby leading to the dyed polylactic acid fiber material. The washing fastness or light fastness is too low, even dye waste and other environmental problems. Therefore, development of a dyeing material suitable for a low-temperature dyeing process and having a good dye uptake and leveling property for a polylactic acid fiber material is a very important subject in the art.

The present invention provides a dyeing composition which has good dye uptake and leveling property for a polylactic acid fiber material, so when the dyeing composition is used to dye a polylactic acid fiber material, the dyeing temperature is lowered and the dyed polylactic acid is lowered. The fiber material has good wash fastness and light fastness.

The dyeing composition of the present invention is suitable for a dyeing method of a polylactic acid fiber material. The dye composition comprises a tetramolecular type auxiliary, a dye and a carrier, wherein the content of the tetramolecular auxiliary is 0.01% by weight to 10% by weight based on the total weight of the dyeing composition; The content is from 0.01% by weight to 10% by weight; The carrier is contained in an amount of from 80% by weight to 99.98% by weight.

In an embodiment of the invention, the tetramolecular type auxiliary agent is an anionic-nonionic tetramolecular type surfactant.

In an embodiment of the invention, the tetramolecular type auxiliary agent is a compound represented by the following formula (1): Wherein R represents an alkyl group of C6 to C22, n is an integer of from 20 to 60, and m is an integer of from 2 to 12.

In an embodiment of the present invention, the content of the above-mentioned tetramolecular auxiliary agent is 0.3% by weight to 1.2% by weight based on the total weight of the dyeing composition, and the content of the above dye is 0.3% by weight to 1.2%. weight%.

In an embodiment of the invention, the dye composition has a pH of from 3 to 6 at room temperature.

The method for dyeing a polylactic acid fiber material of the present invention comprises the following steps. A polylactic acid fiber material is provided. Providing a dye composition, wherein the dye composition comprises a tetramolecular auxiliary in an amount of 0.01% by weight to 10% by weight based on the total weight of the dyeing composition; and a dye content of 0.01% by weight to 10% by weight And a carrier having a content of from 80% by weight to 99.98 by weight. The polylactic acid fiber material is immersed in the dyeing composition. The polylactic acid fiber material is subjected to a dyeing step using the dyeing composition to color the polylactic acid fiber material.

In an embodiment of the invention, the dyeing step described above comprises the following procedure. The retarding procedure was carried out, and the temperature was raised from room temperature at a heating rate of 1 ° C/min to 4 ° C/min to a dyeing temperature of 95 ° C to 130 ° C. A dyeing procedure is carried out, and the temperature is maintained at the dyeing temperature of 95 ° C to 130 ° C for 20 minutes to 60 minutes. The cooling and discharging process is performed, and the temperature is lowered from 1 ° C / min to 4 ° C / min to a temperature of 45 ° C to 75 ° C, and the residual dyeing composition is discharged.

In an embodiment of the invention, the tetramolecular type auxiliary agent is an anionic-nonionic tetramolecular type surfactant.

In an embodiment of the invention, the tetramolecular type auxiliary agent is a compound represented by the following formula (1): Wherein R represents an alkyl group of C6 to C22, n is an integer of from 20 to 60, and m is an integer of from 2 to 12.

In an embodiment of the present invention, the content of the above-mentioned tetramolecular auxiliary agent is 0.3% by weight to 1.2% by weight based on the total weight of the dyeing composition, and the content of the above dye is 0.3% by weight to 1.2%. weight%.

In an embodiment of the invention, the dye composition has a pH of from 3 to 6 at room temperature.

Based on the above, the dyeing composition proposed by the present invention has a tetramolecular type auxiliary agent, thereby making the dyeing composition have good leveling property for the polylactic acid fiber material. And the dyeing rate. Further, in the dyeing method of the polylactic acid fiber material proposed by the present invention, by using the dyeing composition of the present invention, not only the dyeing step can be carried out at a low temperature, but also the dyed polylactic acid fiber material has good washing fastness. And light fastness.

The above described features and advantages of the invention will be apparent from the following description.

S10, S12, S14, S16, S18, S20, S22‧‧

1 is a flow chart of a dyeing method in accordance with an embodiment of the present invention.

2 is a distribution diagram of absorbances of Examples 27-38 and Comparative Examples 27-38.

Figure 3 is a graph showing the distribution of absorbance of Examples 39-50 and Comparative Examples 39-50.

4 is a distribution diagram of absorbances of Examples 51-62 and Comparative Examples 51-62.

Figure 5 is a graph showing the particle size distribution of Examples 27-38 and Comparative Examples 27-38.

Figure 6 is a graph showing the particle size distribution of Examples 39-50 and Comparative Examples 39-50.

Figure 7 is a graph showing the particle size distribution of Examples 51-62 and Comparative Examples 51-62.

In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Accordingly, the recitation of a particular range of values is equivalent to the disclosure of any value in the range of values and the The range is as if written in the specification and the arbitrary value is the same as the smaller value range. For example, the description of the "content of 0.3% by weight to 1.2% by weight" is equivalent to the disclosure of the "content of 0.6% by weight to 0.9% by weight", regardless of whether other values are listed in the specification.

