JP2005154907A - Color deepening agent for cellulosic fiber, color deepening method using the same, and dyed cellulosic fiber treated thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a dyed product having deepened color while keeping water absorption by the color deepening treatment of a dyed cellulosic fiber. <P>SOLUTION: A color deepening agent contains fine silica particles treated with a silane coupling agent having amino group under acidic condition and a polyether-modified polysiloxane. The dyed product having deepened color while keeping water absorption is produced by treating a dyed cellulosic fiber with the color deepening agent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a deep coloring agent for dyed and processed cellulosic fibers, a deep coloration method using the same, and a processed cellulosic fiber dyed product processed thereby. More specifically, it is a deep colorant containing silica fine particles treated with an amino group-containing silane coupling agent under acidic conditions and a polyether-modified polysiloxane, and is excellent in dye fixing properties of dyed cellulose fibers. , A deep coloring agent for cellulosic fibers, which improves the deepness of dyeing, has excellent water absorption, and has excellent resistance to repeated washing and fastness to washing, deep coloration method using the same, and treatment using the same It relates to a processed cellulosic fiber dyed product.

  A deepening method for dyed fibers has been proposed more than 20 years ago, and various deepening agents and deepening methods have been proposed up to the present, and some techniques have already been put into practical use. The deep color technology gives fine unevenness to the dyed fiber surface and improves the color depth by light reflection, refraction, etc. As the unevenness imparting agent, silica fine particles, urethane resin emulsion, acrylic A resin emulsion has been proposed.

  Silica fine particle color deepening agents are described in, for example, Patent Documents 1 to 5. As described in Patent Document 1, the silica fine particle color deepening agent is basically composed of an aqueous suspension containing silica fine particles. Patent Document 2 proposes a color deepening agent that is used by treating a silica fine particle aqueous solution with a silane coupling agent having an amino group and attaching it to a fiber, followed by further low-temperature plasma treatment. The agent is intended for use in polyester fibers, and when applied to cellulosic fibers, its water absorption is insufficient. In Patent Documents 3 and 4, a color deepening agent used for a polyester fiber previously treated with an epoxy compound, which is composed of silica fine particles treated with a silane coupling agent having an amino group, is proposed. However, when this deep colorant is applied to cellulosic fibers, water absorption cannot be expected. Patent Document 5 proposes a color deepening agent composed of silica fine particles and a polysiloxane compound. This color deepening agent is applied to polyester and wool, and emphasizes water absorption and dye fixing. There is no description about application to cellulosic fibers.

  Patent Document 6 proposes a resin emulsion as a color deepening agent that can be applied not only to polyester fibers but also to urethane fibers such as polyamide, acrylic, and rayon. These resin emulsions cannot be expected to have water absorption and dye fixing properties due to the resin structure, and generally have a problem in the stability of the treatment bath during the treatment with the deep colorant, and can be used for simple treatment methods such as an immersion treatment method. Application is difficult.

  As described above, the conventionally proposed deep colorants are mainly for polyester fibers, and many of them are imparted with water repellency when deep color treatment is performed. Recently, there is a proposal that it can be used for wool, but there is no proposal for cellulosic fibers. When a conventional deep color-imparting agent is diverted to cellulosic fibers, there is a problem that water absorption, which is a feature of cellulose fibers, is impaired, although there is a deep color effect.

Japanese Patent Laid-Open No. 56-112585 JP-A-2-259160 JP-A-3-269171 JP-A-4-214482 Japanese Patent Laid-Open No. 9-256280 Japanese Patent Laid-Open No. 9-3774

  An object of the present invention is to provide a cellulosic fiber excellent in dye fixation, deep color effect, water absorption, etc., and excellent in repeated washing resistance and stability of deep color treatment, etc. An object of the present invention is to provide a color deepening agent, a color deepening method using the same, and a cellulosic fiber dyed processed product treated therewith.

As a result of diligent research to solve the above-mentioned problems, the present inventors treated an aqueous silica fine particle solution with an amino group-containing silane coupling agent under acidic conditions, and then mixed a polyether-modified polysiloxane, thereby producing a dye. In order to complete the present invention, it has been found that a deep coloring agent for cellulosic fibers is obtained which is excellent in fixing property, deep color effect, water absorption, etc., and is excellent in repeated washing resistance and stability of deep color treatment. It came.
That is, the present invention relates to a color deepening agent for cellulosic fibers comprising silica fine particles treated with a silane coupling agent having an amino group under acidic conditions and polyether-modified polysiloxane.
Furthermore, the present invention relates to a deep coloration method characterized by treating a dyed and processed cellulosic fiber with the above-mentioned color deepening agent for cellulosic fibers.
Furthermore, the present invention relates to a dyed processed product treated with the above-mentioned deep coloring agent for cellulosic fibers.

