JP4062371B2 - Exhaust dyeing method using cationic aqueous pigment dispersion composition - Google Patents

Description

【００４５】
得られたシルケット加工布青色染色物は、染料だけを使用して得られた染色物に比し、より鮮明で耐光性も向上していた。
【００４６】
（参考例４）
参考例１のC.I.Pigment Green 7 に代えて C.I.Pigment Red 146 を用いてカチオン性水性顔料分散組成物を調製し、実施例３と同様にして本参考例の染料を調製した。
【００４７】
この染浴を用い、実施例３と同様の操作により、分解酵素処理したテンセル（レーヨン）を染色した。その結果、ムラのない青赤色染色物が得られた。また、染色設備の汚れも認められなかった。
【００４８】
（比較例）
アニオン性アクリル系分散剤で分散したC.I.Pigment Blue 15、C.I.Pigment Green 7、C.I.Pigment Red 146、C.I.Pigment white 6 のアニオン性水性顔料分散組成物を用いて染浴を調製し、この染浴を用いて公知の吸尽染色法で染色を行い比較例の染色物を得た。各比較例の染色物と実施例２〜４及び参考例２〜４の染色物とを比較し、その結果を表２に示した。いずれの場合も本発明のカチオン性水性顔料分散組成物を用いて染色したものの方が、比較例の染浴を用いて染色したものより優れていた。
【００４９】
【表２】

【００５０】
本発明のカチオン性水性顔料分散組成物を用いた場合の染色と、従来の吸尽法による染色との差異を明らかにするための比較を表３に示した。
【００５１】
【表３】