In this context, the structure of a compound is sometimes represented by a skeleton formula. This representation can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. Of course, if the atom or atomic group is clearly drawn in the structural formula, the person who prescribes it shall prevail.

In order to prepare a dyeing composition which can be applied to a low-temperature dyeing procedure and which has a good dye uptake and leveling property for a polylactic acid fiber material in a dyeing process to achieve deep dyeing, an embodiment of the present invention provides a dyeing composition. , which can achieve the above advantages.

In the present embodiment, the dyeing composition includes a tetramolecular type auxiliary, a dye, and a carrier. These components will be described in detail below.

[Four molecular additives]

In the present embodiment, the tetramolecular type auxiliary has low foaming property, whereby the dye does not easily aggregate and has good dispersibility. As a result, the contact interface between the dye and the polylactic acid fiber material is increased, so that the dye has good dye uptake and leveling property for the polylactic acid fiber material. That is to say, the tetramolecular type auxiliary agent can uniformly adhere the dye to the surface of the polylactic acid fiber material and increase the adhesion of the dye on the surface of the polylactic acid fiber material.

In the present embodiment, the content of the tetramolecular auxiliary is from 0.01% by weight to 10% by weight based on the total weight of the dyeing composition. In detail, when the four molecules help When the content of the agent is less than 0.01% by weight, the dye dyeing rate and the leveling property of the polylactic acid fiber material are not good; and when the content of the tetra-type auxiliary agent is more than 10% by weight, the dye is easily made from the polylactic acid. The surface of the fibrous material leaves and returns to the dyeing composition, and the dyeing process cannot be performed efficiently. Further, in an embodiment, the content of the tetramolecular auxiliary is, for example, from 0.3% by weight to 1.2% by weight.

The tetramolecular type auxiliary agent is, for example, an anionic-nonionic tetramolecular type surfactant, and it can be represented by the following formula (1): Wherein R represents an alkyl group of C6 to C22, n is an integer of from 20 to 60, and m is an integer of from 2 to 12.

Specifically, the tetramolecular type auxiliary agent represented by the formula (1) contains both a hydrophobic group and a hydrophilic group, wherein the left and right terminals R are hydrophobic groups, and the left and right tetra-terminal -SO ₃ Na dissociates in water to form an anionic hydrophilic group. a base-SO ₃ ^- and a multi-stage polyoxyethylene (PEO) in the central portion (ie ) is a nonionic hydrophilic group.

In detail, the hydrophobic group R makes it easy for the tetramolecular type auxiliary and the dye to form unstable aggregates. In this way, in the dyeing process, the aggregate will enter the interior of the polylactic acid fiber material and gradually release the dye to improve the contact and/or combination of the dye with the polylactic acid fiber material, thereby achieving uniform dyeing effect. In addition, when dyeing When the carrier of the color composition is water, the hydrophobic group R can effectively reduce the surface tension of the water, thereby allowing the dye-containing dye composition to be more effectively dispersed on the surface of the polylactic acid fiber material, lifting the dye and the polylactic acid. The opportunity for the action of fibrous materials.

Further, when the carrier of the dyeing composition is water, the aforementioned hydrophilic group will make the tetramolecular type auxiliary agent more easily dispersed or dissolved in water. As a result, when the tetramolecular type auxiliary and the poorly water-soluble dye form an aggregate, the aggregate having the dye will be more easily dispersed in the water, thereby improving the dispersibility of the dye in water.

From another point of view, since the tetramolecular type auxiliary has a multi-stage polyoxyethylene segment belonging to a soft segment, it can be changed into an appropriate form depending on its characteristics or environment when it acts with the dye. Compared with the conventional auxiliaries, the required amount of addition can be greatly reduced in the case where the desired dyeing effect can be achieved. In detail, when a tetramolecular type auxiliary agent is present in the dyeing system, the soft segments in each of the four molecular type auxiliary agents are bent inward to assume a paw type, wherein one end of the claw type is The structure contains the aforementioned hydrophilic group and the other end is a hydrophobic group R. In this way, the tetramolecular type auxiliary agent is easily aggregated to form a micelle capable of coating the dye and entering the inside of the polylactic acid fiber material, thereby achieving a good dyeing effect. In addition, when the concentration required for the tetramolecular auxiliary is reduced, the soft segments in each of the tetramolecular additives will be extended to a linear state. In this way, the structure formed by the tetra-type auxiliaries being attracted to each other through the hydrophobic bases R at the left and right ends will improve the penetration-promoting effect of the dye.

[dye]

In the present embodiment, the dye is permeable to the dyeing process by molecular forces (for example, hydrogen bonding or van der Waals) is adsorbed on the surface of the polylactic acid fiber material. The dye may be any dye known to those of ordinary skill in the art. Specifically, the dye may be a disperse dye such as blue dye (BLUE SF-3RT 200% GRAN, manufactured by Taiwan Sugar Co., Ltd.), red dye (Dianix Rubine SE-B, manufactured by DyStar Co., Ltd.) Yellow dye (Dianix Yellow AM-42, manufactured by DyStar), black dye (Goldenlon Black DXF, manufactured by Xiejing) or a combination of the foregoing.