  By processing the cellulosic fiber dyed with the deep color agent of the present invention, a cellulosic fiber dyed product excellent in dye fixing property, deep color property, water absorption, and fastness to washing is obtained. Can do. Formal wear of polyester fiber has already been processed deeply, and there is a high demand for high-grade products such as formal wear, but the deepening agent of the present invention makes it difficult to dye. The cellulosic fibers can be subjected to a deep color treatment while maintaining water absorption.

The deep colorant of the present invention contains silica fine particles treated with a silane coupling agent having an amino group under acidic conditions and a polyether-modified polysiloxane. Preferably, an aqueous solution of silica fine particles is added under acidic conditions. Then, it is obtained by treating with a silane coupling agent having an amino group and then mixing polyether-modified polysiloxane.
In the present invention, silica fine particles used for treatment with an amino group-containing silane coupling agent under acidic conditions usually have a particle size of 30 to 85 nm, and are already commercially available in the form of an aqueous solution. Things can be used.
As the silane coupling agent having an amino group, commercially available silane coupling agents such as aminopropyltriethoxysilane and N- (amino ether) -aminopropyltrimethoxysilane can be used.

  When the silane coupling agent having an amino group is treated under acidic conditions, the proportion of the silane coupling agent having an amino group to the silica fine particles is usually 5 to 20% by weight, and the silane coupling having an amino group. When the proportion of the agent used is less than this range, the fastness to washing of the resulting deep colorant is lowered, and when the proportion is greater than this range, the stability of the deep colorant is lowered.

  In treating silica fine particles with an amino group-containing silane coupling agent under acidic conditions, examples of the acidic substance used include inorganic acids and organic acids. Preferably, formic acid, acetic acid, glycolic acid, succinic acid, maleic acid are used. It is a monovalent or divalent organic acid such as an acid. Treatment pH should just be 6 or less, and especially the temporal stability of the deep color agent obtained as pH 3-5 improves. In the treatment under acidic conditions, the silica fine particle concentration in the aqueous silica fine particle solution is usually 5 to 20% by weight. When the concentration is lower than this range, the treatment time becomes longer, and when the concentration is higher than this range, the stability of the solution decreases. The mixing order of silica fine particles, acidic substances, and silica fine particle run coupling agents treated with silane coupling agents having amino groups under acidic conditions is not particularly limited, but silane coupling can be performed on aqueous silica fine particles under acidic conditions. It is preferable to add an aqueous solution of an agent or an alcohol solution. After mixing in this manner, the silica fine particles can be treated with a silane coupling agent having an amino group under acidic conditions, usually by standing at room temperature for several hours.

The polyether-modified polysiloxane used in the present invention is obtained by adding a silane group-containing polysiloxane with an allyl alcohol ethylene oxide, propylene oxide, or a polyether made of a random or block copolymer thereof. Those already commercially available can be used.
By mixing the polyether-modified polysiloxane having a hydrophilic property in this way, the water absorption of the resulting deep colorant is greatly improved and the repeated washing resistance is excellent. This is presumed that the combination with the silane coupling agent prevents a decrease in the water absorption effect.
The proportion of the polyether-modified polysiloxane used is usually 3 to 30% by weight, preferably 5 to 20% by weight, based on the silica fine particles.

The method of mixing the polyether-modified polysiloxane into the aqueous solution of silica fine particles treated with the amino group-containing silane coupling agent under acidic conditions is not particularly limited, but for more uniform dispersion, the polyether-modified polysiloxane is alcohol or the like. It is preferable to mix what was dissolved in.
The deep colorant of the present invention thus obtained can also be obtained from the market as DYMER 05 (manufactured by Inoue Chemical Co., Ltd.).

  Examples of the cellulosic fibers suitable for applying the color deepening agent of the present invention include cotton, cupra, rayon, polynosic, hemp, lyocell and the like alone or a mixed fiber thereof. Furthermore, these fibers and other fibers such as polyester fibers, acetate fibers, polyacrylonitrile fibers, wool fibers, silk fibers, polyamide fibers such as nylon, and the like can be mentioned.

