JP3226324B2 - Dye fastness improver - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye fastness improver, and more particularly to a dye fastness improver for a dyed article dyed with a direct dye and a reactive dye.

[0002]

2. Description of the Related Art A dyed product dyed with a direct dye generally has low color fastness such as fastness to washing, fastness to water and fastness to sweat, and cannot be put to practical use as it is. Further, the dyed material dyed with the reactive dye is superior in dyeing fastness as compared with the dyed material with the direct dye, but still does not provide sufficient dyeing fastness. This is because the covalent bond between the fiber and the reactive dye is gradually broken by hydrolysis in air, and the amount of dye bonded to the fiber decreases with time. Therefore, even in the case of an object to be dyed with a reactive dye, it often occurs that it cannot be put to practical use as it is.

[0003] For these reasons, conventionally, the dyeing treatment of the dyed article using a dye fastness improver has been carried out after dyeing in order to improve the color fastness of the dyed article.

As a dye fastness improver, there have hitherto been used cationic surfactants, condensates of dicyandiamide and formalin, condensates of polyamines such as ethylenediamine and diethylenetriamine and dicyandiamide, and equimolar amounts of secondary amines and epihalohydrins. Reaction products, special cationic water-soluble polymers such as polyamine sulfone and polydimethyldiallylammonium chloride are used.

[0005]

However, even if such a conventional dye fastness improver is used, there are the following problems. That is, even if a cationic surfactant is used, there is still a problem that a sufficient robustness improving effect cannot be obtained, and when a condensate of dicyandiamide and formalin is used, residual formalin is not safe for the human body. This is a problem. When a condensate of polyamine and dicyandiamide is used, since a primary amine, a secondary amine and a tertiary amine are present in addition to the quaternary ammonium salt, discoloration of the dye occurs and light fastness is reduced. There's a problem. In addition, when a reaction product of a secondary amine and epihalohydrin is used, there is a problem that water fastness and sweat fastness are poor. Polyamine sulfone has a problem in that the amount of polyamine sulfone used is large because of its weak binding force with the dye. Furthermore, when polydimethyldiallylammonium chloride is used, an object to be dyed which is excellent in washing fastness, water fastness and sweat fastness can be obtained, but there is a problem that the texture of the object to be dyed is reduced. .

The present invention has been made to solve such a conventional problem, and an object of the present invention is to obtain an excellent effect of improving the color fastness and to improve the safety. An object of the present invention is to provide a dye fastness improver which has no problem and can improve the texture of a material to be dyed.

[0007]

In order to achieve the above-mentioned object, the dye fastness improver of the present invention contains 65 to 99 mol of an ethylene structural unit (I) represented by the general formula (4) in a molecule. % And an acrylamide structural unit (I
II) from 1 to 35 mol%, and a dispersion of a linear cationic copolymer having a weight-average molecular weight of 1,000 to 50,000. Each of the structural units may be arranged regularly or irregularly.

[0008]

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[0009]

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(However, in the chemical formula 5, R ² has 2 to 2 carbon atoms.
8 represents an alkylene group, R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents 1 to 12 carbon atoms.
Represents an alkyl group, an arylalkyl group having 6 to 12 carbon atoms or an alicyclic alkyl group having 6 to 12 carbon atoms, and X ⁻ represents a halogen ion, CH ₃ OSO ₃ ^— or CH ₃ CH ₂ OS.
O ₃ ^- represents, R ² to R ⁵ and X ^- is may be the same or different to each respective structural units. Further, in the dye fastness improver of the present invention, the cationic copolymer may further contain 15 mol% or less of the acrylate structural unit (II) represented by the general formula (6).

[0011]

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(However, in the chemical formula 6, R ¹ has 1 to ¹ carbon atoms.
4 represents an alkyl group, and R ¹ may be the same or different for each structural unit. In the present specification, the term "dispersion" includes macroscopically uniform systems such as those obtained by emulsifying, solubilizing, and dispersing the cationic copolymer in water. It is a concept.

The constitution of the cationic copolymer used in the dye fastness improver of the present invention will be described in more detail below.

In the cationic copolymer, the ethylene structural unit (I) represented by the general formula (4) has 6
It is contained at 5 to 99 mol%, and this content ratio is 6%.
If it is less than 5 mol%, the texture of the material to be dyed will be reduced. On the other hand, when the content of the ethylene structural unit (I) exceeds 99 mol%, the content of the acrylamide structural unit (III) decreases, and the effect of sufficiently improving the color fastness by the acrylamide structural unit (III) can be obtained. Disappears. From the viewpoint of texture and color fastness, the ethylene structural unit (I) is from 85 to 9
More preferably, the content is 7 mol%.

