JPH0429788B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a continuous dyeing method for cellulose and polyester mixed fibers (hereinafter referred to as C/P fibers), and more specifically, a mixed dye of a reactive disperse dye and a polyester disperse dye. This invention relates to a method for dyeing C/P fibers using a continuous dyeing method. (Prior art) In recent years, with the diversification of fiber materials, C/P fibers have come into widespread use.Generally speaking, the dyeing method for these fibers involves dyeing cellulose in advance using a water-soluble reactive dye. Traditionally, methods have been employed to dye the side and then dye the polyester side using a polyester disperse dye. However, in this method, the dyeing conditions (mainly dyeing temperature and pH range) when dyeing the cellulose side and the polyester side were different, so it was necessary to divide the dyeing process into two stages. Therefore, in order to streamline this dyeing process,
A one-step dyeing method using a water-insoluble reactive disperse dye that has a reactive group and can dye cellulose and also dye polyester at the same time, or an improved structure that can be dyed under the same dyeing conditions as polyester. A method has been proposed in which dyeing is carried out in one step under conventional dyeing conditions for polyester using a reactive dye and a disperse dye for polyester. From both of these perspectives, reactive disperse dyes and reactive dyes having various new structures have been developed. (Problem to be solved by the invention) However, in the above method, both the cellulose side and the polyester side are dyed with the same dye;
Depending on the reactive disperse dye used, a slight difference in color tone may occur between the two fibers. In such a case, in order to correct this color tone difference, an improvement measure is taken in which a small amount of a polyester disperse dye is used in combination. However, when C/P fibers are dyed, for example, by the pad continuous dyeing method using a reactive disperse dye containing a small amount of polyester disperse dye,
There was a drawback that the washing fastness and cleaning fastness of the resulting dyed product deteriorated. in short,
During the dyeing process, some of the disperse dyes for polyester stain the cellulose side, but
Since this amount of dye is not easily removed by normal soaping treatment, it is presumed that this is the main cause of the deterioration of the fastness. (Means for Solving the Problems) The present invention improves washing fastness and cleaning properties even when C/P fibers are dyed by a pad continuous dyeing method using a reactive disperse dye containing a polyester disperse dye. The purpose is to provide a dyeing method that does not deteriorate fastness, and this purpose is achieved by washing the dyed product after steam treatment in an alkaline aqueous solution of a specific concentration at a specific temperature according to the method of the present invention. achieved. That is, the gist of the present invention is to use a mixed dye of a reactive disperse dye and a polyester disperse dye,
In a method for continuously dyeing C/P fibers, the dyed object is subjected to a padding treatment using a padding bath containing the mixed dye, a nonionic surfactant, and a reaction catalyst, and then heat treated at a temperature of 170 ° C. or higher,
Contact treatment with an alkaline bath of PH8 or higher, and furthermore, 90~
After steam treatment at a temperature of 130℃, this
A continuous dyeing method for mixed fibers characterized by washing in an alkaline aqueous solution having a concentration of 0.005% by weight or more at a temperature of 100°C. The structure of the reactive disperse dye targeted by the present invention is particularly limited as long as it has a reactive group and can dye cellulose, is water-insoluble, and can dye polyester. Instead, conventionally known reactive disperse dyes can be used. Specific examples of these dyes include the following. The reactive group is usually an addition type reactive group such as a vinyl sulfone group, or the following general formula [] [In the formula, -P represents a fluorine atom, a chloro atom, or a bromine atom, -Q is -P or a -NR ¹ R ² group,
(-R ¹ and -R ² represent a hydrogen atom or an alkyl group, an alkenyl group, a cyclohexyl group, an aryl group, or an aralkyl group which may be substituted with a cyano group, a hydroxyl group, a lower alkoxy group, or a dialkylamino group, or or −
NR ¹ R ² is formed by connecting -R ¹ and -R ² 5
or 6-membered nitrogen-containing heterocycle, the total number of carbon atoms of -R ¹ and -R ² is 18 or less), methyl group, ethyl group, phenyl group, -O-R ³ group, -