  The dyeing method of the dyed cellulose fiber to which the deep colorant of the present invention is applied can be performed according to a known method such as a dyeing method using a reactive dye or a dyeing method using a direct dye. In the dyeing method using reactive dyes, after completion of the dyeing step, washing with water and hot water may be followed by washing in a soaping bath containing a commercially available soaping agent usually 0.1 to 5 g / L. In the dyeing method using a direct dye, washing with water may be performed after the dyeing process is completed. You may perform dye fixing process as needed.

  As a dyeing method using a reactive dye, for example, in the dyeing of cellulose fibers such as cotton, a reactive dye composition is added to the dye bath, and a known inorganic neutral salt such as anhydrous sodium sulfate, sodium chloride and an acid binder such as sodium carbonate are used. Dyeing can be carried out alone or in combination with sodium bicarbonate, caustic soda, sodium triphosphate and the like.

  As a dyeing method using a direct dye, for example, in the dyeing of cellulosic fibers such as cotton, a direct dye composition may be added to a dyeing bath, and dyeing may be performed using a known inorganic neutral salt such as anhydrous sodium sulfate, salt, etc. it can.

  As a color deepening method for treating the cellulosic fibers dyed in this way with the color deepening agent of the present invention, a color deepening agent is usually added to 100 parts by weight of the cellulosic fibers dyed and processed. What is necessary is just to process 5-20 weight part normally at 50-70 degreeC for 10 to 60 minutes normally.

  In particular, as a method for deeply coloring dyed cellulose fibers by the pad processing method, a water bath is usually added to 30 to 70 parts by weight of a deep colorant to prepare a pad bath with a total amount of about 1000 parts by weight, After padding the dyed fabric into this pad bath, the fabric is squeezed with a mangle at a squeezing rate of 80%. .

  The deep coloration method of the present invention can be carried out by a pad method or a dipping method, but a sufficiently stable treatment can be achieved even by a simpler dipping method. It is preferable to treat the amount so as to be 0.2 to 90 parts by weight, preferably 5 to 30 parts by weight with respect to 100 parts by weight.

  In the present invention, a dyed product excellent in deep coloration and water absorption can be obtained by treating the dyed and processed cellulose fiber with the deep colorant of the present invention. Also, the fixing effect is high. Furthermore, the obtained fiber has good light resistance, sweat light resistance, washing fastness and chlorine resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these. In the examples,% and parts are based on weight.

Preparation of test cloth A dyeing process was carried out by a publicly known method using 10% reactive dye (C, I Reactive Black 5) for cotton fibers to prepare a test cloth.

As a deep color treatment deepening agent by a pad treatment method, a commercially available DYMER 05 (manufactured by Inoue Chemical Industry Co., Ltd.) was used. This DYMER 05 was prepared by adding a methanol solution of formic acid and γ-aminopropyltriethoxysilane to a 20% aqueous solution of silica fine particles having a particle diameter of 40 to 50 nm and treating them under acidic conditions at pH 4 and The final composition was obtained by mixing siloxane with a silica fine particle 20% aqueous solution 41%, formic acid 1.9%, γ-aminopropyltriethoxysilane 0.6%, methanol 3.5%, polyether. Modified polysiloxane 1.5% and water 51.5%. Water was added to 50 parts of this DYMER 02 to make a total of 1000 parts of pad bath. After padding the test cloth in this pad bath, the pad was squeezed with a mangle at a drawing rate of 80%. The squeezed cloth was dried at 100 ° C. for 3 minutes and then subjected to dry heat treatment at 150 ° C. for 3 minutes to obtain a dyed processed product of the present invention.

Deepening treatment by dyeing treatment method 10 parts of a deepening agent (DYEMER 05) and 100 parts of a test cloth were treated at 60 ° C. for 30 minutes to obtain a dyed processed product of the present invention.

  Using the dyed processed products of the present invention obtained in Example 1 and Example 2, the following methods were used to obtain a color depth, water absorption, light fastness, sweat light fastness, wash fastness, chlorine fastness, nitrogen gas (NOx) A fastness test was performed. The results of Example 1 are shown in Table 1, and the results of Example 2 are shown in Table 2.

(A) Determination of deep coloration The deep coloration degree of the deep-colored cotton fibers was expressed in density using the QTOTAL value calculated based on the reflectance and the untreated cloth as 100%. The QTOTAL value is a surrogate value (integral value of K / S values) of the surface density considering visual characteristics.

(B) Determination of water absorption A water droplet (0.5 ml) was dropped on the test cloth, and the water absorption time of the water droplet was determined based on the following criteria.
○: Absorbed immediately. Δ: Not absorbed even for 1 to 60 seconds. ×: Does not absorb for more than 1 minute.

