CN107164979A - A kind of polyimide support colouring method - Google Patents

Abstract

The invention discloses a polyimide carrier dyeing method, which belongs to the technical field of textile printing and dyeing. The present invention adopts following technology: (1) pretreatment of polyimide fiber fabric is to remove the impurity attached to the fabric in silk making, weaving and storage process; (2) organic matter containing amide structure is used as the carrier of polyimide dyeing , impart a certain amount of color to the fabric through carrier dyeing; (3) wash, soap and wash the dyed fabric to remove the floating color of the dyeing. In the present invention, the polyimide fabric is dyed under high temperature conditions by using the carrier and the cationic dye, the fabric has a certain color yield, and the dyed fabric has higher color fastness to washing.

Description

A kind of polyimide carrier dyeing method

technical field

The invention relates to a polyimide carrier dyeing method, which belongs to the fields of textile printing and dyeing auxiliaries and textile dyeing and finishing processing.

Background technique

Polyimide fiber (Formula 1) is a high-strength, high-modulus high-performance fiber. Its excellent mechanical properties, high temperature resistance, chemical resistance, radiation resistance and insulation properties make polyimide fibers widely used. Concern, compared with high-performance fibers such as aramid, polyimide has better comprehensive application. Polyimide fiber can be used to develop various protective clothing, can be used as high-temperature filter cotton, high-temperature filter felt, and can also be widely used in special application fields such as aerospace, and has very considerable application prospects.

The main chain of polyimide contains imide rings. The structure is as follows. The molecular structure of the fiber is very tight, the stereoregularity is good, and the glass transition temperature is above 300 ° C. Therefore, it is very difficult to dye polyimide fibers. Under normal high temperature conditions (100-130°C), the dye cannot enter the interior of the fiber to complete the dyeing. Because the imide structure is not alkali-resistant, polyimide fibers can be hydrolyzed under alkaline conditions to generate polar groups, which can be combined with dyes, but after the fibers are hydrolyzed, the polyimide is destroyed The original regular structure of the fiber will cause serious loss of fiber strength and lose the meaning of high-performance fiber. Carrier dyeing is a dyeing method in which small molecule organic solvents close to the fiber structure are used as dyeing carriers. The carrier and the fiber are combined by van der Waals force or hydrogen bond, which weakens the bonding force between the molecular chains in the fiber, increases the cavity inside the fiber, and increases the dye diffusion rate and dyeing percentage. With the help of the carrier, the dye can continue Get inside the fiber to finish the dyeing. Carrier dyeing is a common dyeing process for synthetic fibers. For example, the carriers used in polyester carrier dyeing are mostly aromatic alcohols and aromatic esters.

In the patents CN201410817952.2 and CN201310493553.0, it is mentioned that the polyimide fiber is dyed with a carrier, and the carrier used is a general reagent for polyester carrier dyeing, which is benzyl alcohol, methyl benzoate, acetophenone, methacrylic acid Small organic compounds with non-amide structure such as methyl ester; before dyeing, polyimide is treated with alkaline solution to hydrolyze polyimide molecules to obtain polar groups, but the strength of the fabric will inevitably be affected to a certain extent after the fiber is hydrolyzed. The damage does not meet the requirements of high-performance fibers.

Contents of the invention

Aiming at the chemical molecular structure of polyimide fiber, the present invention mainly selects organic matter containing amide structure as the carrier of polyimide dyeing, and can obtain excellent dyeing effect without alkaline pretreatment process. The carrier used has a similar structure to the polyimide fiber, and has a higher affinity with the fiber. The cationic dye dyes the fiber with the help of the carrier, and the dyed fabric has a deep color, high color fastness to washing, and good fabric strength. .

Polyimide dyeing provided by the present invention is shown in following formula (2) with general formula of carrier structure:

Among them, the amide structure endows the carrier with a certain affinity to the polyimide fiber. _In the carrier structure, R1 can be hydrogen, alkyl, aryl, alkoxyl, or hydroxyl; R2 can be _hydrogen , alkyl, aryl, or alkoxyl. radical, hydroxyl; _R can be hydrogen, alkyl, aryl, alkoxyl, hydroxyl.