S-R ³ group (-R ³ represents a methyl group, ethyl group, ethoxy group, or phenyl group)] and the like. Among the above-mentioned reactive groups, a monofluorotriazinyl group is particularly preferred. Taking this case as an example, the structure of the reactive disperse dye will be explained below. Examples include dyes that can be used. General formula [] Carbocyclic monoazo and disazo dyes, heterocyclic monoazo and disazo dyes represented by; [Formula [], Q is the same as defined in the previous []. -X- represents an -NH- group, an -O- group or an -S- group. -A is a phenyl group; fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, trifluoromethyl group, methoxy group, ethoxy group, phenylazo group, cyano group, nitro group, methylsulfonyl group,
Ethylsulfonyl group, allylsulfonyl group, lower alkoxycarbonyl group, lower alkoxyethoxycarbonyl group, allyloxyethylcarbonyl group, mono-lower alkylaminocarbonyl group, di-lower alkylaminocarbonyl group, diallylaminocarbonyl group, monoallylaminocarbonyl group,
Phenyl group substituted with dimethylaminosulfonyl group, diethylaminosulfonyl group, monomethylaminosulfonyl group, monoethylaminosulfonyl group, acetyl group, phenyl group, etc.; imidazolyl group; dicyanoimidazolyl group; pyridyl group; chlorine atom, bromine atom, nitro group, methyl group, methylsulfonyl group, pyridyl group substituted with cyano group; thiazolyl group; methyl group, chlorine atom, bromine atom, nitro group, lower alkoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, Thiazolyl group substituted with fluoromethyl group, methylsulfonyl group, etc.; thiadiazolyl group; alkylthio group, arylthio group,
1,3,4-thiadiazolyl group substituted with alkenylthio group, aralkylthio group, bromine atom, chlorine atom, trifluoromethyl group, alkylsulfonyl group, etc.; alkylthio group, arylthio group,
1,2,4-thiadiazolyl group substituted with alkenylthio group, aralkylthio group, alkoxycarbonyl group, etc.; thienyl group; cyano group, chlorine atom, bromine atom, acetyl group, formyl group, nitro group, alkoxycarbonyl group, sulfomethyl group,
Thienyl group substituted with arylazo group, etc.; benzisothiazolyl group; benzoizothiazolyl group substituted with nitro group, bromine atom, chlorine atom, acetyl group, alkoxycarbonyl group, sulfomethyl group, etc.; pyridinoisothiazo Lyle group; Pyridinoisothiazolyl group substituted with a cyano group, methyl group, nitro group, etc.; Thienoisothiazolyl group; Thienoisothiazolyl group substituted with a nitro group, bromine atom, chlorine atom, etc.; Thienothiazolyl group ; Thienothiazolyl group substituted with nitro group, bromine atom, chlorine atom, etc.; benzothiazolyl group; methyl group, chlorine atom, bromine atom, nitro group, lower alkoxycarbonyl group, thiocyano group, trifluoromethyl group, methylsulfonyl group, etc. Represents a substituted benzothiazolyl group. -R ⁴ is a hydrogen atom, methyl group, methoxy group, chlorine atom, acetylamino group, chloroacetylamino group, benzoylamino group, methylsulfonylamino group, chloropropionylamino group, ethoxycarbonylamino group, ethylaminocarbonylamino group Represents a group, etc. −R ⁵ is a hydrogen atom, a methoxy group, an ethoxy group,
Represents a chlorine atom. -R ⁶ is a C ₁ to C ₈ linear or branched alkyl group; a C ₁ to _{C 8} linear or branched alkoxyethyl group; a phenoxyethyl group; a benzyloxyethyl group; an allyloxyethyl group ； _C1 ～ _C8
linear or branched hydroxyalkyl group;
Cyano lower alkyl groups such as cyanomethyl group and cyanoethyl group; optionally substituted acyloxy lower alkyl groups such as acetyloxyethyl group, chloroacetyloxyethyl group, chloropropionyloxyethyl group, benzoyloxyethyl group;
Methoxycarbonyloxyethyl group; alkoxycarbonyloxy lower alkyl group such as methoxyethoxycarbonyloxyethyl group; carbamoyl lower alkyl group such as carbamoylmethyl group, carbamoylethyl group; methoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxyethoxycarbonylmethyl group , optionally substituted alkoxycarbonyl lower alkyl groups such as benzyloxycarbonylmethyl group; optionally substituted aralkyl groups such as benzyl group, phenethyl group, chlorobenzyl group; allyloxycarbonylethyl group, allyloxycarbonylmethyl group Allyloxycarbonyl lower alkyl groups such as tetrahydrofurfuryl groups; succinimide lower alkyl groups such as succinimideethyl groups; phthalimide lower alkyl groups such as phthalimidoethyl groups; cyanoethoxyethyl groups, cyanomethoxyethyl groups, etc. cyanoalkoxy lower alkyl group; halogen lower alkyl group such as chloroethyl group; phenyl group,
Represents an aryl group such as a chlorophenyl group or a methylphenyl group. −R ⁷ is a −CH ₂ −CH ₂ − group,

