JP5072496B2 - Method for decoloring flag for recycling and method for recycling flag - Google Patents

Description

The present invention relates to a recycle flag, a decoloring method for a recycle flag, and a recycle method for a rebound flag.

The banners that are used by attaching a hook to one end of an elongated cloth are widely used for the promotion of products in front of gas stations and restaurants, and for the promotion of festivals and events. .
These banners have been collected and discarded after being used for a short period of time. However, in recent years, there has been a demand for more environmentally friendly banners due to increasing environmental problems.
As an environmental measure when discarding the bamboo shoots for this purpose, a paper tube is provided with a waterproof / preservative (Patent Document 1).
As for the banner itself, a banner using a recycled polyester fiber is being studied.

On the other hand, since the banner is often used outdoors, it is desired that the flag is difficult to fade against the sun's light and that the pattern does not bleed even when wet by rain. In addition, the banners used at gas stations and the like were also required to be flame retardant.
Therefore, in order to satisfy the required fastness to sunlight and fastness to water such as rain, the conventional banner is applied to the fiber fabric by screen printing (pigment print) with a binder resin containing a pigment, The ones with letters and patterns were used as banners. In addition, when flame retardancy is required, a flame retardant processing is performed by adding a halogen-based flame retardant such as decabromodiphenyl ether or antimony trioxide into a binder resin containing a pigment.
JP-A-8-199853

As described above, the banner using the recycled polyester fiber is also preferable from the viewpoint of environmental measures. However, as the mixing ratio of the recycled polyester fiber increases, the strength of the banner flag and the fastness may decrease. There was a problem that the mixing rate could not be raised.
Therefore, from the viewpoint of environmental measures, the present inventors tried to make a banner with a polyester fiber fabric, collect it after use, and perform chemical recycling, but the banner is printed with pigment. Therefore, it was difficult to decolorize to a level where chemical recycling was possible.

Furthermore, in order to chemically recycle the banners with flame retardancy, it was necessary to remove the flame retardant, but the flame retardant fixed to the polyester fiber fabric with the binder resin was removed. It was difficult to do. Moreover, when a part is removed, there is a concern about the influence of the halogen-based flame retardant such as removed decabromodiphenyl ether and the emission to the environment such as antimony trioxide.
Accordingly, an object of the present invention is to solve the above-mentioned problems and provide a recycling flag that can be chemically recycled and material recycled, a decoloring method of the recycling flag, and a recycling method of the flag.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention, and the present invention comprises, for example, the following configurations (1) to (13).
(1) A recycling flag characterized by comprising a polyester fiber fabric printed with a disperse dye.
(2) The recycling flag according to (1), wherein the disperse dye includes at least one selected from an azo disperse dye, a benzodifuranone disperse dye, and a phthalimide disperse dye.
(3) The recycling flag according to (2), wherein the azo disperse dye includes at least one selected from monoazo, disazo, thiazole, thiophenazo, and pyrrolidone azo disperse dyes.
(4) The recycling flag according to any one of (1) to (3), wherein the polyester fiber fabric includes a phosphate ester flame retardant.
(5) The color of the polyester fiber fabric printed with the disperse dye after the decoloring treatment with the decoloring treatment liquid containing the alkali agent, the reducing agent, and the nonionic surfactant, and the polyester fiber product is printed. The flag for recycling according to any one of (1) to (4), wherein the color difference ΔE compared with the color of the unprinted polyester fiber fabric before being printed is 13 or less.

(6) A method for decoloring a flag for recycling, in which a polyester fiber fabric printed with a disperse dye constituting a flag is treated with a decoloring treatment solution containing an alkaline agent, a reducing agent and a nonionic surfactant.
(7) The method for decoloring a flag for recycling according to (6), wherein the reducing agent includes hydrosulfite and thiourea dioxide.
(8) The method for decoloring a flag for recycling according to (6) or (7), wherein the nonionic surfactant is a fatty acid ethylene oxide adduct.
(9) The method for decoloring a flag for recycling according to any one of (6) to (8), wherein the treatment liquid for decolorization further contains a chelating agent.
(10) The method for decoloring a flag for recycling according to any one of (6) to (9), wherein the processing solution for decolorization further contains an anionic surfactant.
(11) The method for decoloring a flag for recycling according to (10), wherein the anionic surfactant is sulfated oil.

(12) Step 1 for manufacturing the flag for recycling described in (1), Step 2 for using the flag for recycling by the user, Step 3 for collecting the flag for recycling used by the user, Step 3 for collecting the collected recycling flag A method for recycling a banner flag, comprising: decoloring the flag by the decoloring method described in (6) above; and step 5 using the decolored recycling flag as a raw material for chemical recycling.
(13) Step 1 for producing the flag for recycling described in (1), Step 2 for using the flag for recycling by the user, Step 3 for collecting the flag for recycling used by the user, Step 3 for collecting the collected recycling flag A method for recycling a banner flag, comprising: decoloring the flag by the decoloring method as described in (6) above; and step 5 using the decolored recycling flag as a material recycling material.

