JPS593596B2 - Sansei Kaishitsu Polyester Keisen Innosen Yokuhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for improving light fastness through the combined use of blue cationic dyes having different structures, and more specifically,
In dyeing acid-improved polyester fibers, the general formula (I
) (In the formula, R1 represents a lower alkyl or aryl group which may be substituted with a cyan group or a carbamoyl group, and the aromatic group in the above general formula is a halogen, alkoxy, acyl, acylamino and/or dialkylamino group. Ar represents an aromatic group, and the aromatic group may be substituted with a halogen and/or alkoxy group, R2 and R3 represent an alkyl group or an aryl group, and the alkyl The group can form part of a saturated heterocyclic thread and can be substituted with halogen.

X is an anionic residue such as hydrochloric acid, sulfuric acid, alkyl sulfate,
Indicates acetic or phosphoric acid residues.

) and the naphthostyryl cationic dye represented by the general formula (II) (wherein R1, R2, R3, and R4 represent an alkyl group or an aryl group, and the alkyl or aryl group may be substituted with a halogen or cyan group. , R1t R2t R
3t R4 may be the same or different, R5 represents hydrogen or an alkoxy group, and X represents an anionic residue, such as a hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid residue.

) is a method for dyeing acidic modified polyester fibers, which is characterized by the combined use of oxazine-based cationic dyes.

Cationic dyes have been widely used in acid-modified synthetic fibers such as acrylic fibers, but there is a particular practical need to improve the light fastness of acid-modified polyester fibers.

However, even though the light fastness of cationic dyes on acrylic fibers is excellent without any practical problems, the light fastness of acrylic dyes on acid-modified synthetic fibers, especially on acid-modified polyester fibers, is excellent. When compared with that of other fibers, it is often significantly lower.

In particular, the light fastness of blue cationic dyes often decreases, for example, naphthostyryl cationic dyes and oxazine cationic dyes, but these dyes do not sufficiently satisfy the light fastness required for practical use. However, its use is quite limited.

Therefore, there is no doubt that it lacks versatility and its industrial value is low.

As a result of various studies in view of the above circumstances, the present inventors have found that
By using a naphthostyryl-based cationic dye represented by general formula (1) and an oxazine-based cationic dye represented by general formula (II) together on acidic modified polyester fibers, compared to when each is used alone, The inventors have discovered the groundbreaking new fact that the light fastness is significantly improved, leading to the present invention.

This fact is of great significance from an industrial perspective.

In the present invention, the naphthostyryl cationic dye represented by general formula (I) and the oxazine cationic dye represented by general formula (II) may be blended in any proportion, but usually the former is 10 to 90% and the latter is in charge of 90-10,
More preferably, the former is 30-70, and the latter is 70-30.
I am in charge.

It goes without saying that two or more of the naphthostyryl cationic dye represented by the general formula (I) and the oxazine cationic dye represented by the general formula (If) which are used in combination may be used.

In addition, dyes other than the above, such as diallylmethane, may be used to the extent that they do not adversely affect the light fastness obtained by the combination of the naphthostyryl cationic dye represented by the general formula (I) and the oxazine cationic dye represented by the general formula (II). It is also possible to use one or more types of cationic dyes, such as triallylmethane, thiazole, and benzthiazole cationic dyes, for color toning.

Furthermore, the dye obtained by the above method may contain a dye having a color tone different from that of the dye obtained by the method described above, such as yellow 1.
・It is of course possible to blend one or more cationic dyes with red, purple, etc. tones, and □ this does not impair the characteristics of the present invention in the slightest and can be used without any practical problems. .

The acidic modified polyester fiber targeted in the present invention means a polyester fiber modified by adding a dyeing seat for cationic dyes by a method such as copolymerization, blending, or grafting, for example, by copolymerizing sulfoisophthalic acid. Dacron T-64, Dacron T-65, Dacron T-62,
Dacron T-89, Dacron T-92, etc. (product of DuPont, USA), Trevira 440 (product of Histron, USA)
, Kogel 511 (manufactured by Eastman, USA), and CD Woolly Amundsen (manufactured by Teijin).

As a naphthostyryl cationic dye represented by the general formula (I), which is one of the dyes used in the present invention,
No. 1-20714, No. 47-9099, No. 43-99
Examples include those disclosed in No. 33 and No. 45-30070.

For example, the general formula (1) described in Japanese Patent Publications Nos. 45-30070 and 47-9099 (wherein, X represents a cyan group or a carbamoyl group, and
represents a benzene nucleus or a naphthalene nucleus which may have a nonionic substituent, and R1 and R2 represent an alkyl group, a cycloalkyl group, an allyl group, or an aralkyl group which may have a nonionic substituent. and R1 and R2 may be fused together to form a saturated heterocycle with the adjacent nitrogen atom.

Ye represents an anionic group, and the naphthalene nucleus A may have a nonionic substituent.

) can be used.