In the present embodiment, the content of the dye is from 0.01% by weight to 10% by weight based on the total weight of the dyeing composition. In detail, when the content of the dye is less than 0.01% by weight, the polylactic acid fiber material may not be effectively dyed to give a desired color; and when the content of the dye is more than 10% by weight, excessive dye residue Will cause problems with dye waste or environmental pollution. Further, in an embodiment, the content of the dye is, for example, 0.3% by weight to 1.2% by weight.

[carrier]

In the present embodiment, the carrier functions to provide an environment in which the dye and the tetra-type auxiliary agent in the dyeing composition can be arbitrarily mixed and/or agglomerated. The carrier is, for example, water, ethanol, acetone or a mixed solution thereof. The carrier is contained in an amount of from 80% by weight to 99.98% by weight based on the total weight of the dyeing composition.

Further, in the present embodiment, the dyeing composition may further include a pH adjusting agent for adjusting the pH of the dyeing composition. The pH of the dye composition may be, for example, 3 to 6 at room temperature, and the pH adjuster is, for example, glacial acetic acid, formic acid, phosphoric acid or hydrochloric acid. When the pH of the dyeing composition is in the above range, it will be able to affect the polylactic acid fiber. The dimensional charge of the material, while also increasing the degree of dye dispersion and its speed of bonding with the polylactic acid fiber material.

Based on the above embodiment, it is understood that since the dyeing composition of the present invention includes a tetramolecular type auxiliary agent which is novel in structure and whose form is changed depending on characteristics or environment, when the dyeing composition is used to dye the polylactic acid fiber material, The four-molecule additive can improve the dispersibility of the dye and make the dye easy to enter the interior of the polylactic acid fiber material, thereby improving the dye uptake rate and leveling property of the polylactic acid fiber material.

Hereinafter, a method of dyeing a polylactic acid fiber material using the dyeing composition of the present invention will be described in detail with reference to FIG. 1 is a flow chart of a dyeing method in accordance with an embodiment of the present invention.

First, step S10 is performed to provide a polylactic acid fiber material. In the present embodiment, the polylactic acid fiber material may be any polylactic acid fiber material known to those skilled in the art. For example, the polylactic acid fiber material may be a polylactic acid knitted fabric or a polylactic acid plain woven fabric.

Next, step S12 is performed to provide the dyeing composition described in the above embodiment. It is to be noted that in the present embodiment, the step S10 is performed before the step S12, that is, the polylactic acid fiber material is first supplied to prepare the dye composition, but the present invention is not limited thereto. In other embodiments, the dyeing method may also be followed by step S10 while or after the preparation of the dyeing composition of step S12.

Next, in step S14, the polylactic acid fiber material is introduced into the dyeing composition at room temperature. In detail, in this step, the bath ratio of the polylactic acid fiber material to the dye composition is, for example, about 1:10. For example, if you want to weigh 10 grams The polylactic acid fiber material is dyed, and it can be immersed in a dyeing composition having a weight of 100 g.

Thereafter, in step S16, the polylactic acid fiber material is subjected to a dyeing step using the dyeing composition to color the polylactic acid fiber material. The dyeing step is, for example, immersing the polylactic acid fiber material in the dyeing composition for a period of time and at a specific temperature condition.

In more detail, the above-described dyeing step S16 includes the following procedures: a dyeing process, a dyeing process, and a cooling-out process. Each program will be described in detail below.

First, a retarding process (step S18) is carried out, and the temperature is raised from room temperature at a temperature increase rate of 1 ° C/min to 4 ° C/min to a dyeing temperature of 95 ° C to 130 ° C. In the retarding process (step S18), the dye in the dyeing composition may be initially adsorbed on the surface of the polylactic acid fiber material.

Next, a dyeing procedure (step S20) is carried out, and the temperature is maintained at the dyeing temperature of 95 ° C to 130 ° C for 20 minutes to 60 minutes. It is worth noting that in the dyeing procedure (step S20), since the dyeing composition contains a tetramolecular type auxiliary, its interaction with the dye will improve the dispersibility of the dye and make the dye easy to enter the polylactic acid fiber material. Internally, the dyeing composition has a good dye uptake and leveling property to the polylactic acid fiber material at a low temperature of the dyeing temperature of 95 ° C to 130 ° C. In this way, the dyeing method of the present embodiment not only enables the polylactic acid fiber material to achieve a good deep dyeing effect at a low temperature, but also enables the dyed polylactic acid fiber material to have good washing fastness and light fastness.

After that, the cooling and discharging process is performed (step S22), at 1 ° C / min to After the temperature drop rate of 4 ° C / min was cooled to 45 ° C to 75 ° C, the residual dye composition was drained. Thus, the dyeing step S16 is completed.

Further, after the dyeing step S16, the dyeing method of the present embodiment may further include a step of washing, dehydrating, and air drying the dyed polylactic acid fiber material.