If the flag for recycling of the present invention is used, since the pigment or the like is not applied to the polyester fiber fabric using the binder resin, it is possible to easily remove the dye from the polyester fiber fabric by the decolorization treatment, and the recycling. Possible banners can be provided. In addition, the banner according to the present invention does not require the pigment to be fixed to the polyester fiber fabric using a binder resin when a letter or a picture is applied by printing, so that it can provide a soft banner with a texture. .

By performing the decoloring process by the decoloring method of the present invention, the decoloring process can be performed in a short time by an apparatus used in a conventional dyeing process, without using a titanium plating apparatus that can withstand an oxidation process. Since there is no need to use an organic solvent harmful to the human body, it is possible to provide a banner that is inexpensive and can be safely recycled. In addition, when flame retardancy is imparted, if a banner flag using a polyester fiber fabric containing a phosphate ester flame retardant is obtained, flame retardancy is imparted to the banner flag without using a binder resin. In addition, it is possible to suppress the discharge of halogen-based flame retardants such as decabromodiphenyl ether and antimony trioxide to the environment during the decolorization treatment.

Furthermore, if the recycling method using the recycling flag of the present invention and the decoloring method of the present invention are used, it is possible to safely and safely recycle the banner flag at a lower cost than in the past.

Hereinafter, preferred embodiments of the present invention will be described. However, it should be understood that the present invention is not limited to only these embodiments, and that various modifications can be made within the spirit and scope of implementation.

In the present invention, examples of the polyester fiber fabric include fiber fabrics obtained using polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polylactic acid. It may contain recycled polyester. In addition to the polyester such as polyethylene terephthalate, natural fibers such as cotton, hemp and wool, synthetic fibers such as nylon and acrylic, regenerated fibers such as rayon, and semisynthetic fibers such as acetate may be included. From the viewpoint of fractionation during recycling and purity of components obtained during chemical recycling, those consisting only of polyester are preferred.

Moreover, the form of a polyester fiber fabric can use a woven fabric, a knitted fabric, a nonwoven fabric, etc. Moreover, the thing which attached milk and eyelets for attaching a banner to a bag may be used. Further, these polyester fiber fabrics are subjected to various incidental processes performed on general polyester fiber fabrics such as water repellent processing, antistatic processing, water absorption processing, antibacterial deodorization processing, flame retardant processing, and flexible processing. It may be given. In particular, those used at a gas station or an event venue where many people gather are preferably subjected to flame retardant processing. In addition, ground dyeing may be applied to the polyester fiber fabric as long as the object of the present invention is not impaired.

As the flame retardant used, a phosphate ester flame retardant is preferably used. When a phosphate ester flame retardant is used, a flame retardant is applied to the surface of the polyester fiber fabric by a padding method or the like without using a binder resin like a halogen flame retardant, and then heat treatment at 110 to 200 ° C. is performed. In addition, the polyester fiber fabric contains a phosphate ester flame retardant by exhausting the flame retardant to the polyester fiber fabric in a bath at 120 to 140 ° C. by a bath exhaustion method or the like. You can get a recycling banner with

When a halogen-based flame retardant is applied to a polyester fiber fabric using a binder resin, it may be difficult to remove the flame retardant in the decolorization process, and decabromodiphenyl ether, which is concerned about the environment due to the decolorization process. There is a risk that drainage liquid containing halogen-based flame retardant such as antimony trioxide will be discharged. In addition, when halogen-based flame retardants remain on the banner, it is difficult to remove them during chemical recycling, which hinders chemical recycling. If a phosphate ester flame retardant is used, it is easy to remove the flame retardant at the time of decolorization, and even if the flame retardant remains, it can be easily removed at the time of chemical recycling. The flame retardant processing can be performed before or after printing, but is preferably performed before printing from the viewpoint of fastness and simplification of the process.

The recycling flag of the present invention is composed of a polyester fiber fabric printed with a disperse dye. The disperse dye is selected from azo disperse dyes, benzodifuranone disperse dyes, and phthalimide disperse dyes. It is good to include at least one kind. A textile printed with a binder resin containing a pigment is not preferable from the viewpoint of recycling such as residual pigment and binder. In the present invention, a banner flag is printed on a polyester fiber fabric printed with a disperse dye without using a binder resin. Configure.

The azo disperse dye used in the present invention preferably contains at least one selected from monoazo, disazo, thiazole azo, thiophenazo, and pyrrolidone azo disperse dyes. Those having an alkyl ester group are also preferably used. More specifically, C.I. I. Disperse Yellow 3, C.I. I. Disperse Yellow 126, C.I. I. Disperse Yellow 163, C.I. I. Disperse Yellow 226, C.I. I. Disperse Orange 30, C.I. I. Disperse Red 54, C.I. I. Disperse Red 65, C.I. I. Disperse Red 73, C.I. I. Disperse Red 179, C.I. I. Disperse Red 278, C.I. I. Disperse Red 356, C.I. I. Disperse Violet 12, C.I. I. Disperse Blue 79, C.I. I. Disperse Blue 125, C.I. I. Disperse Blue 148, C.I. I. Disperse Blue 165, C.I. I. Disperse Blue 183, C.I. I. Disperse Green 9, C.I. I. Disperse Yellow 60, C.I. I. Disperse Red 58, C.I. I. Disperse Yellow 7, C.I. I. Disperse Yellow 23, C.I. I. Disperse Orange 29, C.I. I. Disperse Orange 13, C.I. I. Disperse Red 141 etc. are mentioned.