Furthermore, the general formula (IV) described in Japanese Patent Publication Nos. 41-20714 and 43-9933 (wherein R1 represents a lower alkyl or aryl group, and the aromatic group in the above general formula is halogen, alkoxy, acyl) , acylamino and/or dialkylamine groups, Ar represents an aromatic group, R2 and R
3 represents an alkyl or aryl group, and the alkyl group can constitute part of a saturated heterocyclic ring system,
The aromatic ring can be substituted with a halogen and/or an alkoxy group, the alkyl group can be substituted with a halogen, and if the naphthalene ring is unsubstituted, at least one of R2 and R3 is an aryl group, and X represents an anionic residue, such as a hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid residue.

) can be used.

Next, regarding the oxazine-based cationic dye represented by the general formula (1) that can be used in combination with the naphthostyryl-based cationic dye, many known ones can be used, including the following dyes.

In carrying out the present invention, a method may be used in which dyes are mixed in advance in appropriate ratios, or a method in which each dye is added in appropriate ratios during dyeing may be used.

The light fastness of the dyeings according to the invention is such that it provides an excellent light fastness that cannot be expected when each dye is used alone.

It's practical. It is also durable enough for use.

Next, the light fastness results obtained using various blending ratios of these dyes were measured on CD Wooli Amundsen (acid-modified polyester synthetic fiber manufactured by Teijin), and the results are shown in FIG.

The staining density is JIS 1/1 standard density.

The vertical axis shows the light fastness, and the horizontal axis shows the blending ratio of each dye.

In addition, the following dye (5) was used.

As is clear from Fig. 1, the light fastness of all of them is improved by using them together.

Examples of the present invention will be specifically described below, but the present invention is not limited thereto.

Example I When dyeing CD Woolly Amundsen (acid-modified polyester synthetic fiber manufactured by Teijin), 9 parts of the dye represented by the following formula (A) and 16.8 parts of the dye represented by the following formula (O) were used. 0.01 of the dye
Take 5 parts, dissolve in 10 parts of hot water, dilute by adding 250 parts of water, and further add 0.05 part of acetic acid (90%), 0.015 part of anhydrous sodium acetate, and 1 part of anhydrous sodium sulfate to dye. Adjust the bath.

Soak 5 parts of CD Uhliamundsen in this and add 1 part in 40 minutes.
The temperature is increased to 20°C and dyeing is carried out for 40 minutes at the same temperature.

After dyeing, the dyed product is then washed with water and dried.

In this way, the acid-modified polyester synthetic fiber was uniformly dyed in a bright blue color.

The light fastness of the thus obtained dyed product was compared with the light fastness of the previously dyed dye alone, which was used in combination. The results are as follows.

Example 2 Example 1 for dyeing CD Woolly Amundsen
0.015 parts of the dye consisting of 12 parts of the dye (a) and 14.5 parts of the dye (b) used in the above are taken and dyed according to the operating procedure described in Example 1 below.

In this way, the acid-modified polyester synthetic fiber was uniformly dyed in a bright blue color.

The light fastness of the thus obtained dyed product was compared with the light fastness of the previously dyed dye alone, which was used in combination. The results are as follows.

Example 3 When dyeing Dacron T-92 (acid-modified polyester synthetic fiber manufactured by DuPont), 0.0. 015
A sample is taken and dyed according to the operating procedure described in Example 1 below.

In this way, the acid-modified polyester synthetic fiber was uniformly dyed in a bright blue color.

The light fastness of the thus obtained dyed product was compared with the light fastness of the previously dyed dye alone, which was used in combination, and the results are as follows.

Example 4 When dyeing Dacron T-64 (acid-modified polyester synthetic fiber manufactured by DuPont), 12 parts of the dye represented by the following formula (E) and 14.5 parts of the dye represented by the following formula (F) were used. A dye consisting of 0.015
Hereinafter, staining is carried out according to the operating procedure described in Example 1.

In this way, acid-modified polyester synthetic fibers
Uniformly dyed bright blue.

The light fastness of the thus obtained dyed product was compared with the light fastness of the previously dyed dye alone, which was used in combination, and the results are as follows.

[Brief explanation of the drawing]

FIG. 1 is a curve showing the relationship between the blending ratio of dyes and light fastness in the present invention.

Claims (1)

[Scope of Claims] 1. In the dyeing of acidic modified polyester fibers, 7 general formula (I) (wherein s R1 represents a lower alkyl or aryl group which may be substituted with a cyan group or a carbamoyl group, The aromatic group in the above general formula is halogen, alkoxy,
It can be substituted with acyl, acylamino and/or dialkylamine groups, Ar represents an aromatic group and the aromatic group can be substituted with halogen and/or alkoxy groups, R2 and R3 are alkyl or aryl group, the alkyl group can form part of a saturated heterocyclic ring system and can be substituted with halogen. Moreover, X represents an anionic residue. ) and the naphthostyryl cationic dye represented by the general formula (II) (wherein, R1t R2p R3p R4 represents an alkyl group or an aryl group, and the alkyl or aryl group can be substituted with a halogen or cyan group, and R1t R
2y R3y R4 may be the same or different, R represents hydrogen or an alkoxy group, and X represents an anionic residue. ) A dyeing method for acid-modified polyester fibers, characterized by using an oxazine-based cationic dye shown in