According to the above embodiment, in the dyeing method of the polylactic acid fiber material of the present invention, the polylactic acid fiber material is dyed by using the dyeing composition containing the tetramolecular type auxiliary agent, and the dyed polylactic acid fiber material can have a good quality. Wash fastness and light fastness. Further, the dyeing temperature range in the dyeing process is always lower than 130 ° C, so that the dyeing method of the polylactic acid fiber material of the present invention has an advantage that it can be carried out at a low temperature, thereby avoiding polylactic acid fiber, compared with the prior art. The nature of the material changes due to high temperatures.

The features of the present invention will be more specifically described below with reference to Experimental Examples 1-4. Although the following Experimental Examples 1-4 are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the present invention. Therefore, the present invention should not be construed restrictively by Experimental Examples 1-4 described below.

Experimental example 1

The performance of the dyeing composition and the dyeing method proposed in the above embodiments on the washing fastness test was explained in detail by way of Examples 1-12 and Comparative Examples 1-12.

The materials and instruments used in Examples 1-12 and Comparative Examples 1-12 are as follows.

Polylactic acid fiber material: Polylactic acid knitted fabric, 8L0319D specification 63" × 2220g / y, purchased from Weiqi International Co., Ltd.

Four molecular type additives: Where n = 41, m = 6 and the preparation method thereof will be described in detail in the subsequent paragraphs.

Dyes: BLUE SF-3RT 200% GRAN, purchased from Taiwan Sugar Company.

Carrier: water.

pH adjuster: glacial acetic acid (CH ₃ COOH), molecular weight 60.05, reagent level, purchased from Japan Pharmaceutical Company.

RUBI dyeing proofing machine: Model RAPID, purchased from Ruby Instruments.

Washing test machine: Model LEF, purchased from Lianzhou Instrument Company.

<Preparation of four-molecule additives>

The above tetramolecular type auxiliary was prepared in the following synthesis steps in the following order. However, the following synthetic steps are merely illustrative and not limiting the scope of the invention.

First, the compound (A) is synthesized, and its reaction formula is as follows:

In detail, the synthesis reaction of the compound (A) includes the following steps. First, 1 mole of Tetronic 701 (average molecular weight of 2,428 and n=41, m=6, purchased from Sino-Japanese synthesis) and 4 moles of maleic anhydride (molecular weight of 980.6, reagent level, purchased from Lin Chun Pharmaceutical Industry Co., Ltd. was placed in a four-neck reaction flask equipped with a Teflon stir bar and a temperature control rod. Next, the temperature was raised from room temperature to 60 ° C, and stirred to uniformly mix Tetronic 701 with maleic anhydride. Thereafter, 1 gram of titanium isopropoxide (molecular weight 284, purchased from ACROS) was added as a catalyst, and the temperature was gradually raised to 130 °C. Tetronic 701 was reacted with maleic anhydride for 6 hours while maintaining the temperature at 130 ° C to obtain a compound (A).

Next, the compound (B) is synthesized, and its reaction formula is as follows:

In detail, the synthesis reaction of the compound (B) includes the following steps. first First, 4 moles of fatty alcohol (molecular weight: 186.38, reagent grade, purchased from Japanese reagent) and 1 mole of compound (A) were placed in a reaction flask. Next, 1 g of titanium isopropoxide (molecular weight 284, purchased from ACROS) was added as a catalyst, and the temperature was gradually raised to 130 °C. The fatty alcohol was reacted with the compound (A) for 5 hours while maintaining the temperature at 130 ° C to obtain a compound (B).

Thereafter, the aforementioned tetramolecular type auxiliary is synthesized, and the reaction formula is as follows:

In detail, the synthesis reaction of the tetramolecular auxiliary includes the following steps. First, the temperature of the reaction flask in which the aforementioned compound (B) was present was lowered to 90 ° C, and an appropriate amount of an aqueous solution of sodium hydrogen sulfite (concentration: 50% by weight, purchased from a Japanese reagent) was added. Next, the reaction was allowed to proceed for 4 hours under reflux in a state of maintaining the temperature at about 90 ° C to obtain a tetramolecular auxiliary.

<Example 1>

First, 10 g of polylactic acid knitted fabric (8L0319D size 63" × 2220g / y, purchased from Weiqi International Co., Ltd.) was provided. Next, 100 g of the dyeing composition was provided, wherein the tetra-type auxiliaries were 0.05 g, dye 0.3 g, the carrier is Water, glacial acetic acid was 0.04 g and the pH was 4.5. Thereafter, the above dyed composition was poured into a steel cup at room temperature, and the aforementioned polylactic acid knitted fabric was immersed in the dyeing composition. Next, the steel cup was placed in a RUBI dyeing proofing machine, and the temperature was raised to a dyeing temperature of 105 ° C at a heating rate of 2.5 ° C / min and held for 30 minutes, and then the temperature was lowered at a cooling rate of 3 ° C / min. Up to the cylinder temperature of 60 ° C. Next, the remaining dyeing composition is drained and collected for retention. Thereafter, the dyed polylactic acid knitted fabric was washed with water, and then dehydrated and air-dried to obtain a dyed polylactic acid knitted fabric of Example 1.