Examples of the benzodifuranone-based disperse dye include C.I. I. Disperse Red 356 and the like. In addition, as phthalimide-based disperse dyes, Teraspec WW Red WW-DS, Terasil WW Red WW-FS, Terasil WW Red-3BS, Terasil WW Red WW-BFS 200%, Terasil manufactured by Ciba Specialty Chemicals Co., Ltd. WW Violet WW-2RS, Terasil WW Blue WW-2GS, Terasil WW Navy WW-GSN, Terasil WW Black WW-KSN, and the like. In addition to azo disperse dyes, benzodifuranone disperse dyes, and phthalimide disperse dyes, even quinone disperse dyes, etc., as long as the remaining dye color is not a problem in the following decolorization treatment, combined use May be.

The polyester fiber fabric printed with the above-mentioned disperse dye is printed with a printing paste containing the disperse dye (hereinafter also referred to as a color paste) on an arbitrary pattern or character using a flat screen printing machine, a rotary printing machine or the like. ,Obtainable. The color paste may be printed on the entire surface of the polyester fiber fabric or may be printed partially. As the paste used for printing paste, starch-based, seaweed-based, fiber-based and derivatives thereof can be used, and these pastes can be removed from polyester-based fiber fabrics by soaping after coloring. Should be used. These printing pastes may be used in the state of either emulsion paste or solution paste. However, from the viewpoints of removability and feel of the paste, it is preferable to use emulsion paste or half emulsion paste containing emulsion paste and solution paste. After the color paste is printed, the polyester fiber fabric is subjected to color development treatment at a temperature of 150 ° C. to 200 ° C. for 1 minute to 60 minutes by dry heat or wet heat. Next, soaping is performed by a known method to remove the paste and the undyed disperse dye.

The dye concentration in the color paste may be any of light to dark, and may be 0.001 to 15% by mass as a commercially available dye concentration with respect to the color paste. Further, the hue of the printed pattern may be any color such as red, blue, yellow, green, and black. Also, disperse dye printing can be performed using a transfer printing machine or an ink jet printing machine, but when a binder or an ink receiving layer is formed during printing with these, by soaping after printing, It is necessary to use a polyester fiber fabric that can remove the binder and the ink receiving layer. The banner according to the present invention is composed of a polyester fiber fabric printed with the disperse dye. The banner flag using the polyester fiber fabric may be manufactured in a known configuration, such as one with milk for fixing the flag banner to the banner, or one with eyelets for passing the string.

The banner according to the present invention preferably has a light fastness level 4 or higher, a water fastness level 4 or higher, and a sublimation fastness level 4 or higher. If it has such fastness, it can be used without problems even when used outdoors as a banner.

In addition, the color difference of the polyester fiber fabric compared with the color of the portion printed with the disperse dye after the decoloring treatment as described below and the color of the unprinted polyester fiber fabric before the polyester fiber fabric is printed. ΔE is preferably 13 or less, more preferably 10 or less, and even more preferably 6 or less. If the color difference ΔE is 13 or less, chemical recycling can be performed. Moreover, when performing material recycling, the range of uses can be expanded. The smaller the numerical value ΔE, the closer to the color of the white unprinted polyester fiber fabric before printing. Here, the color difference ΔE is obtained from CIE 1976 LAB ΔE = √ (ΔL ² + Δa ² + Δb ² ), light source D65, and 10 ° field of view. As a spectrophotometer, COLOR-7X diffused / 8 manufactured by Kurashiki Boseki Co., Ltd. is used. °, 6 inch integrating sphere, color management system AUCOLOR-NF2 was used. In addition, when background dyeing (including fluorescent whitening) was applied to the polyester fiber fabric before printing, it was printed with the white fabric before the background dyeing and the disperse dye after the decoloring process. A color difference ΔE of the color of the part is obtained.

The recycling flag decoloring method of the present invention is such that a polyester fiber fabric printed with a disperse dye constituting a banner is treated with a decoloring treatment solution containing an alkali agent, a reducing agent and a nonionic surfactant. It is characterized by doing. In addition, as another decolorization method, after reducing decolorization using caustic soda and hydrosulfite, oxidative decoloring using oxalic acid, acetic acid, formic acid and sodium chlorite etc. is combined, and reducing decoloration and oxidative decoloration are combined. It is also possible to decolorize or decolorize with an organic solvent that can dissolve the disperse dye. However, when oxidative decolorization is performed, a processing machine made of stainless steel generally used for dyeing processing corrodes the processing machine, so that an expensive processing machine made of titanium plating is required. In the case of using an organic solvent, there is a concern that the organic solvent has an adverse effect on the human body and the environment, and the decolorization time is very long, and decoloration treatment can be performed only about 1 batch per day. Therefore, from the viewpoint of the cost, safety, and processing time of the processing machine, it is preferable to perform the treatment with a decoloring treatment liquid containing an alkaline agent, a reducing agent, and a nonionic surfactant.