【formula】 base or

[Formula] represents a group. ] General formula [ ] Carbocyclic monoazo and disazo dyes, heterocyclic monoazo and disazo dyes represented by; [formula []], Q is the same as defined in the above formula [], -
X- and -A are the same as defined in the formula [] above. -R ⁸ is the same as the definition of -R ⁵ in the above formula [], and -R ⁹ and -R ¹⁰ are the same as the definition of -R ⁶ in the above formula []. ] General formula [ ] Disazo dye represented by: [Formula [], where K is

【formula】

【formula】

【formula】

【formula】 or

【formula】 represents,

[Formula] is a phenyl group, a lower alkyl group, a lower alkoxy group, a phenoxy group, a nitro group, a cyano group, a halogen atom, a trifluoromethyl group, a carbamoyl group which may be substituted with an acetylamino group or a lower alkyl group, a lower Sulfamoyl group optionally substituted with alkyl group, carbamoyl group optionally substituted with acetylamino group or lower alkyl group, sulfamoyl group optionally substituted with lower alkyl group, lower alkylcarbonyl group or lower alkylsulfonyl group represents a phenyl group which may be substituted with a group,

[Formula] represents a naphthylene group or a phenylene group optionally substituted with a lower alkyl group, a lower alkoxy group, a halogen atom or an acetylamino group,

[Formula] represents a lower alkyl group, a lower alkoxy group, an acetylamino group, or a phenylene group optionally substituted with a halogen atom,

[Formula] represents a phenyl group optionally substituted with a halogen atom, a sulfamoyl group or a lower alkylsulfamoyl group,

[Formula] represents a phenyl group optionally substituted with a halogen atom, a lower alkyl group, or a lower alkoxy group, and -Y ¹ is substituted with a halogen atom, a trifluoromethyl group, a lower alkyl group, or a lower alkoxy group. phenyl group or ^-Y2 represents an allyl group, benzyl group or alkyl group which may be substituted with a hydroxyl group, cyano group or lower alkoxy group, ^-Y3 may be substituted with a lower alkoxy group It represents an alkyl group, an allyl group or an aralkyl group, -V represents a cyano group or a _-CONH2 group, and -X- and -Q are the same as defined in the above formula []. ] General formula [ ] Pyridone dye represented by: [wherein -T is a hydrogen atom, a lower alkyl group,
Represents a nitro group or a halogen atom, -Y ⁴
represents a substituted or unsubstituted alkyl group or aralkyl group, -A ¹ - is a -CH ₂ - group, -C ₂ H ₄
- group, -OC ₂ H ₄ - group,

[Formula] represents a -SO ₂ NHC ₂ H ₄ - group or -SO ₂ C ₂ H ₄ - group, n represents 0 or 1, -X- and -Q are as defined in the above [] formula. It's the same. ] General formula [ ] Anthraquinone dye represented by: [Formula [], -R ¹¹ represents an amino group or a hydroxyl group, -R ¹² and -R ¹³ represent a hydrogen atom, an amino group, a hydroxyl group, a nitro group, a chlorine atom or a bromine atom ^-R14 is a hydrogen atom, a chlorine atom, a bromine atom, a cyano group, or -R14
SO ₂ R ¹⁵ (-R ¹⁵ represents a methyl group, ethyl group or phenyl group). -E- represents a linking group of -O- or -S-. One of −X ₁ and −X ² represents a hydrogen atom, and the other represents a hydrogen atom.