<Example 2-12 and Comparative Example 1-12>

The dyed polylactic acid knitted fabrics of Examples 2 to 12 and Comparative Examples 1 to 12 were prepared in the same manner as in Example 1. The difference is that when the dyed polylactic acid knitted fabric of Examples 2-12 and Comparative Examples 1-12 was prepared, the content of the dye, the content of the tetramolecular auxiliary, and the dyeing temperature were not completely the same as those of Example 1, and the details thereof are detailed. Table 1 below.

Next, the dyed fast lactic acid knitted fabrics obtained in Examples 1-12 and Comparative Examples 1-12 were tested for washing fastness, and the test results are shown in Table 2, respectively.

<Test for washing fastness>

The test for washing fastness was carried out in accordance with the AATCC 61 2A test method.

Preparation of test samples: The dyed polylactic acid knitted fabrics obtained in Examples 1-12 and Comparative Examples 1-12 were respectively cut into test pieces of 5 cm × 15 cm, and various fiber-attached cloths No. 10 were nailed in each using a stapler. On the test sample, a variety of fiber attachments 10 include acetate woven fabric (Ace), cotton woven fabric (C), nylon woven fabric (N), polyester woven fabric (T), acrylic woven fabric (Acr). ) and wool woven fabric (W).

Test procedure: First, the heating temperature of the water washing tester (Model H-12C, purchased from Linault Instruments) was set to 49 ° C (± 2 ° C). Next, each test sample was placed in a steel cup, and 150 ml of WOB solvent (standard detergent for AATCC washing fastness test) and 50 steel balls were added. After that, separate the steel cups In the water washing tester, after running at a set temperature of 49 ° C (± 2 ° C) for 45 minutes, each test sample was taken out, washed with water and dried.

Evaluation criteria: AATCC contamination is compared with each test sample using a gray scale to assess the level of wash fastness, with grades 5, 4-5, 4, 3-4, 3, 2 - Level 3, Level 2, Level 1-2, Level 1, and the higher the number of stages, the higher the wash fastness.

From the results of Table 2, it was found that the dyed polylactic acid knitted fabrics obtained in Examples 1-12 had higher washing fastness than the dyed polylactic acid knitted fabrics obtained in Comparative Examples 1-12. . In other words, compared to the absence of tetramolecular help The dyeing composition of the agent, when dyed using the dye composition having the tetramolecular auxiliary, the polylactic acid knitted fabric dyed by the same has good washing fastness.

Experimental example 2

The performance of the dyeing composition and the dyeing method proposed in the foregoing embodiments on the sunlight fastness test was explained in detail by way of Examples 13-17 and Comparative Examples 13-17.

The materials and instruments used in Examples 13-17 and Comparative Examples 13-17 are as follows.

Polylactic acid fiber material: polylactic acid knitted fabric, product code is 8L0319D, specification 63" × 2220g / y, purchased from Weiqi International Co., Ltd., and hereinafter referred to as polylactic acid knitted fabric A; polylactic acid knitted fabric, product code is 8L0319D1 , Specification 62" × 260g / y, purchased from Weiqi International Co., Ltd., and hereinafter referred to as polylactic acid knitted fabric B; polylactic acid knitted fabric, product code is 8L0309D, specification 61" × 215g / y, purchased from Weiqi International Ltd., and hereinafter referred to as polylactic acid knitted fabric C.

Four molecular type additives: n = 41, m = 6 and the preparation method thereof has been disclosed in the above Experimental Example 1.

Dyes: BLUE SF-3RT 200% GRAN, purchased from Taiwan Sugar Company.

Carrier: water.

pH adjuster: glacial acetic acid (CH ₃ COOH), molecular weight 60.05, reagent level, purchased from Japan Pharmaceutical Company.

RUBI dyeing proofing machine: Model RAPID GD-02, purchased from Ruby Instruments.

Light fastness tester: Model: CI 300+, purchased from Linault Instruments.

<Example 13>

First, 10 g of polylactic acid knitted fabric B was provided. Next, 100 g of the dye composition was provided, wherein the tetramolecular auxiliary was 0.05 g, the dye was 0.9 g, the carrier was water, glacial acetic acid was 0.04 g, and the pH was 4.5. Thereafter, the above dyed composition was poured into a steel cup at room temperature, and the aforementioned polylactic acid knitted fabric was immersed in the dyeing composition. Next, the steel cup was placed in a RUBI dyeing proofing machine, and the temperature was raised to a dyeing temperature of 105 ° C at a heating rate of 2.5 ° C / min and held for 30 minutes, and then the temperature was lowered at a cooling rate of 3 ° C / min. Up to the cylinder temperature of 60 ° C. Next, the remaining dyeing composition is drained and collected for retention. Thereafter, the dyed polylactic acid knitted fabric was washed with water, and then dehydrated and air-dried to obtain a dyed polylactic acid knitted fabric of Example 13.

<Examples 14-17 and Comparative Examples 13-17>

The dyed polylactic acid knitted fabrics of Examples 14-17 and Comparative Examples 13-17 were prepared in the same manner as in Example 13. The difference is that when preparing the dyed polylactic acid knitted fabric of Examples 14-17 and Comparative Examples 13-17, the dye content, the four-molecule type assists The content of the agent, the dyeing temperature and the type of the polylactic acid fiber material were not exactly the same as in Example 13, and the details thereof are shown in Table 3 below.