Here, as the alkali agent, sodium hydroxide, sodium carbonate, potassium hydroxide, or the like can be used. These alkaline agents are preferably used as an aqueous solution having a concentration of 0.5 to 100 g / l, particularly 1 to 10 g / l. If the concentration of this aqueous solution is less than 0.5 g / l, the decoloring effect may not be sufficient, and if it exceeds 100 g / l, the polyester fibers may be dissolved.

Examples of useful reducing agents include hydrosulfite, thiourea dioxide, zinc sulfoxylate / formaldehyde, sodium sulfoxylate / formaldehyde and the like. These may be used alone or in combination of two or more. In particular, it is preferable to use hydrosulfite and thiourea dioxide in combination. These reducing agents are preferably used as an aqueous solution having a concentration of 1 to 100 g / l, particularly 1 to 30 g / l. If this concentration is less than 1 g / l, decolorization may not be sufficient, and if it exceeds 100 g / l, there is no significant difference in decolorization effect, which is disadvantageous in cost.

Useful nonionic surfactants include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, fatty acid amide ethylenes. Oxide adduct, Fatty acid ethylene oxide adduct, Polypropylene glycol ethylene oxide adduct, Glycerol fatty acid ester, Pentaerythritol fatty acid ester, Sorbitol or sorbitan fatty acid ester, Sucrose fatty acid ester, Polyhydric alcohol alkyl ether, Alkanol Examples thereof include fatty acid amides of amines. Of these, fatty acid ethylene oxide adducts are preferred, and unsaturated fatty acid ethylene oxide adducts are more preferred. More specifically, polyethylene glycol oleic acid monoester and polyethylene glycol oleic acid diester are mentioned.

These nonionic surfactants are preferably used as an aqueous solution having a concentration of 0.1 to 100 g / l. If this concentration is less than 0.1 g / l, decolorization may not be sufficient, and if it exceeds 100 g / l, there is no significant difference in decolorization effect, which is disadvantageous in terms of cost, and a large amount of bubbles may be generated. there is a possibility.

Furthermore, the decoloring treatment solution used in the present invention may contain a chelating agent. Useful chelating agents include sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate as condensed phosphates, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA) as aminocarboxylic acid types Examples thereof include gluconic acid as the oxycarboxylic acid type, hydroxyethylidene diphosphonic acid as the phosphonic acid type, and polyacrylic acid soda and polymaleic acid soda as the polycarboxylic acid type. Among these, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and diethylenetriaminepentaacetic acid (DTPA) are preferable, and these may be used alone or in combination of two or more. These chelating agents are preferably used as an aqueous solution having a concentration of 0.01 to 1 g / l. If this concentration is less than 0.01 g / l, decolorization may not be sufficient, and if it exceeds 1 g / l, there is no significant difference in decolorization effect, which is disadvantageous in cost.

Further, the decoloring treatment liquid may contain an anionic surfactant. Anionic surfactants include soap, higher alcohol sulfate, higher alkyl ether sulfate, sulfated oil, sulfated fatty acid ester, sulfated olefin, alkylbenzene sulfonate, alkyl naphthalene sulfonate, paraffin sulfonate. And higher alcohol phosphoric acid ester salts. More preferred is sulfated oil, and even more preferred is sulfated castor oil. These anionic surfactants are preferably used as an aqueous solution having a concentration of 0.01 to 50 g / l. If this concentration is less than 0.01 g / l, decolorization may not be sufficient, and if it exceeds 50 g / l, there is no significant difference in decolorization effect, which is disadvantageous in cost.

Further, when the decolorization treatment solution contains a carrier that may be used during dyeing, the decolorization effect is further improved. Specific examples include relatively low molecular weight alkyl benzoates, alkyl salicylates, phenyl glycols, phenyl diglycols, benzyl benzoates, dibenzyl ethers, N-butylphthalimide, chlorobenzene, and diphenyl derivatives. These may be used alone or in combination of two or more. From the viewpoint of decolorization and odor, benzyl benzoate and N-butylphthalimide are preferable, and it is more preferable to use these in combination. These aromatic compounds can be used as an aqueous solution having a concentration of 0.1 to 100 g / l from the viewpoint of decolorization.

However, in the decolorization method of the present invention, it is preferable not to use the above carrier from the viewpoint of safety. By using the preferred dye and the preferred decoloring method of the present invention, the polyester-based fiber fabric printed without using a carrier is decolorized to a level that can be sufficiently used as a raw material for chemical recycling. Can be provided.

Moreover, it is preferable that a decoloring process is performed at 110-145 degreeC, especially 120-140 degreeC for 10 to 180 minutes. If this temperature falls below 110 ° C., decolorization may not be possible, and if it exceeds 145 ° C., the polyester fiber fabric may become brittle. In addition, the bath ratio of the flag flag and the decoloring solution to be decolored varies depending on the density and area of the flag flag printed, but is preferably about 1: 5 to 1: 500. If the bath ratio is less than 1: 5, sufficient decolorization may not be obtained, and if it exceeds 1: 500, there is no significant difference in decolorization effect, which is disadvantageous in terms of cost.

Moreover, as a device used for the decoloring treatment, a drum-type high-pressure rotary washer usually used for dyeing and scouring of polyester fiber products can be appropriately selected and used, and can be treated under the above-mentioned treatment conditions. There is no particular limitation as long as it is present. The decoloring process may be performed by repeating the above process twice or more as necessary. After the decolorization treatment, it is preferable to perform water washing before drying.