In the cationic copolymer used for the dye fastness improver of the present invention, the acrylamide structural unit (III) represented by the general formula (5) is a cationic acrylamide structural unit having a quaternary ammonium salt. Unit
It is contained at 1 to 35 mol% in the molecule. When the content is less than 1 mol%, the color fastness cannot be sufficiently improved, and when the content exceeds 35 mol%, the feeling of the material to be dyed is reduced. From the viewpoint of the effect of improving the color fastness and the texture, the acrylamide structural unit (II
The content ratio of (I) is more preferably 3 to 15 mol%.

In the acrylamide structural unit (III) of the general formula 5, R ² represents an alkylene group having 2 to 8 carbon atoms. Specific examples of R ² include an ethylene group, a propylene group, a hexamethylene group and a neopentylene group. These alkylene groups may be mixed in one molecule. Among these alkylene groups,
From the viewpoints of easiness of production and economy, an ethylene group and a propylene group are preferred, and a propylene group is particularly preferred.

R ³ and R ⁴ in the acrylamide structural unit (III) each independently represent an alkyl group having 1 to 4 carbon atoms. These alkyl groups may be mixed in one molecule. Specific examples of R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these alkyl groups, a methyl group and an ethyl group are preferred from the viewpoint of the effect of improving the color fastness.

R ⁵ of the acrylamide structural unit (III) is
Represents an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 6 to 12 carbon atoms, or an alicyclic alkyl group having 6 to 12 carbon atoms. These alkyl groups may be mixed in one molecule. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, an n-octyl group, and an n-lauryl group. Specific examples of the arylalkyl group include a benzyl group and a 4-methylbenzyl group. Specific examples of the alicyclic alkyl group include a cyclohexyl group and a methylcyclohexyl group. Among these, from the viewpoint of color fastness improving effect, a linear alkyl group and arylalkyl group are preferable as R ^5, in particular methyl and ethyl groups are preferred.

X in the acrylamide structural unit (III)
^{- is, Cl -, Br -, I} - halogen such as ions, C
H ₃ OSO ₃ ^— or CH ₃ CH ₂ OSO ₃ ^— , and these anions may be present in one molecule. Among these anions, from the viewpoint of the effect of improving the color fastness, Cl ⁻ , CH ₃ OSO ₃ ⁻ and CH ₃ CH ₂ OSO are used.
₃ ^- is preferable. Further, the cationic copolymer used in the dye fastness improver of the present invention may contain the acrylate structural unit (II) represented by the general formula (6) in a molecular amount of 15 mol% or less. . It is preferable to contain the acrylate structural unit (II) because it has the effect of improving the texture. When the content ratio of the acrylate structural unit (II) is 15
If it exceeds mol%, the texture will be reduced.

In the acrylate structural unit (II) represented by the general formula 6, R ¹ represents an alkyl group having 1 to 4 carbon atoms. Specific examples of R ¹ include a methyl group, an ethyl group, n-
Propyl group, iso-propyl group, n-butyl group, is
An o-butyl group can be mentioned. These alkyl groups may be mixed in one molecule. Among these alkyl groups, a methyl group and an ethyl group are preferable from the viewpoint that they do not adversely affect the feeling.

The weight average molecular weight of the cationic copolymer used in the dye fastness improver of the present invention is measured by gel permeation chromatography (GPC).
Ultra high temperature GPC as weight average molecular weight in terms of polystyrene
Method (Kinukawa, Journal of Polymers, Vol. 44, No. 2, 139-141
1987). According to the measurement results, the preferable range of the weight average molecular weight is 1,000 to 5
It is 0000. When the weight average molecular weight is less than 1,000, the molecular weight is too small and the effect of improving the color fastness, which is the object of the present invention, cannot be sufficiently exhibited. When the weight average molecular weight exceeds 50,000, the texture is lowered. The preferred range of the weight average molecular weight of the cationic copolymer is from 3,000 to 30,000.

The cationic copolymer used in the dye fastness improver of the present invention can be produced, for example, as follows. That is, an ethylene-acrylate copolymer obtained by copolymerizing ethylene and an acrylate by a high-pressure polymerization method is subjected to thermal degradation simultaneously with hydrolysis by the method described in JP-A-60-79008. To the desired molecular weight. By partially performing this hydrolysis reaction, an ethylene-acrylate-acrylic acid copolymer is obtained from the ethylene-acrylate copolymer. Further, the obtained ethylene-acrylic acid ester-acrylic acid copolymer is amidated with N, N-dialkylaminoalkylamine or the like to obtain an acrylamide copolymer, which is then converted to an alkyl halide, dialkyl sulfate or the like. The cationic copolymer can be obtained by cation modification with a quaternizing agent and isolation. In addition, by completely hydrolyzing the above-mentioned ethylene-acrylate copolymer, an acrylate structural unit (I
A cationic copolymer free of I) is obtained.