Next, the dyed polylactic acid knitted fabrics obtained in Examples 13 to 17 and Comparative Examples 13 to 17 were subjected to the test for fastness to sunlight, and the test results are shown in Table 4, respectively.

<Test for fastness to sunlight>

The solar fastness test was carried out in accordance with the AATCC 16 test method.

Preparation of Test Samples: The dyed polylactic acid knitted fabrics obtained in Examples 13-17 and Comparative Examples 13-17 were respectively cut into test pieces of 4 cm × 7 cm.

Test procedure: First, each test sample is loaded into the sample holder, and the sample holder is placed on the holder of the light fastness tester. Next, the light fastness The test machine was started to expose the test sample for 20 hours.

Evaluation criteria: AATCC faded color is compared with each test sample by gray scale to evaluate the level of light fastness, which is grade 5, grade 4-5, grade 4, grade 3-4, grade 3, 2-3, 2, 1-2, and 1, and the higher the number, the higher the fastness to sunlight, that is, the smaller the fade.

From the results of Table 4, it was found that the dyed polylactic acid knitted fabrics obtained in Examples 13-17 had higher light fastness than the dyed polylactic acid knitted fabrics obtained in Comparative Examples 13-17. . That is to say, the polylactic acid knitted fabric dyed by the dyed composition having the tetramolecular type auxiliary agent has good light fastness when compared with the dyeing composition not containing the tetramer type auxiliary. .

Experimental example 3

The performance of the dyeing composition and the dyeing method proposed in the foregoing embodiments on the strength test are explained in detail by Examples 18-26 and Comparative Examples 18-26.

The materials and instruments used in Examples 18-26 and Comparative Examples 18-26 are as follows.

Polylactic acid fiber material: polylactic acid knitted fabric, product code is 8L0319D, specification 63" × 2220g / y, purchased from Weiqi International Co., Ltd., and hereinafter referred to as polylactic acid knitted fabric A; polylactic acid knitted fabric, product code is 8L0319D1 , Specification 62" × 260g / y, purchased from Weiqi International Co., Ltd., and hereinafter referred to as polylactic acid knitted fabric B; polylactic acid knitted fabric, product code is 8L0309D, specification 61" × 215g / y, purchased from Weiqi International Ltd., and hereinafter referred to as polylactic acid knitted fabric C.

Four molecular type additives: n = 41, m = 6 and the preparation method thereof has been disclosed in the above Experimental Example 1.

Dyes: BLUE SF-3RT 200% GRAN, purchased from Taiwan Sugar Company.

Carrier: water.

pH adjuster: glacial acetic acid (CH ₃ COOH), molecular weight 60.05, reagent level, purchased from Japan Pharmaceutical Company.

RUBI dyeing proofing machine: Model RAPID GD-02, purchased from Ruby Instruments.

Spectrophotometer: Model: Color-Eye 2180, purchased from Linault Instruments.

<Example 18>

First, 10 g of polylactic acid knitted fabric B was provided. Next, 100 g of the dye composition was provided, wherein the tetramolecular auxiliary was 0.05 g, the dye was 0.3 g, the carrier was water, glacial acetic acid was 0.04 g, and the pH was 4.5. Thereafter, the above dyed composition was poured into a steel cup at room temperature, and the aforementioned polylactic acid knitted fabric was immersed in the dyeing composition. Next, the steel cup was placed in a RUBI dyeing proofing machine, and the temperature was raised to a dyeing temperature of 105 ° C at a heating rate of 2.5 ° C / min and held for 30 minutes, and then the temperature was lowered at a cooling rate of 3 ° C / min. Up to the cylinder temperature of 60 ° C. Next, the remaining dyeing composition is drained and collected for retention. Thereafter, the dyed polylactic acid knitted fabric was washed with water, and then dehydrated and air-dried to obtain a dyed polylactic acid knitted fabric of Example 18.

<Examples 19-26 and Comparative Examples 18-26>

The dyed polylactic acid knitted fabrics of Examples 19-26 and Comparative Examples 18-26 were prepared in a similar manner to Example 18. The difference is that the dye content, the content of the tetramolecular auxiliary, the dyeing temperature, and the type of the polylactic acid fiber material are incomplete with the example 18 when preparing the dyed polylactic acid knitted fabric of Examples 19-26 and Comparative Examples 18-26. The same details are detailed in Table 5 below.

Next, the dyed polylactic acid knitted fabrics obtained in Examples 18-26 and Comparative Examples 18-26 were respectively subjected to the calculation of the strength, and the test results are shown in Table 6, respectively.