Next, the recycling method of the present invention will be described.

Chemical Recycling The recycling method of the present invention is a step 1 for producing the flag for recycling according to the present invention, a step 2 for using the flag for recycling by the user, a step 3 for collecting the flag for recycling used by the user, and The recycling method includes step 4 of decoloring the flag for recycling by the decoloring method of the present invention, and step 5 of performing chemical recycling using the decolored recycling flag as a raw material for chemical recycling.

In Step 1, an arbitrary pattern and an arbitrary character are printed on a polyester-based fiber fabric using the disperse dye, and a milk for attaching to a raft or a string for passing a string as necessary. To manufacture the recycling flag of the present invention. In this step 1, in order to manage easily so that it is a flag for recycling of the present invention, an identification display such as a tag with a barcode or the like attached to the flag for recycling is given and input to the database. It is good to leave.

In step 2, the user uses a recycling flag. The use of banners is almost never used by individuals, but is used by companies, organizations, groups, etc. at events such as festivals, campaigns, etc., so the administrator is clear and easy to collect, The recovery rate is improved and the probability of being discarded as garbage is low, which is very good from the viewpoint of reducing the environmental load. In step 3, the flag used by the user is collected. If an identification display is given in step 1 at the time of collection, it can be easily identified even when the recycling flag of the present invention and other textile products are mixed. In addition, as described in Step 2, companies, organizations, groups, etc. are used at festivals and other events and campaigns, so the manager is clear and easy to prevent other textile products from being mixed. Even if other products are mixed, it can be easily identified.

In step 4, the collected recycling flag is decolored by the decoloring method of the present invention. By this decolorization treatment, a color difference ΔE comparing the color of the portion printed with the disperse dye after the decolorization treatment of the polyester fiber fabric and the color of the unprinted polyester fiber fabric before the polyester fiber fabric is printed is obtained. When it is 13 or less, the constituent monomer obtained in the next step 5 is preferably obtained with less impurities. In Step 5, in the chemical recycling step, the constituent monomer of the polyester fiber fabric is separated and generated and can be reused, and the recycling is further promoted.

Material Recycling In addition, the recycling method of the present invention includes a step 1 for producing the flag for recycling of the present invention, a step 2 for using the flag for recycling by the user, a step 3 for collecting the flag for recycling used by the user, The recycling method includes step 4 for decoloring the collected flag for recycling by the decoloring method of the present invention, and step 5 for performing material recycling using the decolored recycling flag for material recycling.

In Step 1, an arbitrary pattern and an arbitrary character are printed on a polyester-based fiber fabric using the disperse dye, and a milk for attaching to a raft or a string for passing a string as necessary. To manufacture the recycling flag of the present invention. In this step 1, in order to manage easily so that it is a flag for recycling of the present invention, an identification display such as a tag with a barcode or the like attached to the flag for recycling is given and input to the database. It is good to leave.

In step 2, the user uses a recycling flag. The use of banners is almost never used by individuals, but is used by companies, organizations, groups, etc. at events such as festivals, campaigns, etc., so the administrator is clear and easy to collect, The recovery rate is improved and the probability of being discarded as garbage is low, which is very good from the viewpoint of reducing the environmental load. In step 3, the flag used by the user is collected. If an identification display is given in step 1 at the time of collection, it can be easily identified even when the recycling flag of the present invention and other textile products are mixed. In addition, as described in Step 2, companies, organizations, groups, etc. are used at festivals and other events and campaigns, so the manager is clear and easy to prevent other textile products from being mixed. Even if other products are mixed, it can be easily identified.

In step 4, the collected recycling flag is decolored by the decoloring method of the present invention. By this decolorization treatment, a color difference ΔE comparing the color of the portion printed with the disperse dye after the decolorization treatment of the polyester fiber fabric and the color of the unprinted polyester fiber fabric before the polyester fiber fabric is printed is obtained. When it is 13 or less, when performing material recycling obtained in the next step 5, there is little coloring and the use is expanded. In Step 5, material recycling can be performed to form various products such as fibers, cotton, trays, etc., without decomposing polyester into monomers in the material recycling step. Since the product obtained by the present invention is less contaminated with dyes, it can be used in applications that have been limited by being colored in the past.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited at all by these Examples. The fastness and flame retardancy in this example were measured by the following methods. 1) Light fastness JIS L0842: 1996 Third exposure method 2) Water fastness JIS L0846: 1996 In addition, cotton and nylon were used for the attached fabric. 3) Sublimation fastness JIS L0850: 1994 It tested according to the electric iron method (B method) drying test. Nylon (JIS L0803: 1998 single fiber cloth (1)) was used for the attached cloth instead of the white cotton cloth. The temperature was 180 ° C. 4) Flame retardancy performance Evaluation was performed by JIS L1091 A-1 method (micro burner method) and JIS L1091 D method (coil method). In the micro-burner method, if the residual flame is within 3 seconds, the residual dust is within 5 seconds, and the carbonized area is within 30 cm2 for both heating for 1 minute and heating for 3 seconds after flameing, it is acceptable. Passed. In the coil method, those having a flame contact number of 3 or more were considered acceptable. In addition, the sample used for the test was subjected to a test after a hot water immersion treatment (50 ° C. warm water × 30 minute immersion) before drying with a constant temperature dryer.

