JPS59630B2 - Ester Keisen Isei Keitai Osenshiyokusuruhouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing an ester fiber molded article, which is characterized by attaching a disperse dye to the ester fiber molding and then fixing and developing the color by heat treatment. The purpose is to obtain a fast dyed product.

In the present invention, ester fibers are polyester fibers made of long-chain synthetic polymers in which the bonding portion between monomers is mainly ester bonds (-C-O-), and cellulose acetate containing 45% or more of acetic acid dust. A molded article refers to a fiber containing 20% or more of diacetate fiber or triacetate fiber, and the term "molded article" refers to anything composed of fibrous materials such as cotton yarn, tow, top, filament, or knitted fabric.

Furthermore, the disperse dye in the present invention refers to a nonionic dye that does not itself have an ionic group.

After attaching the dye to the fiber molding, it is fixed by heat treatment,
Dyeing methods that develop color have been used for some time, but they have recently attracted attention because they allow continuous staining compared to dip dyeing methods.

This dyeing method is roughly divided into a step of attaching the dye to the ester fiber molded article and a heat treatment step for fixation and color development, but problems remain in the heat treatment step from the viewpoint of continuity.

There are two methods of heat treatment: drying treatment and steaming treatment, and the steaming treatment methods generally include normal pressure treatment, high temperature and high pressure treatment (
There are two methods: the HP method (hereinafter referred to as the HP method) and the superheated steam treatment method (hereinafter referred to as the HT method), but the HP method has the drawback of not being able to achieve a complete seal, and is currently not in practical use, and continuous processing using the HT method is not possible. The reality is that it is being done.

However, the HT method has the drawbacks of lower dyeing density and poor level dyeing than the HP method, making it difficult to carry out continuous dyeing without solving these drawbacks.

Dry heat treatment is generally called the thermosol method, but this method also has the problem of improving dye density and level dyeing properties.

The present inventors have carried out intensive research from the viewpoint that it is possible to improve dyeing density and level dyeing properties in the HT method etc. by adjusting the state at the interface between the fiber and the dye. The present invention was achieved based on the discovery that a rich, uniform, and durable dyed product can be obtained by attaching a dye to the fiber molding, fixing it, and developing color.

Regarding a dyeing method in which a dye is attached to an ester fiber molded article and then fixed and colored by heat treatment, a method of adding a dye and an auxiliary agent is being considered.

Method of adding phosphite triester (Publication Publication 1972)
-39777), it is difficult to constantly obtain stable effects because the phosphorous triester easily undergoes hydrolysis.

Although the method of adding urea is quite effective, when the operation is stopped in the middle of the work, the color paste may harden due to crystallization of urea or the influence of superheated steam.

Furthermore, it decomposes during steaming and heat treatment, generating ammonia gas, which significantly worsens the working environment and makes long-term continuous work difficult.

In the present invention, by dyeing an ester fiber molded article using a disperse dye in the presence of a phosphorus compound represented by the following general formula (1), a rich, uniform, and fast dyed product can be simultaneously obtained.

[However, R is an alkyl group having 6 to 24 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group having at least one benzene ring (an alkyl group having 1 to 24 carbon atoms, an alkenyl group, a cycloalkyl group, and a halogen) Contains substituted aryl groups.

), R' is ethylene and/or propylene group,
■ indicates an integer from 1 to 200].

The phosphorus compound represented by the general formula (1) can be prepared by reacting 3 moles of a monohydroxy compound with 1 mole of phosphorus trichloride (
As a scavenger for the hydrochloric acid gas generated at this time, it is necessary to add 3 moles of triethylamine, tributylamine, etc.), 1 mole of phosphite compounds such as tributyl phosphite, triphenyl phosphite, and tricresyl phosphite. is added, and a compound of general formula (2) is obtained by performing dealcoholization or dephenolization reaction,
Thereafter, the compound used in the present invention represented by general formula (1) can be easily synthesized by adding a small amount of alkyl...ride such as lauryl bromide or lauryl chloride and carrying out an isomerization reaction. .