【００５２】
【発明の効果】
本発明のカチオン性水性顔料分散組成物を繊維材料の染色に用いた場合、被染物が未縫製であると既縫製であるとに関わりなく均一な染色を行うことができる。また、従来の染色に際して行われる吸尽染色に於いて必要であったカチオン化のための工程が不要となり、少ない工程で染色を行うことができる。また、カチオン化のための設備が不要となり、染色を行う際に必要となる設備の低減を図ることができる。更に、染色設備の汚染が殆どなく、洗浄などの工程を短縮することができる。そして、染色廃液に着色はなく、無色透明であり、排水着色の問題はない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to dyeing of a fiber material with a pigment, and more specifically, the dyeing material can be uniformly dyed at a desired dyeing concentration regardless of whether it is already sewn or not sewn, and does not contaminate the dyeing apparatus. In addition, the present invention relates to a pigment dispersion composition having no coloring of the dyeing waste liquid, a dye bath using the same, and a method for dyeing a fiber material using the dye bath.
[0002]
[Prior art]
The dyeing of the fiber material with a pigment is useful because the pigment has excellent fastness to sunlight and dry cleaning. However, since the pigment itself is poor in dyeability, it is necessary to bind to the fiber by using an appropriate binder. As the method, a printing method, a padding dyeing method and the like are known. Further, Japanese Patent Application Laid-Open Nos. Hei 2-221470 and Hei 6-136672 have proposed methods in which a fiber material is pretreated with a cationic auxiliary agent and then dyed by an exhaust method.
[0003]
However, printing and padding dyeing have a drawback that they cannot be applied to already-sewn clothing. In addition, the method of pretreating the fiber material with a cationic auxiliary agent makes it difficult to equalize the degree of cationization of the fiber material, which causes uneven dyeing or staining equipment staining, or coloring waste liquid is colored. Has drawbacks. Furthermore, it is not only necessary to separately provide a preliminary process for cationization of the fiber material, but also has the complication that cationization treatment, exhaust dyeing and binder treatment must be performed in separate facilities. .
[0004]
[Problems to be solved by the invention]
The present invention solves the above-mentioned disadvantages in conventional dyeing methods such as textile printing, padding dyeing, exhaust dyeing after pretreatment with a cationic auxiliary agent. A pigment dispersion composition that can perform uniform dyeing irrespective of sewing, does not require a cationization process and equipment, is free from staining of the dyeing equipment, and does not color the dyeing waste liquid, and uses this A dye bath and a method for dyeing a fiber material using the dye bath are provided.
[0005]
As a result of intensive studies to solve the above-mentioned problems, the present invention directly immerses a fiber material by using a dye bath containing a cationic aqueous pigment dispersion composition containing a cationic polymer as a pigment dispersant. It has been found that the above-mentioned purpose can be achieved simply by doing.
[0006]
That is, a cationic aqueous pigment dispersion composition containing the cationic polymer of the present invention as a pigment dispersant is optionally mixed and diluted with water so as to obtain a desired dyeing concentration, or a dye bath is prepared if necessary. Prepare a dyeing bath to which a cationic polymer and / or a cationic compound is added, immerse the fiber material in this, remove the dyeing solution after the dyeing is completed, wash in the same apparatus without removing the fiber material, It has been found that the fiber material can be uniformly dyed at a desired dyeing density regardless of whether it is already sewn or not sewn by performing a binder treatment when necessary. That is, when a dye bath containing the dispersion composition of the present invention is used, dyeing can be performed without cationization with a cationizing agent in the process, as in cationization by a conventional method. Moreover, there is no contamination of the dyeing apparatus and coloring of the dyeing waste liquid.
[0007]
In addition, if the pigment dispersion composition of the present invention is used, all the dyeing steps can be performed with one dyeing device as described above. However, in consideration of workability and the like, different devices may be used for each step. No problem.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The cationic aqueous pigment dispersion composition according to the present invention is applicable to dyeing of all natural fibers and synthetic fibers, such as cotton, wool, silk, polyester, polyamide, polypropylene, polyacryl, rayon, polynosic rayon, tencel. It can also be applied to those in which various fibers are blended or woven. Further, the dyeing method of the present invention can be applied to dyeing various fiber materials in addition to woven fabrics, knitted fabrics, and knitwear. Although the object of dyeing of the pigment dispersion composition of the present invention is not particularly limited, it can be suitably used for dyeing clothes that have already been sewn with cotton and blended jeans or casual wear products.
[0009]
The cationic aqueous pigment dispersion composition of the present invention is prepared by mixing a pigment and a cationic aqueous polymer in an aqueous system, and then known pigment dispersing machines such as a high-pressure homogenizer, a bead mill type dispersing machine, an attritor, a ball mill, and a high-speed stirring dispersing machine For example, it is prepared by a dispersion treatment. The ratio of the pigment to the cationic polymer is preferably 100: 5 to 100: 300, although it varies depending on the properties of the two used.
[0010]
Examples of the pigment contained in the cationic aqueous pigment dispersion composition include known organic pigments, inorganic pigments, fluorescent whitening pigments, and fluorescent pigments. Examples of organic pigments include azo pigments, dyed lake pigments, phthalocyanine pigments, condensed polycyclic pigments (such as anthraquinone pigments), quinacridone pigments, dioxazine pigments, perinone pigments, diketopyrrolopyrrole pigments and isoindolinone pigments. Examples of inorganic pigments include petals, titanium oxide, yellow iron oxide, carbon black, and precipitated barium.
[0011]
Examples of the fluorescent whitening pigment include diphenylethylene derivatives, and examples of the fluorescent pigment include a benzoguanamine formaldehyde resin containing a basic dye, an oily dye, and an organic pigment.
[0012]
As the cationic polymer used for the preparation of the cationic aqueous pigment dispersion composition, a known polymer or prepolymer containing a tertiary amino group or a quaternary ammonium group in the molecule or both may be used. it can.
[0013]
This cationic polymer may be used for the preparation of a cationic aqueous pigment dispersion composition as described above, or may be used to separately add this dispersion composition to a diluted dye bath. . Moreover, the cationic polymer used for the cationic aqueous pigment dispersion composition and the cationic polymer added to the dyeing bath separately may be the same or different from each other.
[0014]
Furthermore, in the present invention, a cationic compound may be added to the dye bath. The cationic compound added to the dyebath may be one generally used as a cationizing agent.
[0015]
Examples of the tertiary amino group-containing polymer used as the cationic polymer include the following. (A) a polymer of alkylaminoalkyl (meth) acrylamide, for example, a polymer such as dimethyl or diethylaminoethyl (meth) acrylamide, dimethyl or diethylaminopropyl (meth) acrylamide, (b) dialkylaminoalkyl (meth) acrylate Polymers such as dimethyl or diethylaminoethyl (meth) acrylate, polymers such as dimethyl or diethylaminopropyl (meth) acrylate, (c) acrylamide / styrene copolymer, (d) tertiary amino group-containing urethane heavy polymer Such as coalescence.
[0016]
Examples of the quaternary ammonium group-containing polymer used as the cationic polymer include the following. That is, (a) a polymer of (meth) acryloyloxyalkyltrialkylammonium salt, for example, 2- (meth) acryloyloxyethyltrimethylammonium chloride, 3- (meth) acryloyloxy-2-hydroxypropyltrimethylammonium chloride (B) (meth) acrylamidoalkyltrialkylammonium salt polymers such as (3- (meth) acrylamidopropyltrimethylammonium chloride, 3- (meth) acryloylamino-2-hydroxypropyltrimethylammonium chloride, etc. A polymer of (c) 2- (meth) acryloyloxyalkylbenzylammonium salt, such as 2- (meth) acryloyloxyethylbenzylammonium chloride, 2- (meth) a Polymer of leuroyloxyethyldimethylbenzylammonium chloride, former two monomers and copolymers such as acrylamide, dimethylaminoethyl acrylate, (d) acrylamidopropyldimethylbenzyl chloride, N, N-dimethylacrylamide and N-methyl A copolymer of -N-benzylallylamine salt and N-methyl-N-hydroxyethylaminopropylacrylamide, etc. (e) other, for example, dimethyl or diethyldiallylammonium chloride, β-vinyloxyethyltrialkylammonium salt, vinyl Polymers such as benzylammonium salts.
[0017]
Examples of the cationic compound include (f) a quaternary ammonium group-containing compound such as hexamethylene-bis (3-chloro-2-hydroxypropyl-dimethylammonium chloride), trimethylene-bis (3-chloro-2-hydroxypropyl-). Dimethylammonium chloride), hexamethylene-bis (2,3-epoxypropyl-dimethylammonium chloride), trimethylene-bis (2,3-epoxypropyl-dimethylammonium chloride), 3-chloro-2-hydroxypropyl-trimethylammonium chloride A cationizing agent such as 2,3-epoxypropyl-trimethylammonium chloride can be used.
[0018]