The present invention also provides a method for dyeing polyimide using the carrier, comprising the steps of:

Step 1, removing the impurities attached to the surface of the polyimide fiber and drying;

Step 2, adding the polyimide fibers after washing to remove impurities into the dye solution containing cationic dyes and carriers for dyeing;

Step 3, after the dyeing is completed, the polyimide fiber is washed with water, soaped, and washed with water to remove the floating color of the dye.

In one embodiment of the present invention, in step 1, polyimide fibers are added with 2-3g/L nonionic surfactant and 1-2g/L degreasing agent, such as nonionic surfactant AEO- 7. CT-3 degreaser. The liquor ratio is 20-30:1, treat at 85-95°C for 30-60min, fully wash with water and then dry.

In one embodiment of the present invention, in step 2, the polyimide fiber after drying is added in the dye liquor containing carrier and cationic dyestuff, and the liquor ratio of dye liquor and fiber fabric is (15:1)～ (30:1); the cationic dye is 2.5%-10% to the weight (owf) of the fiber fabric; the carrier is a compound of one or more carriers in the present invention, and the carrier concentration is 10-100 g /L.

In one embodiment of the present invention, in step 2, the polyimide fiber after washing to remove impurities is added to the dyeing liquor containing carrier and cationic dye, and the temperature is raised to 120-130 °C at a speed of 1.5-3 °C/min. ℃, keep warm for 40-120min.

In one embodiment of the present invention, step 3, after dyeing is completed, polyimide fiber is added to the solution containing soaping agent and sodium carbonate, the liquor ratio is 20:1-30:1, and treated at 85°C Wash thoroughly with water after 15 minutes. The soaping agent is a nonionic surfactant, such as AEO-7, with a concentration of 2-3g/L and a sodium carbonate concentration of 2-3g/L.

Applying the carrier provided by the invention to dye polyimide fibers does not require complicated pretreatment process, the amount of dyeing is large, the fading fastness of the obtained polyimide fabrics is improved, and the strength is not significantly lower than that before dyeing .

detailed description

Example 1

A substance in which R ₁ is phenyl, R ₂ is methyl, and R ₃ is hydrogen is selected as the carrier.

Get 2g polyimide knitted fabric, put into the solution that contains nonionic surfactant AEO-7 (2g/L) and degreasing agent CT-3 (1g/L), bath ratio is 30:1, at 95 Treat at ℃ for 30 minutes, fully wash with water and dry.

Put the polyimide fabric washed to remove impurities into the carrier dye solution containing 5% cationic red SD-GRL and 50g/L of the weight of the fabric, wherein the bath ratio of the dye solution to the fabric is 15:1, at 1.5 ° C /min speed up to 120°C for 40min.

After the dyeing is completed, put the fabric into the soaping solution containing 2g/L nonionic surfactant AEO-7 and 2g/L sodium carbonate, the bath ratio is 20:1, and fully treat the fabric at 85°C for 15min. Wash and tumble dry.

The color parameters and washing fastness of the dyed samples are shown in Table 1.

Example 2

A substance in which R ₁ is methyl, R ₂ is methyl, and R ₃ is hydrogen is selected as the carrier.

Get 2g polyimide knitted fabric, put into the solution that contains nonionic surfactant AEO-7 (2g/L) and degreasing agent CT-3 (1g/L), bath ratio is 30:1, at 95 Treat at ℃ for 30 minutes, fully wash with water and dry.

Put the polyimide fabric washed to remove impurities into the carrier dye solution containing 5% cationic blue SD-GSL and 50g/L of the weight of the fabric, wherein the bath ratio of the dye solution to the fabric is 30:1, at 3°C /min speed to 130 ° C for 120 min.

After the dyeing is completed, put the fabric into the soaping solution containing 2g/L nonionic surfactant AEO-7 and 2g/L sodium carbonate, the bath ratio is 20:1, and fully treat the fabric at 85°C for 15min. Wash and tumble dry.