The dye fastness improver of the present invention can be obtained by dispersing the above-mentioned cationic copolymer in water.
For example, the dye fastness improver of the present invention can be obtained by emulsifying the above-mentioned cationic copolymer in water by a high-pressure emulsification method. In the high-pressure emulsification method, a dyeing fastness improver can be obtained as an emulsion by charging a cationic copolymer together with water into an autoclave and stirring the mixture under pressure at a temperature of 110 to 140 ° C. The cationic copolymer can be made into a dispersion without using a surfactant, but a surfactant may be added during emulsification, solubilization, and dispersion.

The method for treating a dyed article using the dye fastness improver of the present invention is not particularly limited, and a conventionally known method can be appropriately selected and used. For example, a dyeing object to be treated is immersed in a dispersion prepared by dissolving the dye fastness improver of the present invention so that the content of the cationic copolymer is 0.2 to 20 g / l, and then washed with water. And dry it. The bath ratio at the time of immersion, that is, the ratio between the material to be dyed and the dispersion is preferably 1:10 to 1:20, the treatment temperature is usually preferably normal temperature to 80 ° C, and the immersion treatment time is usually 5 to 20 minutes. Preferably it is.

The dye fastness improver of the present invention can be used for a dyeing material such as a yarn dyed with a direct dye or a reactive dye.

[0026]

In the dye fastness improver of the present invention, the cationic copolymer has polyethylene as a main chain, and a quaternary alkyl ammonium salt is bonded to the polyethylene via an amide group. It is considered that this polyethylene main chain shows affinity for the dyeing material, improves the feeling of the dyeing material, and binds the quaternary alkylammonium salt to the dye to fix the dye.

[0027]

According to the dye fastness improver of the present invention, a quaternary alkylammonium salt forming a bond with a dye is bonded to a polyethylene main chain having an affinity for an object to be dyed via an amide group. Therefore, the dye fastness is improved, and a dyed article having excellent dyeing fastness such as washing fastness, water fastness and sweat fastness can be obtained. In addition, the texture of the object can be improved. In addition, the dye fastness improver of the present invention has no problem in terms of safety to the human body.

[0028]

EXAMPLES Examples of the dye fastness improver of the present invention will be described. First, specific production examples of the cationic copolymer used in the dye fastness improver of the present invention will be described.

<Preparation Example 1> (Preparation of a cationic copolymer) 400 ml of xylene, ethylene acrylic, and a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a Dean-Stark separator were used. 150 g of an ethyl acrylate / acrylic acid copolymer (ethylene / ethyl acrylate / acrylic acid = 93/3/4) and 1.0 g of paratoluenesulfonic acid were charged.

Next, 21.1 g of N, N-dimethylaminopropylamine was charged and the mixture was heated at 140 ° C. using an oil bath.
, And the generated water was continuously removed by azeotropy with xylene. Further, the reaction was carried out at 140 ° C. for 17 hours, and the amidation reaction was continued until no water was generated and no azeotropy of water was observed. .

458 g of the obtained reaction product was cooled to 80 ° C., and methyl iodide 2 was added to the reaction mixture from a dropping funnel.
8.7 g was gradually added dropwise over 1 hour. During this time, heat generation was observed, but the reaction temperature was reduced to 90 ° C. by cooling.
Maintained. After completion of the dropwise addition, an aging reaction was performed at 100 ° C. for 4 hours. The reaction product thus obtained was poured into a large amount of methanol, and the formed precipitate was recovered and dried to obtain a cationic copolymer.

The weight average molecular weight of this cationic copolymer was 19,400.

<Production Examples 2 to 9> In the same manner as in Production Example 1, according to the method described in Japanese Patent Application No. 2-331082, cationic copolymers shown in Production Examples 2 to 9 in Table 1 were prepared. The raw materials used in Production Examples 2 to 9 were as follows in Production Example 1
Is different.

In Production Examples 8 and 9, R in the ethylene / ethyl acrylate / acrylic acid copolymer of the raw material copolymer was used.
¹ is each n-propyl group and n-butyl group,
In Production Examples 5 and 7, an ethylene / acrylic acid copolymer was used as a raw material copolymer. In Production Examples 4 and 8, N, N-dimethylaminoethylamine was used as an aminating agent,
In Production Example 6, N, N-dimethylaminoneopentylamine was used as an aminating agent, in Production Example 7, N, N-diethylaminopropylamine was used as an aminating agent, and in Production Example 9, N, N-dimethylaminoneopentylamine was used as an aminating agent. Diethylaminoethylamine was used. In Production Examples 2, 5, 6, and 8, diethyl sulfate was used as a quaternizing agent.
In Example 3, benzyl chloride was used as a quaternizing agent, and in Production Example 3, p-methylbenzyl chloride was used as a quaternizing agent.