Of the above-mentioned cationic polymers, polydialkylamino (meth) acrylate, polydimethyldiallylammonium chloride, and tertiary amino group-containing urethane polymers are more preferable for the preparation of the cationic aqueous pigment dispersion composition.
[0019]
In the present invention, (c) (d) (e) (f) exemplified above are more preferable as the cationic polymer and the cationic compound which are separately added to the dyeing bath of the cationic aqueous pigment dispersion composition. It is a compound of this.
[0020]
In the dyeing method of the present invention, as proposed by the inventor in Japanese Patent Laid-Open No. 5-331780, an anionic activator may be added to these cationic polymers to form a poly salt. In that case, the anionic activator is preferably used in an amount corresponding to 5 to 70 mol% of the cationic monomer constituting the cationic polymer. In this case, the anionic activator used in combination is alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, naphthalene sulfonate formalin condensate, alkyl naphthalene sulfonate formalin Condensates, aromatic sulphonic acid formalin condensates, lignin sulfonates, etc. Among these, a formalin condensate of aromatic sulfonic acid and naphthalene sulfonic acid is preferable.
[0021]
The fiber material wet-treated by a known method is dipped and dyed in a dye bath to which a cationic aqueous pigment dispersion composition, water, and a cationic polymer, a cationic compound, etc. are added if necessary.
[0022]
The dyeing bath is further added with water, a cationic aqueous pigment dispersion composition and, if necessary, a cationic polymer, a cationic compound, etc. so that the bath ratio is 1:10 to 1:50 (preferably 1:20). Prepared.
[0023]
What is necessary is just to select suitably the addition rate of the cationic aqueous pigment dispersion composition with respect to a fiber according to the dyeing density desired. The cationic aqueous polymer and / or cationic compound to be further added to the dyeing bath as required is 1 to 100% by weight, preferably 1 to 20% by weight, based on the cationic aqueous pigment dispersion composition.
[0024]
Dyeing is performed by immersing the wet, dehydrated and washed fiber material in the dye bath. Although the dyeing conditions are not particularly limited, it is preferable to hold at 35 to 70 ° C. for 10 to 30 minutes.
[0025]
After dyeing is completed, the dyeing solution is removed, washed with water and dehydrated to obtain a dyed product having a uniform color tone and density as expected.
[0026]
In dyeing using the pigment dispersion composition of the present invention, a dye, an acid dye, or a reactive dye can be added directly to the dye bath, and dyeing with the dye can be performed simultaneously with dyeing with the pigment. In this case, the fiber material may be treated in the same manner as described above, but it is preferable to use a known leveling agent and inorganic salt such as bow glass.
[0027]
In dyeing using the pigment dispersion composition of the present invention, it is preferable to perform a binder treatment in order to obtain a preferable dyeing strength. For this binder treatment, a known binder such as polyurethane, polyester, polyacrylic ester or the like is used.
[0028]
In the binder treatment, a binder ratio of 0.5 to 30% by weight (preferably 1 to 10% by weight) is added to the fiber material, and the bath ratio is 1: 5 to 1:50 (preferably 1:20 to 1). : 30) is used. After dyeing, the washed and dehydrated fiber material is dried at 180 ° C. for 5 to 30 minutes and cured.
[0029]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples.
[0030]
The aforementioned cationic polymers and anionic activators are commercially available for various industries, and can be used for the preparation of a cationic aqueous pigment dispersion composition in the method of the present invention. Can be used as an additive to be added to the dye bath in the present invention.
[0031]
(Example 1) (Preparation of cationic aqueous pigment dispersion composition (1))
Polyurethane-based cationic prepolymer (commercially available product: BYK, Disperbyk-182 or Disperbyk-185) 22 parts (parts by weight, the same applies hereinafter), water 40 parts, preservative 0.4 parts, antifoaming agent 0.2 parts , And 30 parts of CIPigment Blue 15 were stirred and dispersed for 60 minutes with a pre-disperser equipped with a stirrer, and the pre-dispersed slurry was transferred into a sand mill using 1 m / m glass beads, and dispersed at 1000 rpm for 60 minutes. Water was added so that the total amount was 200 parts, and a cationic aqueous pigment dispersion composition of CIPigment Blue 15 was obtained.
[0032]
( Reference Example 1 ) (Preparation of a cationic aqueous pigment dispersion composition (2))
104 parts of polydimethyldiallylammonium chloride (commercially available product: Merck 100, Merquat 100) and 820 parts of water are sufficiently mixed, and a solution obtained by dissolving 16 parts of sodium alkylbenzenesulfonate in 36 parts of water is added to the mixture. To mix. Next, 200 parts of CIPigment Green 7 was added and predispersed for 60 minutes, transferred to a sand mill charged with 1 m / m glass beads, dispersed at 1000 rpm for 60 minutes, and further diluted with 200 parts of water to 1370 parts. A cationic aqueous pigment dispersion composition of CIPigment Green 7 was obtained.
[0033]
( Example 2 )
Using the CIPigment Blue 15 cationic aqueous pigment dispersion composition prepared in Example 1, a dyeing bath was prepared by adding 1% by weight of the cationic aqueous pigment dispersion composition to the fiber at a bath ratio of 1:20. The dye bath of the example was obtained.
[0034]
Using this dye bath, dyeing in the following steps was performed. First, the cotton cotton thus sewed was wet-treated for 10 minutes at a bath ratio of 1:20 with hot water at 50 ° C. in a washer dyeing machine, and then spin-dehydrated. In the same dyeing machine, the dyeing bath of this example was added at 40 ° C., the temperature was raised to 60 ° C. over 10 minutes, and dyeing was performed at the same temperature for 20 minutes. After draining the dyeing liquor, washing with water using the same dyeing machine, dehydrating, adding water so that the bath ratio becomes 1:20, adding 3% by weight of acrylic binder to the cotton jeans, and treating the binder at 40 ° C. For 5 minutes. This was dehydrated and tumbler dried at 100 to 110 ° C. to obtain a thick and uniformly dyed cotton jeans. Blue cotton jeans were obtained by subjecting the dyed cotton jeans to known biotreatment and softening treatment (stone washing, etc.). Further, the washer dyeing machine after the dyeing process was not contaminated with blue, and the dyeing waste liquid was colorless and transparent.
[0035]
( Example 3 )
In Example 2 , after adding the CIPigment Blue 15 cationic aqueous pigment dispersion composition, as a cationic polymer, 1 weight of 2- (meth) acryloyloxyethyldimethylbenzylammonium chloride polymer was added to cotton jeans. % To obtain a dye bath of this example.
[0036]
Using this dyebath, cotton jeans were dyed in the same manner as in Example 2. As a result, dark blue cotton jeans were obtained. Also in this case, there was no contamination of the washer dyeing machine, and the dyeing waste liquid was colorless and transparent.
[0037]
( Example 4 )
Instead of CIPigment Blue 15 in Example 1, CIPigment white 6 (titanium oxide) was used to obtain a cationic pigment dispersion composition of this example , and this was used in the same manner as in Example 3. A dye bath of this example was obtained.
[0038]
Using this dyebath, the stitched polynosic rayon and polyester casual pants were dyed by the same operation as in Example 3 . As a result, the uniformly dyed casual pants showed an excellent effect in preventing see-through. Also in this case, there was no contamination of the dyeing machine, and the dyeing waste liquid was colorless and transparent.
[0039]
( Reference Example 2 )
A dye bath was prepared in the same manner as in Example 2 using the cationic aqueous pigment dispersion composition of CIPigment Green 7 prepared in Reference Example 1 .
[0040]
Using this dyebath, the cotton knitwear sewn was dyed by the same operation as in Example 2 . As a result, cotton knitwear dyed uniformly and green was obtained. Also in this case, there was no contamination of the dyeing machine, and the dyeing waste liquid was colorless and transparent.
[0041]
( Reference Example 3 )
After adding the CIPigment Green 7 cationic aqueous pigment dispersion composition in Reference Example 2 , a copolymer of acrylamidopropyldimethylbenzyl chloride and N, N-dimethylamide as a cationic polymer was added to the cotton knitwear. The dyeing bath of this reference example was prepared by adding 1% by weight.
[0042]
Using this dyebath, the cotton knitwear sewn was dyed by the same operation as in Example 2 . As a result, dark green cotton clothing was obtained. Also in this case, there was no contamination of the dyeing machine, and the dyeing waste liquid was colorless and transparent.
[0043]
( Example 5 ) (Co-dying with direct dye)
Using the CIPigment Blue 15 cationic aqueous pigment dispersion composition of Example 1 and the direct dye Kayaru Supra Blue 4BL Conc (manufactured by Nippon Kayaku Co., Ltd.), the dye bath of this example shown in Table 1 was prepared. Prepared. Using this dyebath, cotton-knitted mercerized fabric was dyed under the conditions shown in Table 1 and treated with a binder.
[0044]
[Table 1]