The original paste described in the following examples was as follows.

Original glue Cellpearl SL100 (Guar gum glue, manufactured by Adachi glue) 10% by mass
Reducer 50% by mass
40% by weight of water

Reducer turpen 70% by mass
Emulsifier 20% by mass
10% by weight of water

(Example 1) Polyester taffeta (polyethylene terephthalate, warp yarn 83 dtex / 72 filament, weft yarn 83 dtex / 72 filament, density warp 114 / 2.54 cm, width 92 / 2.54 cm) as a polyester fiber fabric Using. Next, an aqueous dispersion containing an aromatic phosphate ester flame retardant was applied to the polyester fiber fabric surface by a padding method, dried at 120 ° C., and then heat treated at 180 ° C. for 30 seconds. Using a screen printing machine, the polyester fiber fabric was printed in a color different from “gasoline” by using the following color paste.

Color paste 1 ("Ga" character)
Original paste 60% by mass
Disperse dye Dianix YELLOW 7GL 200% 1% by mass
(Pyrrolidone azo type, CI Disperse Yellow 126, manufactured by Dystar Japan Co., Ltd.)
39% by weight of water

Color paste 2 ("So" character)
Original paste 60% by mass
Disperse dye Palanil Dark Blue 3RT 2% by mass
(Nitrobenzothiazole azo type, CI Disperse Blue 148, manufactured by Dystar Japan Co., Ltd.)
38% by weight of water

Color paste 3 ("Li" character)
Original paste 60% by mass
Disperse dye Kayalon Polyester Rubin BLS200
3% by mass
(Nitrobenzene thiazole azo type, CI Disperse Red 179, manufactured by Nippon Kayaku Co., Ltd.)
37% by weight of water

Color paste 4 (letter “n”)
Original paste 60% by mass
Disperse dye Dianix Green CC 2% by mass
(Thiophenazo type, CI Disperse Green 9, manufactured by Dystar Japan Co., Ltd.)
38% by weight of water

After the color paste was printed, heat treatment was performed at 190 ° C. for 3 minutes for color development. Next, using a continuous soaping machine, it was soaped at 80 ° C. for 10 minutes and dried.

Next, padding is performed with a 0.5% aqueous solution of antistatic agent Nicepol FL (manufactured by Nikka Chemical), antistatic processing is performed, and then finishing is set at 150 ° C. for 30 seconds, and printing is performed with disperse dyes A polyester fiber fabric was obtained. Next, the obtained polyester fiber fabric was cut into the size of a banner, and the polyester fabric was used to apply milk for passing through a banner to obtain a banner for recycling. The resulting banners are light fastness grade 4 or higher, water fastness color change 4-5 grade pollution 4-5 grade (both cotton and nylon), sublimation fastness grade 4-5 grade, flame retardant performance (Both with and without letters) Micro-burner method Passed Coil method Passed The result was equivalent to the performance of a banner printed with a binder resin containing pigment, and a soft texture was obtained.

Next, the obtained flag was attached to the flagbox and used outdoors for a week and then collected. The banner was removed from the collected banner, and the banner was heated to 140 ° C. while raising the temperature at 2 ° C./min from room temperature using the following decolorization solution with a high-pressure rotary washer. Demineralization treatment for 1 minute was performed once (bath ratio 1:50).

Decolorization treatment solution Caustic soda 3g / l
Hydrosulfite 5g / l
Thiourea dioxide 2g / l
Polyethylene glycol oleic acid monoester 10 g / l
Sulfated castor oil 1g / l
Chelating agent (DTPA) 0.1 g / l
Water remaining

After washing with water and drying, the decolored banner was decolorized to such an extent that the printed part had a slight color. Next, the color of the portion printed with the disperse dye after the decoloring treatment of the polyester fiber fabric and the color (white fabric) of the unprinted polyester fiber fabric before the polyester fiber fabric is printed are measured, When the color difference ΔE was obtained, it was 4.58 for color paste 1, 5.12 for color paste 2, 5.15 for color paste 3, and 4.72 for color paste 4.

Next, the decolored recycling flag was crushed and subjected to a chemical recycling process. As a result, dimethyl terephthalate and ethylene glycol, which had almost the same coloring problems as those obtained by conventional solvent decolorization treatment, were recovered. As described above, the step 1 for producing the recycling flag of the present invention, the step 2 for the user to use the recycling flag, the step 3 for collecting the recycling flag used by the user, and the collected recycling flag The polyester used as the flag of one time is easily chemically recycled by the recycling method including the step 4 of decoloring by the decoloring method of the present invention and the step 5 of performing chemical recycling using the decolored recycling flag as a raw material for chemical recycling. be able to.

(Example 2) The following are used as the color paste and the color removal treatment liquid, and the user uses the flag for recycling, Step 1 for producing the flag for recycling, except that the temperature of the color removal treatment is set to 135 ° C. Step 2, collecting the recycling flag used by the user, step 3, decoloring the collected recycling flag by the decoloring method of the present invention, using the decolored recycling flag as a raw material for chemical recycling, In the same manner as in Example 1 including Step 5 in which chemical recycling was performed, a flag for recycling was obtained, and decolorization and chemical recycling were performed.