(C) Determination of light fastness Light resistance test (JIS L0842 carbon irradiation 20, 40 hours) Discoloration was determined by JIS blue scale.

(D) Determination of fastness to sweat light (alkali JIS 5-fold method) Light fastness test (JIS L0888, carbon irradiation for 10 hours) Discoloration was determined using a gray scale for JIS color fading.

(E) Determination of fastness to washing Washing test (JIS L0844 A-2 method) Contamination of the white cloth attached to silk was determined by a gray scale for JIS contamination.

(F) Determination of chlorine fastness Chlorine test (JIS L0884 JIS strong) Discoloration was determined using a gray scale for JIS discoloration.

(G) Determination of fastness to nitrogen gas (NOx) Chlorine test (JIS L0855 1 unit) Discoloration was determined using a gray scale for JIS discoloration.

Comparative Example 1
As silica fine particles, 40 parts Snowtech OL (Nissan Chemical Co., Ltd.) and 0.8 parts KBE903 (Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having an amino group were adjusted to pH 4 with formic acid to obtain silica fine particles. To obtain a comparative deep colorant containing no polyether-modified polysiloxane.
In place of the deep color agent (DYEMER 05) in Example 1, this was subjected to a deep color treatment by a pad treatment method in the same manner as in Example 1. A fastness test or the like was performed in the same manner as in Example 2 using the obtained comparative dyed product. The results are shown in Table 1.

Comparative Example 2
Except for using the comparative deep colorant prepared in Comparative Example 1, the deep color treatment by the dyeing method was performed in the same manner as in Example 2. A fastness test or the like was performed in the same manner as in Example 2 using the obtained comparative dyed product. The results are shown in Table 2.

Comparative Example 3
As silica fine particles, 40 parts Snowtech OL (Nissan Chemical Co., Ltd.) and 0.8 parts KBE903 (Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having an amino group were adjusted to pH 4 with formic acid to obtain silica fine particles. After the treatment, 2 parts of Polon MF-18 (manufactured by Shin-Etsu Chemical Co., Ltd., epoxy-modified polysiloxane) was used to obtain a deepening agent for comparison.
This was replaced with a deep color agent (DYEMER-05) in Example 1, and a deep color treatment by a pad treatment method was performed in the same manner as in Example 1. A fastness test or the like was conducted in the same manner as in Example 2 using the comparative dyed product obtained. The results are shown in Table 1.

Comparative Example 4
Except for using the comparative deep coloring agent prepared in Comparative Example 3, deep color treatment by the dyeing method was performed in the same manner as in Example 2. A fastness test or the like was performed in the same manner as in Example 2 using the obtained comparative dyed product. The results are shown in Table 2.

Comparative Example 5
A fastness test or the like was performed in the same manner as in Example 2 using an untreated test cloth. The results are shown in two tables, Table 1 and Table 2.

Comparative Example 6
A fastness test was conducted in the same manner as in Example 2 using the test cloth that was dyed twice in the above-mentioned section for producing the test cloth. The results are shown in two tables, Table 1 and Table 2.

  From Table 1, the dyed processed product of Example 1 has a higher degree of deep color compared to Comparative Examples 1, 3, 5, and 6, and the water absorption is Comparative Examples 5 and 6 that are not subjected to the deep color treatment. It can be seen that it is the same level and is higher than Comparative Examples 1 and 3 treated with a comparative deep colorant. Light fastness, sweat light fastness, washing fastness, chlorine fastness, and nitrogen gas resistance are the same as those of Comparative Examples 5 and 6 in which no deep color treatment is performed. It was confirmed that there was no lowering. The same consideration as in Table 1 can be made for Table 2.

Claims (5)

  A deep colorant for cellulosic fibers, comprising silica fine particles treated with a silane coupling agent having an amino group under acidic conditions and polyether-modified polysiloxane.   The deep color agent for cellulosic fibers according to claim 1, obtained by treating an aqueous solution of silica fine particles with an amino group-containing silane coupling agent under acidic conditions and then mixing polyether-modified polysiloxane.   The deep coloring agent for cellulosic fibers according to claim 1 or 2, wherein the content of the polyether-modified polysiloxane is 5 to 20% by weight based on the silica fine particles.   The deepening method characterized by processing the cellulosic fiber dyed and processed with the deepening agent for cellulose fibers in any one of Claims 1-3. A cellulosic fiber dyed processed product treated with the deep coloring agent for cellulosic fibers according to any one of claims 1 to 3.