To explain in more detail, when a small amount of alkyl halide such as lauryl bromide is added to the compound of general formula (2) in the presence of an isomerizing agent and the isomerization reaction of the compound of general formula (2) is carried out at 180 to 230°C for 5 to 8 hours, the alkyl Halide is added,
After the phosphonium salt is generated, the alkyl group of the alkyl bromide is substituted with RO(R'0)l and R', and RO(R'0)1 and R'-X (X represents a halogen) are eliminated and C Five phosphonates with -P bonds are formed.

The released RO(R'0)1-1R'-X acts sequentially as an isomerizing agent to generate phosphoauto, and finally a small amount of RO(R'O)2 and R'-X are released into the system. Remaining inside,
99% or more of the phosphonate compound represented by general formula (1) is obtained.

(Oil Chemistry, V13, 9th page 3 (1964)) R□, R2 and R of the compound represented by general formula (1)
Examples of monohydroxy compounds having an alkyl group, an alkenyl group, and a cycloalkyl group corresponding to 3 include hexyl alcohol, octyl alcohol, tecanol, dodecyl alcohol, tritethyl alcohol, cetyl alcohol, palmitylla/L/cole, and sulf”'allyl. Examples include alcohol, oleyl alcohol, octadecyl alcohol, and synthetic alcohols having 6 or more carbon atoms, as well as cyclohexanol, cyclodecanol, cyclododecanol, and the like.

Monohydroxy compounds having an allyl group include phenol, cresol, xylenol, ethylphenol, butylphenol, dibutylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, tritesylphenol, tetradecylphenol, octadecylphenol, and benzyl alcohol. , methyl pendel alcohol, etc., and their logen-substituted products, such as chloro(mono-penta)phenol, from(mono-penta)phenonopefluoro(mono-penta)phenol, iodo(mono-penta)phenol, etc. Phenylphenol, cyclohexylphenol, cumylphenol, naphthol, butylnaphthol, dibutylnaphthol, etc. and their halogen-substituted products, and furthermore, these phenols and naphthols are treated with benzyl chloride, methyl under catalysts such as anhydrous aluminum chloride and boron fluoride. The following examples are reaction products obtained by reacting 1 mole or more of benzyl halide such as benzyl chloride, styrene, α-methylstyrene, etc.

The raw material alcohols, phenols, and naphthols to which alkylene oxide is added have slightly different effects aimed at in the present invention due to differences in structure and carbon number.

For alcohols with 6 or more carbon atoms, the size of the carbon number,
The difference is greater depending on the type of alkylene oxide added and the number of moles added rather than the type, and the phenol is generally preferably a compound represented by the general formula (1) synthesized from a compound having 2 to 4 benzene rings. but,
It also varies depending on the type of alkylene oxide and the number of moles added.

The reason for using adducts of alcohols, phenols, and naphthols with ethylene oxide and/or propylene oxide as the monohydroxy compound used in the synthesis of the compound represented by general formula (1) is that the addition of alkylene oxides is not suitable for dyes, glues, etc. This is to improve compatibility with agents, and block adducts of ethylene oxide and propylene oxide play a role in foam suppression, foam breaking, and penetration of color pastes and banding liquids. In this case, the purpose is to improve the dyeing rate.

Generally, the most preferable range of the number of moles of ethylene oxide and propylene oxide added to these alcohols, phenols, and naphthols is determined from the viewpoint of the purpose of the present invention, compatibility with sizing agents and dyes, foaming properties of dye liquor, etc. When both ethylene oxide and propylene oxide are added within a range of 1/2 to 5 times the weight of alcohol, phenol, and naphthol, the weight of ethylene oxide is 1/2 to 5 times the weight of propylene oxide. A range of 1 such that /2 or less is preferable.

- The compound represented by general formula (1) has one C-P bond in the molecule, and even if it is synthesized using a hydroxy compound with a high number of added moles of ethylene oxide, it is hardly soluble in water. Does not dissolve.

Therefore, when adding to a color paste with a fairly high viscosity, it is possible to disperse it uniformly by stirring, but when adding to a liquid padding liquid, well-known surfactants and solvents are added as dispersants, emulsifiers, etc. Therefore, care must be taken to ensure uniform dispersion in a stable state.