The color parameters and washing fastness of the dyed samples are shown in Table 1.

Example 3

_A substance in which R1 is methyl, _R2 is methyl, and _R3 is methyl is selected as the carrier.

Get 2g polyimide knitted fabric, put into the solution that contains nonionic surfactant AEO-7 (3g/L) and degreaser CT-3 (2g/L), bath ratio is 15:1, at 85 Treat at ℃ for 30 minutes, fully wash with water and dry.

Put the polyimide fabric washed to remove impurities into the carrier dye solution containing 2.5% cationic red SD-GRL and 10g/L of the weight of the fabric, wherein the bath ratio of the dye solution to the fabric is 15:1, at 2 ° C /min speed up to 120 ° C for 120 min.

After the dyeing is completed, put the fabric into the soaping solution containing 3g/L nonionic surfactant AEO-7 and 3g/L sodium carbonate, the liquor ratio is 30:1, and fully treat the fabric at 85°C for 15min. Wash and tumble dry.

The color parameters and washing fastness of the dyed samples are shown in Table 1.

Example 4

A substance in which R ₁ is phenyl, R ₂ is hydrogen, and R ₃ is methyl is selected as the carrier.

Get 2g polyimide knitted fabric, put into the solution that contains nonionic surfactant AEO-7 (3g/L) and degreaser CT-3 (2g/L), bath ratio is 15:1, at 85 Treat at ℃ for 30 minutes, fully wash with water and dry.

Put the polyimide fabric washed to remove impurities into a carrier containing 2.5% cationic blue SD-GSL and 10g/L of the weight of the fabric, wherein the bath ratio of the dye solution to the fabric is 15:1, at 2°C/min Speed up to 120°C for 40 minutes.

After the dyeing is completed, put the fabric into the soaping solution containing 3g/L nonionic surfactant AEO-7 and 3g/L sodium carbonate, the liquor ratio is 30:1, and fully treat the fabric at 85°C for 15min. Wash and tumble dry.

The color parameters and washing fastness of the dyed samples are shown in Table 1.

Example 5

_A substance in which R1 is phenyl, R2 is methyl, _R3 is _hydrogen and _a substance in which R1 is methyl, R2 is methyl, and _R3 is _hydrogen is selected as a carrier.

Get 2g polyimide knitted fabric, put into the solution that contains nonionic surfactant AEO-7 (2g/L) and degreasing agent CT-3 (1g/L), bath ratio is 30:1, at 85 Treat at ℃ for 30 minutes, fully wash with water and dry.

The polyimide fabric that washing removes impurity is put into the carrier that contains 5% cationic red SD-GRL to fabric weight and 5% cationic blue SD-GSL and 100g/L to fabric weight (two kinds of carriers each 50g/L), The liquor ratio of the dye liquor to the fabric is 20:1, and the temperature is raised to 120°C at a speed of 2°C/min and kept for 40 minutes.

After the dyeing is completed, put the fabric into the soaping solution containing 2g/L nonionic surfactant AEO-7 and 2g/L sodium carbonate, the bath ratio is 30:1, and fully treat the fabric at 85°C for 15min Wash and tumble dry.

The color parameters and washing fastness of the dyed samples are shown in Table 1.

Comparative example 1

Get 2g polyimide knitted fabric, put into the solution that contains nonionic surfactant AEO-7 (2g/L) and degreasing agent CT-3 (1g/L), bath ratio is 30:1, at 95 Treat at ℃ for 30 minutes, fully wash with water and dry.

Put the polyimide fabric washed to remove impurities into the cationic red SD-GRL containing 5% of the weight of the fabric, in which the bath ratio of the dye solution to the fabric is 15:1, and the temperature is raised to 130°C at a speed of 1.5°C/min. 60min.

After the dyeing is completed, put the fabric into the soaping solution containing 2g/L nonionic surfactant AEO-7 and 2g/L sodium carbonate, the bath ratio is 20:1, and fully treat the fabric at 85°C for 15min. Wash and tumble dry.