[0045]
The obtained mercerized cloth blue dyeing was clearer and light-resistant than the dyeing obtained using only the dye.
[0046]
( Reference Example 4 )
A cationic aqueous pigment dispersion composition was prepared using CIPigment Red 146 instead of CIPigment Green 7 of Reference Example 1 , and a dye of this Reference Example was prepared in the same manner as Example 3 .
[0047]
Using this dye bath, Tencel (rayon) treated with a degrading enzyme was dyed by the same operation as in Example 3 . As a result, a bluish red dyeing product having no unevenness was obtained. Also, no stain on the dyeing equipment was observed.
[0048]
(Comparative example)
A dye bath is prepared using an anionic aqueous pigment dispersion composition of CIPigment Blue 15, CIPigment Green 7, CIPigment Red 146, and CIPigment white 6 dispersed with an anionic acrylic dispersant. Dyeing was performed by the exhaust dyeing method to obtain a dyed product of a comparative example. The dyeings of each comparative example were compared with the dyeings of Examples 2 to 4 and Reference Examples 2 to 4, and the results are shown in Table 2. In any case, the dyed using the cationic aqueous pigment dispersion composition of the present invention was superior to the dyed using the dye bath of the comparative example.
[0049]
[Table 2]

[0050]
Table 3 shows a comparison for clarifying the difference between the dyeing using the cationic aqueous pigment dispersion composition of the present invention and the dyeing by the conventional exhaust method.
[0051]
[Table 3]