In addition to the compound represented by the general formula (1), the effect of the present invention can be enhanced by adding a penetrating agent.

In the present invention, methods for attaching the disperse dye to the fiber molded article include methods such as impregnation, spraying, coating, printing, and transfer.

Heat treatment is relative humidity 0-100%R, H170-220℃
Perform within the range of.

For example, as in the thermosol dyeing method, the fiber molding is impregnated with a dye solution, then mangled, and then dry heat treated at 205°C for 1 to 3 minutes, as in the thermosol dyeing method, or printed with a color paste containing a sizing agent. After printing, it is continuously passed through a dryer and steamed with superheated steam at 170°C for 5 to 10 minutes, or the dye solution is coated and dried, and then steamed in a closed container with saturated steam at 110 to 140°C. I do.

In the present invention, when adding the compound represented by the general formula (1) to the dye, if necessary, a dye solubilizer, a sizing agent, P
It is permissible to add an H regulator, a reduction inhibitor, an antifoaming agent, a sequestering agent, etc. at the same time.

However, by adding these, it is necessary to carefully select the proportion within a range that does not impede the uniformity and stability of the system in which the dye of the color paste exists.

When adding the compound represented by the general formula (1) used in the present invention to the dye solution, stir well after addition to ensure uniform dispersion, or add the compound represented by the general formula (1) used in the present invention to the dye solution. It is necessary to dissolve the represented compound in water and a solvent in advance and add it to ensure uniform dispersion, and after confirming this, adjust the pH of the dye solution to the required range.

The amount of the compound represented by the general formula (1) used in the present invention is 1 to 10% by weight based on the color paste impregnation liquid, coating liquid, or spray liquid containing dye and sizing agent.
It is preferable to use the range.

Even if it is used below or above this range, it is difficult to further improve the objective of simultaneously obtaining a rich and uniformly fast dyed product.

Next, examples of the present invention will be shown.

Example 1 (A) Hydroxy compound 1086f (3 moles) obtained by adding 3 moles of ethylene oxide to industrial lauryl alcohol by a known method and triphenyl phosphite 311f (1 mole) were added to a thermometer, a stirring device, and a condenser. , put it in a four-eye flask equipped with a pressure reducing device and a distillation device, add 2 grams of caustic potash, and add 5 to 10 mr/LHg180.
The dephenolization reaction was carried out at ~180°C for 7 hours, phenol 282z was distilled off, and the remaining product was filtered.

Next, 700 g of the obtained residual product was placed in a four-eye flask equipped with a thermometer, a stirrer, a condenser, a pressure reducer, and a distiller, and 4 g of industrial lauryl bromide were added thereto.
Reaction was carried out at 160-220°C for 20 hours, and then at 10 mmH.
g, 4 g of lauryl bromide were distilled off at 160-180°C.

The obtained compound (synthetic product &1) was a colorless and transparent oil at 25°C, and had an acid value (KOH7/l&/7) of 0.3 and a hydroxyl value of 1.0.

In addition, the phosphorus compound (phosphite) before isomerization contains iodine,
When treated with a chloroform solution, a specified amount of iodine was consumed, but the compound obtained after isomerization consumed almost no iodine, indicating that the isomerization reaction was complete.

This synthetic product A1 was added to the dye paste, and the dyeing improvement rate, surface concentration, level dyeing property, and
Perform a dye test for fastness.

(B) Using a hydroxy compound obtained by adding alkylene oxide to alkylphenol, allylphenol, alcohol, etc. in exactly the same manner as in (A), a phosphorus compound (
Synthesized products 2 to 16) were synthesized.

The obtained synthetic products 2 to 16 were added to the dye paste, and (A
) A similar dyeing test is carried out on Tetoron-treated yarn fabric under the same conditions.