Table 1 CIE Lab, K/S, washing fastness series and strength of polyimide fabric carrier after dyeing

Note: The color fastness and staining fastness are determined according to the textile color fastness test standard GB/T 3921-2008; the breaking strength is the yarn strength, according to the standard GB/T 3921-2008 for the determination of the breaking strength and elongation of a single textile yarn T 3916-2013 Determination.

As can be seen from the data in Table 1, when other dyeing conditions are exactly the same, when using carrier (embodiment 1) and not containing carrier dyeing (comparative example 1), the CIELab value of carrier-dyed fabric and the difference of undyed fabric than not containing carrier dyed The size of the fabric is large, indicating that the color change of the carrier-dyed fabric is greater than that of the non-carrier-dyed fabric, that is, the amount of dyeing is large. At the same time, the fading fastness of the carrier-dyed polyimide fabric is improved.

Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore The scope of protection of the present invention should be defined by the claims.

Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore The scope of protection of the present invention should be defined by the claims.

Claims (10)

1. a kind of method that carrier dyeing is carried out to polyimides, it is characterised in that using contain the organic matter of amide structure as The carrier of polyimides dyeing.

2. a kind of method that carrier dyeing is carried out to polyimides according to claim 1, it is characterised in that the carrier General structure such as following formula (2) shown in：

3. a kind of method that carrier dyeing is carried out to polyimides according to claim 1 or 2, it is characterised in that described Carrier is one or more of compounding.

4. a kind of method that carrier dyeing is carried out to polyimides according to claim 2, it is characterised in that described load R in body structure₁For hydrogen, alkyl, aryl, alkoxy or hydroxyl, R₂For hydrogen, alkyl, aryl, alkoxy or hydroxyl, R₃For hydrogen, alkane Base, aryl, alkoxy or hydroxyl.

5. according to any a kind of described method that carrier dyeing is carried out to polyimides of Claims 1 to 4, it is characterised in that Comprise the following steps：

Step one, the impurity of polyimide fiber surface attachment, drying are removed；

Step 2, goes the polyimide fiber after the removal of impurity to be added in the dye liquor containing the dye of positive ion and carrier washing, Dyed；

Step 3, washes polyimide fiber after the completion of dyeing, soap boiling, washing to be to remove dyeing loose colour.

6. a kind of method that carrier dyeing is carried out to polyimides according to claim 5, it is characterised in that step one, Polyimide fiber, which is added, contains 2-3g/L non-ionic surfaces surfactant and 1-2g/L degreasers, and bath raio is 20-30:1, 30-60min is handled at 85-95 DEG C, is fully dried after washing.

7. a kind of method that carrier dyeing is carried out to polyimides according to claim 5 or 6, it is characterised in that step Two, the polyimide fiber after drying is added in the dye liquor containing carrier and the dye of positive ion, dye liquor and fabric Bath raio is (15:1)~(30:1)；The dye of positive ion is 2.5%-10% to fabric weight, and carrier concn is 10- 100g/L。

8. a kind of method that carrier dyeing is carried out to polyimides according to claim 5, it is characterised in that step 2, By washing go the polyimide fiber after the removal of impurity to be added in the dye liquor containing carrier and the dye of positive ion, with 1.5-3 DEG C/ Min speed is warming up to 120-130 DEG C, is incubated 40-120min.

9. a kind of method that carrier dyeing is carried out to polyimides according to claim 5 or 8, it is characterised in that step Three, polyimide fiber is added in the solution containing soaping agent and sodium carbonate after the completion of dyeing, bath raio is 20:1-30:1, Fully washed after handling 15min at 85 DEG C.

10. a kind of polyimides dyeing carrier, it is characterised in that shown in general structure such as following formula (2)：

Wherein, R₁For hydrogen, alkyl, aryl, alkoxy or hydroxyl；R₂For hydrogen, alkyl, aryl, alkoxy or hydroxyl；R₃For hydrogen, alkane Base, aryl, alkoxy or hydroxyl.