Color paste 1 ("Ga" character)
Original paste 60% by mass
Disperse dye Dispersol Red CBN 3% by mass
(Benzodifuranone, CI Disperse Red 356, manufactured by Dystar Japan Co., Ltd.)
37% by weight of water

Color paste 2 ("So" and "N" characters)
Original paste 60% by mass
Disperse dye Dispersol Black FD95 5 mass%
(Azo-based disperse dye compound, manufactured by Nikka Fine Techno Co., Ltd.)
35% by weight of water

Color paste 3 ("Li" character)
Original paste 60% by mass
Disperse dye Terasil WW Blue WW-2GS 3% by mass
(Phthalimide, Ciba Specialty Chemicals Co., Ltd.)
37% by weight of water

Decolorization treatment solution Caustic soda 3g / l
Hydrosulfite 5g / l
Thiourea dioxide 2g / l
Polyethylene glycol oleic acid monoester 10 g / l
Chelating agent (DTPA) 0.1 g / l
Chelating agent (NTA) 0.1 g / l
Water remaining

The resulting banners are light fastness grade 4 or higher, water fastness color change 4-5 grade pollution 4-5 grade (both cotton and nylon), sublimation fastness grade 4-5 grade, flame retardant performance (Both with and without letters) Micro-burner method Passed Coil method Passed The result was equivalent to the performance of a banner printed with a binder resin containing pigment, and a soft texture was obtained.

The decolored banner was decolorized to such an extent that the printed part had a slight color. Next, the color of the portion printed with the disperse dye after the decoloring treatment of the polyester fiber fabric and the color (white fabric) of the unprinted polyester fiber fabric before the polyester fiber fabric is printed are measured, When the color difference ΔE was determined, it was 7.39 for color paste 1, 8.87 for color paste 2, and 7.88 for color paste 3.

Next, the decolored recycling flag was crushed and subjected to a chemical recycling process. As a result, dimethyl terephthalate and ethylene glycol, which had almost the same coloring problems as those obtained by conventional solvent decolorization treatment, were recovered. As described above, the step 1 for producing the recycling flag of the present invention, the step 2 for the user to use the recycling flag, the step 3 for collecting the recycling flag used by the user, and the collected recycling flag The polyester used as the flag of one time is easily chemically recycled by the recycling method including the step 4 of decoloring by the decoloring method of the present invention and the step 5 of performing chemical recycling using the decolored recycling flag as a raw material for chemical recycling. be able to.

(Example 3) Step 1 for producing a flag for recycling, Step 2 for using a flag for recycling by the user, and collecting the flag for recycling used by the user, except that the following are used as the decoloring treatment liquid The recycling banner was obtained in the same manner as in Example 1 including Step 3 in which the collected recycling flag was decolored by the decoloring method of the present invention, and decolorization was performed.

Decolorization treatment solution Caustic soda 3g / l
Hydrosulfite 5g / l
Thiourea dioxide 2g / l
Polyethylene glycol oleic acid monoester 10 g / l
Sulfated castor oil 1g / l
Chelating agent (DTPA) 0.1 g / l
Sodium polyacrylate 0.1g / l
Water remaining

The resulting banners are light fastness grade 4 or higher, water fastness color change 4-5 grade pollution 4-5 grade (both cotton and nylon), sublimation fastness grade 4-5 grade, flame retardant performance (Both with and without letters) Micro-burner method Passed Coil method Passed The result was equivalent to the performance of a banner printed with a binder resin containing pigment, and a soft texture was obtained.

The decolored banner was decolorized to such an extent that the printed part had a slight color. Next, the color of the portion printed with the disperse dye after the decoloring treatment of the polyester fiber fabric and the color (white fabric) of the unprinted polyester fiber fabric before the polyester fiber fabric is printed are measured, When the color difference ΔE was determined, it was 4.33 for the color paste 1, 5.03 for the color paste 2, 5.51 for the color paste 3, and 4.70 for the color paste 4.

Next, in order to recycle the material, the decolored flag for recycling was pulverized, melted, added with a blue pigment, and formed into a tray as it was. The resulting tray was a blue tray with no problem but a slight dullness. As described above, the step 1 for producing the recycling flag of the present invention, the step 2 for the user to use the recycling flag, the step 3 for collecting the recycling flag used by the user, and the collected recycling flag Decoloring by the decoloring method of the present invention Step 4 Using the decolored recycling flag as a raw material for material recycling, and using the recycling method having Step 5 for material recycling, the polyester used as the flag once is made into a material such as a tray. It can be recycled.

(Comparative Example 1) Polyester taffeta (polyethylene terephthalate, warp yarn 83 dtex / 72 filament, weft yarn 83 dtex / 72 filament, density warp 114 / 2.54 cm, width 92 / 2.54 cm) as a polyester fiber fabric Using. Using a screen printing machine, the polyester fiber fabric was printed in a color different from “gasoline” by using the following color paste. After printing the color paste, drying was performed at 140 ° C. for 2 minutes.