The test results are shown in Table 2. (1) Printing method Color paste prescription Dye (C, I Desperse 5 (%) Rad 91) Locust bean-based sizing agent 30 (10%) Starch-based sizing agent (10%) 30 Citric acid (25% aqueous solution) 2 Examples Compound obtained in step 1 1.5 Water 31.5 total
-100,0 (%) Printing condition screen; Flat screen Mesh number of screen; Hardness of 100 mesh spatula;
55° Speed: 8 m/min 1 time drying; 130°C, 5 minutes heat treatment; 170°C, 5 minutes steaming Hydrosulfur 11/L light/conc reduction cleaning; Soda ash 11/LPRA-6C
(Higashi 1g/L manufactured by Hokkaido) Bath ratio 1:30.70°Cl2O Washing with water after separation (2) Measurement method (a) Dyeing improvement rate (%): Equivalent situation of chlorophenol and dimethylformamide The dye was extracted using the combined solution, and the amount of dye in the dyed fabric when the synthetic product obtained in Example 1 after reduction washing was not added was taken as 100, and the dyeing improvement rate when it was added was taken as the dyeing improvement rate. .

(b) Surface concentration (%): Using a spectrophotometer, /S was determined from the reflectance using the Kupertamunk equation, and the same as in (a) was obtained in the case where the synthetic product obtained in Example 1 was not added. /S
The value was set as 100, and the value when added was used as a comparative value (%).

(e) Level dyeing property: Visually evaluated the overall uniformity, density unevenness, texture, etc. in 3 grades: A, B, and C.

A: There is no unevenness and is uniform throughout.

B: Some unevenness is noticeable.

C: There is considerable unevenness.

(d) Light fastness, wet abrasion fastness: For dyed cloth after reduction washing, light fastness was irradiated with carbon puke for 24 hours using a fade meter according to JIS L-0481, and wet abrasion was JIS-L-0489 and Gakushin type. The friction test was conducted 100 times using a testing machine.

Example 2 Dye C0I in Example 1, Desperse Orange 5
5 to 8, synthetic products Nakabana 5 to 8 of Example 1 were used to print on Toshi Tetron processed thread in the same manner as in Example 1, and fixed and colored with saturated steam at 130°C for 30 minutes using the usual method. Perform reduction washing and dyeing.

Obtained.

The dyed products obtained are rich and uniform. It was sturdy.

Example 3 50 parts of dye (C61, Desperse Blue 94), a commercially available thickening agent based on locust bean gum (solid content 8%)
), 20 parts of a 25% aqueous citric acid solution, 10 parts of sodium metanitrobenzenesulfonate, 80 parts of the synthetic product &5 obtained in Example 1, and 30 parts of a homogeneous mixture of 20 parts of an ethylene oxide adduct with an average of 8 moles of nonylphenol. The Toyobo ester processed yarn fabric was impregnated with a dye solution made up to 1000 parts by adding
0%).

Next, after drying at 130°C for 5 minutes, dry heat treatment was performed at 205°C for 2 minutes.

Thereafter, reduction washing was performed in the same manner as in Example 1 to obtain a dyed product.

The dyed products fixed and colored using the dye solution obtained by adding the synthetic product 5 obtained in Example 1 were thicker, more uniform, and more durable than the amount without addition. A product with good permeability to the back side was obtained.

Example 4 50 parts of dye (C,1, Desperse Blue 87), 120 parts of a commercially available thickening agent based on locust bean gum (8% solids content), 20 parts of 25% citric acid, metanitrobenzenesulfone 10 parts of acid soda, 80 parts of synthetic product A16 obtained in Example 1,
) 30 parts of a homogeneous mixture of 20 parts of the compound obtained by adding an average of 20 moles of ethylene oxide to the compound, and 1 part of water.
A uniform pad bath was prepared to give a total of 0.000 parts.

A triacetate (manufactured by Mitsubishi Acetate) fabric was soaked and squeezed so that the weight increase of the fabric was 70%.

After drying at 120° C. for 10 minutes and treating at 205° C. for 2 minutes to develop color, reduction washing was performed in a conventional manner to obtain a dyed product.

The dyed products obtained by adding Synthesis 1 A and 16 obtained in Example 1 were thicker and more uniform than the amount without addition.
It was sturdy.