[0052]
【The invention's effect】
When the cationic aqueous pigment dispersion composition of the present invention is used for dyeing fiber materials, uniform dyeing can be performed regardless of whether the article to be dyed is unsewed or already sewn. Further, the step for cationization which is necessary in the exhaust dyeing performed in the conventional dyeing is not necessary, and the dyeing can be performed with few steps. Moreover, the equipment for cationization becomes unnecessary and the equipment required when dyeing can be reduced. Furthermore, there is almost no contamination of the dyeing equipment, and the steps such as washing can be shortened. The dyeing waste liquid is not colored and is colorless and transparent, and there is no problem of drainage coloring.

Claims (6)

An exhaust dyeing method characterized by immersing unsewed or already sewn fiber material in a dye bath containing a cationic polymer comprising a tertiary amino group-containing urethane polymer as a pigment dispersant.   The dye bath contains the cationic polymer as a poly salt to which 5 to 70 mol% of an anionic active agent of the cationic monomer constituting the cationic polymer is added. The exhaust dyeing method according to claim 1.   The exhaust dyeing method according to claim 1 or 2, wherein a cationic polymer and / or a cationic compound is added to the dye bath separately from the cationic polymer.   The exhaust dyeing method according to any one of claims 1 to 3, wherein the dye bath further contains a direct dye.   The exhaust dyeing method according to any one of claims 1 to 3, wherein the dye bath further contains an acid dye.   The exhaust dyeing method according to any one of claims 1 to 3, wherein the dye bath further contains a reactive dye.