[Formula] (-X- and -Q are the same as the definitions of the above formula [], -
^R16 represents a hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, chlorine atom, or bromine atom)
represents. k is 0 or 1. However, when -X ² is a hydrogen atom, k is 0. ] General formula [ ] Quinophthalone dye represented by: [Formula [], -X- and -Q- are the same as defined in the above formula []. -X ³ represents a hydrogen atom, a chlorine atom or a bromine atom, and j represents an integer of 0 or 1. ] General formula [ ] Perinone dye represented by: [Formula [], -X- and -Q are the above formula []
^-X4 represents a hydrogen atom, a chlorine atom, a bromine atom, a _C1 - _C4 alkoxy group or a phenoxy group. ] General formula [ ] Phthalocyanine dye represented by: [Formula [], -X- and -Q are the above formula []
is the same as the definition, [Pc] represents a copper phthalocyanine residue or a nickel phthalocyanine residue, -R ¹⁷ , -R ¹⁸ and -R ¹⁹ are a hydrogen atom, a substituted or unsubstituted alkyl group, a cyclohexyl group,
represents an allyl group or a substituted or unsubstituted aryl group, -W- represents an alkylene group or an arylene group, n ¹ represents a number from 0 to 2, m represents a number from 1 to 4, l represents 0 -Z represents a metal atom or an alkylammonium salt. ] General formula [ ] A benzothiazole monoazo dye represented by [In the formula, M represents hydrogen or a halogen atom, L represents a halogen atom, R ²⁰ and R ²¹
represents an ethylene group or a propylene group, and R ²²
represents an alkyl group which may be substituted with a lower alkoxy group or a lower alkoxyalkoxy group. On the other hand, examples of disperse dyes for polyester include commonly known monoazo dyes, and those having the structure shown below are particularly preferred. The proportion of the disperse dye for polyester used is usually 0.1 to 1 times, preferably 0.3 to 0.7 times the weight of the reactive disperse dye. Examples of disperse dyes for polyester include dyes represented by the following general formulas (1) to (5). General formula (1) [In the formula, -R ²³ represents a lower alkyl group. General formula (2) [During the ceremony,

[Formula] represents a phenyl group optionally substituted with a nitro group, a halogen atom, a lower alkoxy group, a lower alkoxycarbonyl group or a phenoxyethyloxycarbonyl group,
R ²⁴ represents a hydrogen atom, a lower alkyl group, a lower alkoxyalkyl group or a lower alkoxycarbonylethyl group. ] General formula (3) [In the formula, -R ²⁵ and -R ²⁶ are lower alkyl groups,
Represents a lower alkoxyalkyl group or phenoxyethyl group. ] General formula (4) [During the ceremony,

[Formula] represents a phenyl group which may be substituted with a halogen atom cyano group, nitro group, lower alkyl group, lower alkoxy group, or lower alkoxyalkyl group, and -R ²⁷ represents a lower alkyl group or a lower alkoxyalkyl group. represent ] General formula (5) [In the formula, D ¹ is

[Formula] group (-R ²⁷ is the same as the above definition),

[Formula] Group (where -R ³¹ represents a hydrogen atom or a methyl group) or

[Preparation of pad bath]

(Mixture of about 1:1 para: meta) 10.8 parts of navy blue reactive disperse dye represented by the above structural formula [A] and the above structural formula [] ~
The following disperse dye composition (pulverized with a sand grinder at room temperature) was prepared using a mixed dye consisting of 0.45 parts, 1.7 parts, and 2.1 parts of yellow, red, and blue polyester disperse dyes shown in []. was prepared and then used to prepare a pad bath having the following composition. Disperse dye composition Dye component 15 parts Polyoxyethylene type nonionic surfactant 4 parts Lignosulfonate 3 parts Ethylene glycol 5 parts Water 73 parts Pad bath composition Disperse dye composition 10 parts CH ₃ O (-CH ₂ CH ₂ O ) ₇ -H 8 parts Sodium benzoate 5 parts Urea 1 part Penetrant [Dia Server PN-SR ^* ] 0.1 part Migration inhibitor [Dia Server MG
-N ^* ] 0.1 part water 75.8 parts *All are product names of Mitsubishi Chemical Industries, Ltd. [Dyeing test] Using the above pad bath, a blended fabric of polyethylene terephthalate and cotton at a mixing ratio of 65:35 was prepared as shown below. When a dyeing test was carried out by continuous processing using the processing steps and processing conditions shown, a good dyed product with a high dyeing rate and uniformly dyed in navy blue throughout was obtained.

[Table] ↓
Washing process 40℃×10 minutes

Claims (1)

[Claims] 1. In a method for continuously dyeing cellulose and polyester mixed fibers using a mixed dye of a reactive disperse dye and a polyester disperse dye, the dyed object is subjected to a pad bath containing the mixed dye, a nonionic surfactant, and a reaction catalyst. After padding treatment using
Contact treatment with an alkaline bath with a pH of 8 or higher, and further
After steam treatment at a temperature of 130℃, this
A continuous dyeing method for mixed fibers characterized by washing treatment in an alkaline aqueous solution with a concentration of 0.005% by weight or more at a temperature of 100°C.