Example 5 5Q parts of dye (C0I, Desperse Blue 94), 600 parts of a commercially available thickening agent based on locust bean gum (solids content 8%), 20 parts of 25% citric acid, sodium metanitrobenzenesulfonate A homogeneous color paste was prepared by adding 10 parts of synthetic product 5 obtained in Example 1, 15 parts of Boiled 16, and 1000 parts of water. ) Printed on textiles.

After drying at 130° C. for 5 minutes, it was treated with superheated steam at 170° C. for 10 minutes, and reduction washing was performed in a conventional manner to obtain a dyed product.

Compared to the product obtained in Example 1 without the addition of the synthetic product, the dyed product obtained with the addition of the synthetic product was thicker, more uniform, and more durable.

Example 6 50 parts of dye (C,1, Desperse Orange 55), 300 parts of a commercially available thickening agent based on starch-based sizing agent, 20 parts of 25% citric acid, 10 parts of sodium metanitrobenzenesulfonate
40 parts of the synthetic product 3 obtained in Example 1, 30 parts of Boiled 15, and compound 3 obtained by adding an average of 20 moles of ethylene oxide to the hydroxy compound (Example 3).
Add water to 30 parts of a homogeneous mixture of 0 parts to make 1000 parts.
A uniform coating solution was prepared so that

Ester/triacetate mixed fabric (30% ester,
This was coated on triacetate (70%), and 130
It was dried at 170°C for 5 minutes and then treated with superheated steam at 170°C for 5 minutes to fix and develop color.

A staining method was obtained by carrying out reduction washing using a conventional method.

The dyed product obtained using the synthetic product obtained in Example 1 was thicker, more uniform, and more durable than the product without additives.

Example 7 50 parts of dye (C01, Desper Red 91), 550 parts of a commercially available thickening agent (solid content 10%) based on starch-based sizing agent
1 part, 20 parts of a 25% citric acid aqueous solution, 10 parts of metanitrobenzenesulfonic acid, 30 parts of the synthetic product &14 obtained in Example 1, and water to make a uniform color paste of 1,000 parts. It was adjusted.

Apply this color paste to Nippon Cloth's non-woven fabric Springlon #2.
Printed on 9-450 (Tetron 100%), then 130℃
, dried for 5 minutes, and treated with superheated steam at 170° C. for 10 minutes.

After reduction washing was carried out in a conventional manner, a dyed product was obtained.

The dyed product obtained using the synthetic product A14 obtained in Example 1 was thicker, more uniform, and more durable than the product without additives.

Example 8 50 parts of dye (C, I, Desperse Yellow 117), 540 parts of starch-based sizing agent (solid content 10%), 20 parts of 25% citric acid aqueous solution, 80 parts of synthetic product A3 obtained in Example 1 Department,
Add 30 parts of a homogeneous mixture of 20 parts of the compound obtained by adding an average of 20 moles of ethylene oxide to the hydroxy compound (Example 6), 10 parts of sodium metanitrobenzene sulfonate, and water to make 1000 parts. Prepare a uniform color paste, print on Tetron (manufactured by Toshi) processed yarn, dry at 130℃ for 5 minutes, and then treat with superheated steam at 170℃ for 10 minutes to develop and fix the color. A dyed product was obtained by reduction washing according to the method.

The dyed product obtained using Synthesis Amount 3 obtained in Example 1 was thicker, more uniform, and more durable than the product without additives.

Claims (1)

[Scope of Claims] 1 When dyeing an ester-based fiber molded article, the following general formula [where R is an alkyl group having 6 to 24 carbon atoms, an alkenyl group, a cycloalkyl group, or a benzene ring (one or more) is used. (including alkyl groups having 1 to 24 carbon atoms, alkenyl groups, cycloalkyl groups, and aryl groups substituted with halogen), R' is ethylene and/or
A disperse dye is attached to the fiber molded article in the presence of at least one compound represented by a propylene group, ■ represents an integer from 1 to 200, and then fixed and colored by heat treatment. A method for dyeing an ester fiber molded article.