<calculation of strength>

The dyed polylactic acid knitted fabrics of Examples 18-26 and Comparative Examples 18-26 were separately measured using a spectrophotometric colorimeter to obtain respective reflectances. Next, according to Kubelka-Munk Theory, the results obtained by Example 18, Example 22, Example 25, Comparative Example 18, Comparative Example 22, and Comparative Example 25, respectively. The dyed polylactic acid knitted fabric was used as a standard sample, and the dyed polylactic acid obtained in Examples 19-21, Examples 23-24, Example 26, Comparative Example 19-21, Comparative Examples 23-24, and Comparative Example 26 was calculated. The strength of the knitted fabric. In detail, in Table 6 below, the tempo of Example 18, Example 22, Example 25, Comparative Example 18, Comparative Example 22, and Comparative Example 25 (ie, the standard sample) was set to 100.00.

From the results of Table 6, it was found that the dyed polylactic acid obtained in Example 18, Example 22, Example 25, Comparative Example 18, Comparative Example 22, and Comparative Example 25 in which the dye content in the dye composition was 0.3% by weight. When the knitted fabric was used as a standard sample, compared with the comparative examples 19-21, the comparative examples 23-24, and the comparative example 25 in which the dyeing composition did not contain the tetra-type auxiliary agent, the dyeing composition had the tetra-molecular auxiliary agent. The polylactic acid knitted fabrics dyed in Examples 19-21, Examples 23-24, and Example 25 all had greater strength. This means that, in the case of the same dye content, the dyeing composition having the tetramolecular type auxiliary agent can make the polylactic acid knitted fabric dyed into a deeper color, that is, the dyeing composition having the tetramolecular type auxiliary can achieve the concentration of the poly The effect of lactic acid knitted fabric for deep dyeing.

Experimental example 4

The residual dye detection and particle size detection of the dye composition remaining after dyeing by the dyeing composition and the dyeing method proposed in the above embodiments were explained in detail by way of Examples 27-62 and Comparative Examples 27-62.

The materials and instruments used in Examples 27-62 and Comparative Examples 27-62 are as follows.

Polylactic acid fiber material: polylactic acid knitted fabric, product code is 8L0319D, specification 63" × 2220g / y, purchased from Weiqi International Co., Ltd., and hereinafter referred to as polylactic acid knitted fabric A; polylactic acid knitted fabric, product code is 8L0319D1 , Specification 62" × 260g / y, purchased from Weiqi International Co., Ltd., and hereinafter referred to as polylactic acid knitted fabric B; polylactic acid knitted fabric, product code is 8L0309D, specification 61" × 215g / y, purchased from Weiqi International Ltd., and hereinafter referred to as polylactic acid knitted fabric C.

Four molecular type additives: n = 41, m = 6 and the preparation method thereof has been disclosed in the above Experimental Example 1.

Dyes: BLUE SF-3RT 200% GRAN, purchased from Taiwan Sugar Company.

Carrier: water.

pH adjuster: glacial acetic acid (CH ₃ COOH), molecular weight 60.05, reagent level, purchased from Japan Pharmaceutical Company.

RUBI dyeing proofing machine: Model RAPID GD-02, purchased from Ruby Instruments.

Ultraviolet Spectrometer: Model: Lambda UV-Vis, available from Perkin Elmer.

Particle size analyzer: Model: LB-550, purchased from HORIBA.

<Example 27>

First, 10 g of polylactic acid knitted fabric A was provided. Next, 100 g of the dye composition was provided, wherein the tetramolecular auxiliary was 0.05 g, the dye was 0.3 g, the carrier was water, glacial acetic acid was 0.04 g, and the pH was 4.5. Thereafter, the above dyed composition was poured into a steel cup at room temperature, and the aforementioned polylactic acid knitted fabric was immersed in the dyeing composition. Next, the steel cup was placed in a RUBI dyeing proofing machine, and the temperature was raised to a dyeing temperature of 105 ° C at a heating rate of 2.5 ° C / min and held for 30 minutes, and then the temperature was lowered at a cooling rate of 3 ° C / min. Up to the cylinder temperature of 60 ° C. Next, the residual dyeing composition was drained and collected to be retained to obtain the residual dyeing composition of Example 27.

<Examples 28-62 and Comparative Examples 27-62>

Examples 28-62 and Comparative Examples 27-62 were obtained in a similar manner to Example 27. The remaining dyeing composition. The difference is that the residual dyeing compositions of Examples 28-62 and Comparative Examples 27-62 are not identical to Example 27 by the use of the dye content, the content of the tetramolecular auxiliary, the dyeing temperature, and the type of the polylactic acid fiber material. The details obtained after the dyeing composition was dyed are detailed in Table 7 below.

Next, the residual dyeing compositions of Examples 27-62 and Comparative Examples 27-62 were subjected to residual dye detection and particle size detection by an ultraviolet spectrometer and a particle size analyzer, respectively, and the detection results are shown in FIGS. 2 to 7, respectively. .

2 is a distribution diagram of absorbances of Examples 27-38 and Comparative Examples 27-38. Figure 3 is a graph showing the distribution of absorbance of Examples 39-50 and Comparative Examples 39-50. 4 is a distribution diagram of absorbances of Examples 51-62 and Comparative Examples 51-62. Figure 5 is a graph showing the particle size distribution of Examples 27-38 and Comparative Examples 27-38. Figure 6 is a graph showing the particle size distribution of Examples 39-50 and Comparative Examples 39-50. Figure 7 is a graph showing the particle size distribution of Examples 51-62 and Comparative Examples 51-62.