Next, padding was performed using a 0.5% aqueous solution of the antistatic agent Nicepol FL (manufactured by Nikka Chemical), antistatic processing was performed, and then finishing was set at 150 ° C. for 30 seconds, and the pigment was printed. A polyester fiber fabric was obtained. Next, the obtained polyester fiber fabric was cut into the size of a banner, and the polyester fabric was used to apply milk for passing through a banner to obtain a banner.

Color paste 1 ("Ga" character)
Binder FRU-5NN (urethane resin, manufactured by Hayashi Chemical Industry Co., Ltd.) 69% by mass
Nonen SM-18 25% by mass
(Halogen flame retardant + antimony flame retardant, manufactured by Maruhishi Oil Chemical Co., Ltd.)
Ryudye W Blue FF2R 4% by mass
(Pigment, manufactured by Dainippon Ink & Chemicals, Inc.)
2% by weight of water

Color paste 2 ("So" character)
Binder FRU-5NN (urethane resin, manufactured by Hayashi Chemical Industry Co., Ltd.) 69% by mass
Nonen SM-18 25% by mass
(Halogen flame retardant + antimony flame retardant, manufactured by Maruhishi Oil Chemical Co., Ltd.)
New Lacquitimine A275 Yellow 4% by mass
(Pigment, Dainichi Seika Kogyo Co., Ltd.)
2% by weight of water

Color paste 3 ("Li" character)
Binder FRU-5NN (urethane resin, manufactured by Hayashi Chemical Industry Co., Ltd.) 69% by mass
Nonen SM-18 25% by mass
(Halogen flame retardant + antimony flame retardant, manufactured by Maruhishi Oil Chemical Co., Ltd.)
Ryudye W Red FFGR 4% by mass
(Pigment, manufactured by Dainippon Ink & Chemicals, Inc.)
2% by weight of water

Color paste 4 (letter “n”)
Binder FRU-5NN (urethane resin, manufactured by Hayashi Chemical Industry Co., Ltd.) 69% by mass
Nonen SM-18 25% by mass
(Halogen flame retardant + antimony flame retardant, manufactured by Maruhishi Oil Chemical Co., Ltd.)
Ryudye W Black RC 6% by mass
(Pigment, manufactured by Dainippon Ink & Chemicals, Inc.)

The banners thus obtained are all light fastness grade 4 or higher, water fastness color change 4-5 grade, contamination 4-5 grade (both cotton and nylon), and sublimation fastness grade 4-5. Flame performance Partial pass with character part, partial reject without character (both micro burner method and coil method), a hard texture was obtained.

Next, the banner flag obtained in the same manner as in Example 1 was attached to the banner and used outdoors for one week, and then collected. The collected banners were decolorized in the same manner as in Example 1. The area where the decolored banners were printed remained quite colored. Next, the color of the portion of the polyester fiber fabric that has been printed with the pigment after the decoloring treatment and the color of the unprinted polyester fiber fabric before the polyester fiber fabric is printed (white fabric) are measured, and the color difference When ΔE was obtained, it was 33.88 for color paste 1, 39.28 for color paste 2, 32.51 for color paste 3, and 34.65 for color paste 4. Since there are many residual pigments after decolorization, the color is dark and cannot be used as a raw material for chemical recycling.

As described above, the flag of the present invention has excellent fastness, has a soft texture, and can be used for chemical recycling and material recycling after being used as a flag. In addition, the flag flag obtained by fixing the pigment of the comparative example with a binder resin has a hard texture and cannot be sufficiently decolored, so that it cannot be used as a raw material for chemical recycling.

According to the present invention, the banner can be easily recycled, so that the present invention can be used industrially advantageously.

Claims (8)

  A recycling method for decoloring a flag for recycling, wherein a polyester fiber fabric printed with a disperse dye constituting a banner is treated with a decoloring treatment solution containing an alkaline agent, a reducing agent and a nonionic surfactant. The method of decoloring a flag for recycling according to claim 1 , wherein the reducing agent includes hydrosulfite and thiourea dioxide. The method for decoloring a flag for recycling according to claim 1 or 2 , wherein the nonionic surfactant is a fatty acid ethylene oxide adduct. The method for decoloring a flag for recycling according to any one of claims 1 to 3 , wherein the decolorization treatment liquid further contains a chelating agent. The method of decoloring a flag for recycling according to any one of claims 1 to 4 , wherein the decoloring treatment liquid further contains an anionic surfactant. The method for decoloring a flag for recycling according to claim 5 , wherein the anionic surfactant is sulfated oil. Step 1 for manufacturing a recycling flag composed of a polyester fiber fabric printed with disperse dye, Step 2 for using the flag for recycling by the user, Step 3 for collecting the flag for recycling used by the user A step 4 of decoloring the collected flag for recycling by the decoloring method according to claim 1 , and a step 5 for performing chemical recycling using the decolored recycling flag as a raw material for chemical recycling. Step 1 for manufacturing a recycling flag composed of a polyester fiber fabric printed with disperse dye, Step 2 for using the flag for recycling by the user, Step 3 for collecting the flag for recycling used by the user A step 4 of decoloring the collected flag for recycling by the decoloring method according to claim 1, and a method for recycling the flag flag comprising step 5 for performing material recycling using the decolored recycling flag as a raw material for material recycling.