Table 1 shows R ^{1 to} R ⁵ and X ⁻ in each structural unit of the cationic copolymers of Production Examples 1 to 9, their molar ratios, and weight average molecular weights.

[0036]

[Table 1]

Next, specific examples of the dye fastness improver of the present invention and specific comparative examples for comparison with the examples will be described. <Examples 1 to 9> (Preparation of dye fastness improver) The dye fastness improver of Example 1 was prepared using the cationic copolymer produced in Production Example 1. This dye fastness improver is prepared by charging the cationic copolymer of Production Example 1 together with water in an autoclave so as to have a solid content of 20% at 120 ° C. under a high temperature and pressure of ^{2 to} 2.5 kg / cm 2. Obtained by stirring for hours. Similarly, the cationic copolymers of Production Examples 2 to 9 were mixed at a solid content of 20%.
In the same manner as described above, dye fastness improvers of Examples 2 to 9 were obtained.

<Comparative Example> A comparative example used polydimethyldiallylammonium chloride as a dye fastness improver.

<Dyeing Fastness Test> Using the dyeing fastness improvers of Examples 1 to 9, tests such as dyeing fastness were performed. The same test was performed for the comparative example. The details of the color fastness test are as follows.

(1) Preparation of Dyeing Cloth for Test A test cloth (Kanakin No. 3) was dyed using the following dye,
A test dyeing cloth was prepared.

Direct Dye @ Kayaras Supra Red 6B
L Reactive dye: Mikasion Brilliant Red 5BS The staining method is as follows. That is, a dyeing solution was prepared by dissolving 3% by weight of the above-mentioned dye with respect to 100% by weight of the test cloth at a bath ratio of 1:20. Next, a test cloth was dyed using this dyeing solution to prepare a test cloth.

(2) Treatment with a dye fastness improver The test solution prepared by diluting the dye fastness improvers of Examples 1 to 9 with water so that the solid content of the cationic copolymer becomes 0.05%. Was prepared. Test liquids were prepared for the comparative examples at the same solid content ratio. Using these test solutions, bath ratio 1:
20, the test dyeing cloth was immersed at a treatment temperature of 60 ° C. for 20 minutes, washed with water and dried.

(3) Test Method The test items are wash fastness, water fastness, sweat fastness and texture. The test method for each test item is the following J
Compliant with IS. Fastness to washing: JIS-L-1045 Conforms to A-2 for direct dyes Conforms to A-4 for reactive dyes Fastness to water conforms to JIS-L-0846 against sweat Fastness ‥‥ Based on JIS-L-0847 A-1 Each of the above-described dyeing fastnesses was determined by using the gray scale for staining to determine the degree of staining of the attached white cloth (cotton or silk).

The hand was determined by the touch of a test dyeing cloth which had been dipped in a dye fastness improver and dried. The criteria are shown below.

…: Good Δ: slightly poor ×: poor The results of these tests are shown in Table 2.

[0046]

[Table 2]

As shown in Table 2, the test dyed fabrics treated with the dye fastness improvers of Examples 1 to 9 were all different from the comparative examples using polydimethyldiallylammonium chloride as the dye fastness improver. Also showed high color fastness. In addition, better results were obtained for the texture than in the comparative example.

Continuation of the front page (56) References JP-A 1-272887 (JP, A) JP-A 4-198307 (JP, A) JP-A 62-156374 (JP, A) JP-A 56-31088 (JP, A) JP-A-63-92788 (JP, A) JP-A-63-227870 (JP, A) JP-A-2-80681 (JP, A) JP-A-61-231283 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) D06P 5/08

Claims (2)

(57) [Claims] 1. An ethylene structural unit (I) represented by the general formula 1
It contains 99 mol% and 1 to 35 mol% of the acrylamide structural unit (III) represented by the general formula (2), and has a weight average molecular weight of 1,000.
A dye fastness improver comprising a linear cationic copolymer dispersion of 0 to 50,000. Embedded image Embedded image (However, in the chemical formula 2, R ² represents an alkylene group having 2 to 8 carbon atoms, R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents 1 to 4 carbon atoms. 12 alkyl groups, arylalkyl groups having 6 to 12 carbon atoms or 6 carbon atoms
It represents 12 alicyclic alkyl group, X ^- is a halogen ion, CH ₃ OSO ₃ ^- represents, R ² to R ⁵ and X ^{- -} or CH ₃ CH ₂ OSO ₃ is a identical to each respective structural units Or different. ) 2. The cationic copolymer further comprises 15 mol% of an acrylate structural unit (II) represented by the general formula (3).
The dye fastness improver according to claim 1, which is contained in the following. Embedded image (However, in Chemical formula 3, R ¹ represents an alkyl group having 1 to 4 carbon atoms, and R ¹ may be the same or different for each structural unit.)