In detail, as is apparent from Fig. 2 to Fig. 4, the residual dye compositions of Examples 27-62 had lower absorbances than the residual dye compositions of Comparative Examples 27-62, indicating that they all had lower The residual concentration of the dye. That is to say, the dye can have a better dye uptake rate to the polylactic acid knitted fabric when dyed using the dye composition having the tetramolecular type auxiliary agent as compared with the dye composition which does not contain the tetramolecular type auxiliary.

Further, as is apparent from Fig. 5 to Fig. 7, the particles in the remaining dyeing compositions of Examples 27-62 had smaller particle diameters than the residual dyeing compositions of Comparative Examples 27-62. That is to say, compared to the dyeing composition without the tetra-type auxiliaries When the dyeing composition has a tetramolecular type auxiliary, the dye is less likely to be agglomerated and has better dispersibility.

In summary, the dyeing composition proposed by the present invention has a tetramolecular type auxiliary agent, wherein the tetramolecular type auxiliary agent has both a hydrophobic group and a hydrophilic group but has low foaming property, and the structure can be based on its characteristics or environment. Change to the appropriate type. In this way, in the dyeing method of the polylactic acid fiber material proposed by the present invention, by using the dyeing composition having the tetramolecular type auxiliary agent, the dispersibility of the dye is improved and the affinity of the dye to the polylactic acid fiber material can be obtained. The dye has good dyeing rate, leveling property and deep dyeing property for the polylactic acid fiber material, and the dyed polylactic acid fiber material has good washing fastness and light fastness. Furthermore, the dyeing method of the polylactic acid fiber material of the present invention can be carried out at less than 130 ° C and has a good dyeing effect, so that the dyeing composition of the present invention can be applied to a low-temperature dyeing procedure, thereby avoiding polylactic acid fiber material. The nature of the change in the staining procedure.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

S10, S12, S14, S16, S18, S20, S22‧‧

Claims (9)

A dyeing composition suitable for a dyeing method of a polylactic acid fiber material, the dyeing composition comprising: a tetramolecular type auxiliary agent, wherein the content of the tetramolecular type auxiliary agent is 0.01 based on the total weight of the dyeing composition a weight% to 10% by weight; a dye having a content of the dye of 0.01% by weight to 10% by weight based on the total weight of the dyeing composition; and a carrier, based on the total weight of the dyeing composition, The content of the carrier is from 80% by weight to 99.98% by weight, wherein the tetramolecular type auxiliary agent is a compound represented by the following formula (1): Wherein R represents an alkyl group of C6 to C22, n is an integer of from 20 to 60, and m is an integer of from 2 to 12. The dyeing composition according to claim 1, wherein the content of the tetramolecular auxiliary is from 0.3% by weight to 1.2% by weight based on the total weight of the dyeing composition. The dyeing composition according to claim 1, wherein the dye is contained in an amount of from 0.3% by weight to 1.2% by weight based on the total weight of the dyeing composition. The dyeing composition of claim 1, wherein the dyeing composition has a pH of from 3 to 6 at room temperature. A method for dyeing a polylactic acid fiber material, comprising: providing a polylactic acid fiber material; providing a dyeing composition, the dyeing composition comprising: a tetramolecular type auxiliary agent, the four molecules based on the total weight of the dyeing composition The content of the type auxiliary is from 0.01% by weight to 10% by weight, wherein the tetramolecular auxiliary is a compound represented by the following formula (1): Wherein R represents an alkyl group of C6 to C22, n is an integer of from 20 to 60, and m is an integer of from 2 to 12; and the dye is contained in an amount of 0.01% by weight based on the total weight of the dyeing composition to 10% by weight; and a carrier, the carrier is contained in an amount of 80% by weight to 99.98% by weight based on the total weight of the dyeing composition; and the polylactic acid fiber material is immersed in the dyeing composition; The polylactic acid fiber material is subjected to a dyeing step using the dyeing composition to color the polylactic acid fiber material. The method for dyeing a polylactic acid fiber material according to claim 5, wherein the dyeing step comprises: performing a dyeing process, and heating to a dyeing temperature at a temperature rising rate of 1 ° C/min to 4 ° C/min at room temperature. Temperature 95 ° C to 130 ° C; Performing a dyeing process, holding the temperature at the dyeing temperature of 95 ° C to 130 ° C for 20 minutes to 60 minutes; and performing a cooling and discharging process, cooling at a cooling rate of 1 ° C / min to 4 ° C / min to a cylinder temperature of 45 ° C After 75 ° C, the residual dye composition was drained. The method for dyeing a polylactic acid fiber material according to claim 5, wherein the content of the tetramolecular auxiliary agent is from 0.3% by weight to 1.2% by weight based on the total weight of the dyeing composition. The method for dyeing a polylactic acid fiber material according to claim 5, wherein the dye is contained in an amount of from 0.3% by weight to 1.2% by weight based on the total mass of the dyeing composition. A method of dyeing a polylactic acid fiber material according to claim 5, wherein the dye composition has a pH of 3 to 6 at room temperature.